Resin composition, cured product, laminate, method for manufacturing a cured product, method for manufacturing a laminate, method for manufacturing a semiconductor device, and, semiconductor device

Abstract

A resin composition comprising at least one resin selected from the group consisting of a polyimide precursor, polyimide, a polyamideimide precursor, polyamideimide, and polyamide, and a solvent, wherein the respective contents of N-methylpyrrolidone and γ-butyrolactone relative to the total mass of the resin composition are both 0.1 mass% or less; a cured product formed by curing the resin composition; a laminate comprising the cured product; a method for manufacturing the cured product; a method for manufacturing the laminate; a method for manufacturing a semiconductor device comprising the method for manufacturing the laminate; and a semiconductor device comprising the cured product or the laminate.

Description

Technology Field

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

[0002] In modern times, resin materials manufactured from resin compositions containing resin are being utilized in various fields.

[0003] For example, polyimide is applied in various uses due to its excellent heat resistance and insulation properties. While such applications are not particularly limited, taking semiconductor devices for mounting as an example, it is used as a material for insulating films or sealants, or as a protective film. It is also used as a base film or cover layer for flexible substrates.

[0004] For example, in the above-described use, the polyimide is used in the form of a resin composition comprising a polyimide precursor.

[0005] A resin composition of this kind can be applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, by performing exposure, development, heating, etc., a cured product can be formed on the substrate.

[0006] Polyimide precursors are cyclized, for example, by heating, and become polyimide during curing.

[0007] Since the resin composition can be applied using known coating methods, it can be said to have excellent manufacturing adaptability, such as a high degree of design freedom regarding the shape, size, and application location of the resin composition when applied. In addition to the high performance of polyimide, the development of industrial applications of the aforementioned resin composition is increasingly anticipated from the perspective of such excellent manufacturing adaptability.

[0008] For example, Patent Document 1 describes a negative-type photosensitive resin composition comprising the following components: (A) at least one resin selected from the group consisting of polyimide precursors, polyamide, polyamideimide, and polyimide: 100 parts by mass, (B) a compound of a specific structure, (C) a photosensitive agent: 0.5 to 30 parts by mass, and (D) a solvent, wherein the total of the compounds represented by chemical formula (b1) of n=1 to 5 is less than 0.01 parts by mass. Prior art literature

[0009] Patent Document 1: Japanese Published Patent Application No. 2022-073737 The problem to be solved

[0010] In the resin composition described above, excellent stability during storage (stability over time) is required. Specifically, for example, it is required that the viscosity of the composition does not change easily after storage at room temperature for several weeks.

[0011] The present invention aims to provide a resin composition having excellent stability over time, a cured product formed by curing the resin composition, a laminate comprising the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device comprising the method for manufacturing the laminate, and a semiconductor device comprising the cured product or the laminate. means of solving the problem

[0012] Examples of representative embodiments of the present invention are shown below.

[0013] <1> At least one resin selected from the group consisting of polyimide precursors, polyimide, polyamideimide precursors, polyamideimide, and polyamide, and

[0014] Contains a solvent,

[0015] The respective contents of N-methylpyrrolidone and γ-butyrolactone relative to the total mass of the resin composition are both 0.1 mass% or less.

[0016] Resin composition.

[0017] <2> As the above solvent, containing γ-valerolactone, <1> Resin composition described in

[0018] <3> At least one resin selected from the group consisting of polyimide precursors, polyimide, polyamideimide precursors, polyamideimide, and polyamide, and

[0019] containing γ-valerolactone

[0020] Resin composition.

[0021] <4> The content of the above γ-valerolactone is 60 mass% or more with respect to the total mass of the solvent, <2> or <3> Resin composition described in

[0022] <5> As the above solvent, further comprising dimethyl sulfoxide, <1> inside <4> A resin composition described in any one of the following.

[0023] <6> further comprising a polymerizable compound and a photopolymerization initiator, <1> inside <5> A resin composition described in any one of the following.

[0024] <7> Used for forming an interlayer insulating film for a redistribution layer, <1> inside <6> A resin composition described in any one of the following.

[0025] <8> <1> inside <7> A cured product formed by curing a resin composition described in any one of the following.

[0026] <9> <8> A laminate comprising two or more layers made of the cured material described in the above, and a metal layer between any one of the layers made of the cured material.

[0027] <10> <1> inside <7> A method for manufacturing a cured product comprising a film-forming process in which a resin composition described in any one of the above is applied to a substrate to form a film.

[0028] <11> A method comprising an exposure process for selectively exposing the above film and a development process for developing the above film using a developer to form a pattern, <10> Method for manufacturing a cured product as described in

[0029] <12> A heating process comprising heating the above membrane at 50 to 450°C, <10> or <11> Method for manufacturing a cured product as described in

[0030] <13> <10> inside <12> A method for manufacturing a laminate comprising a method for manufacturing a cured product as described in any one of the following.

[0031] <14> <10> inside <12> A method for manufacturing a semiconductor device comprising a method for manufacturing a cured product as described in any one of the above.

[0032] <15> <8> The hardened material or listed in <9> A semiconductor device comprising a laminate as described in Effects of the invention

[0033] According to the present invention, a resin composition having excellent stability over time, a cured product formed by curing the resin composition, a laminate comprising the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing the laminate, a method for manufacturing the semiconductor device comprising the method for manufacturing the laminate, and a semiconductor device comprising the cured product or the laminate are provided. Specific details for implementing the invention

[0034] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified.

[0035] In this specification, a numerical range indicated by the symbol "~" means a range that includes the values ​​listed before and after "~" as a lower limit and an upper limit, respectively.

[0036] In this specification, the term "process" includes not only independent processes but also processes that are not clearly distinguishable from other processes insofar as they can achieve the desired function of the process.

[0037] In the notation of groups (atomic groups) in this specification, notations that do not specify substitution or non-substitution include groups (atomic groups) that have substituents along with groups (atomic groups) that do not have substituents. For example, "alkyl group" includes not only alkyl groups that do not have substituents (non-substituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).

[0038] In this specification, the term "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams, unless specifically explained otherwise. In addition, light used for exposure may include active light or radiation such as the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams.

[0039] In this specification, "(meth)acrylate" means either "acrylate" or "methacrylate," "(meth)acryl" means either "acryl" or "methacryl," and "(meth)acryloyl" means either "acryloyl" or "methacryloyl."

[0040] In the present specification, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group in the structural formula.

[0041] In this specification, "total solid content" refers to the total mass of the components excluding the solvent from the total components of the composition. Also in this specification, "solid content concentration" refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition.

[0042] In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) unless specifically stated otherwise, and are defined as polystyrene equivalent values. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by Dosho Co., Ltd.) and connecting in series guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Dosho Co., Ltd.) as columns. Unless specifically stated otherwise, their molecular weights are to be measured using THF (tetrahydrofuran) as the eluent. However, if THF is not suitable as the eluent, such as in cases of low solubility, NMP (N-methyl-2-pyrrolidone) may be used. In addition, unless otherwise specified, detection in GPC measurement is assumed to use a detector with a wavelength of 254 nm of UV rays (ultraviolet rays).

[0043] In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient for another layer to exist on the upper or lower side of the reference layer among the multiple layers being considered. That is, a third layer or element may be additionally interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact. Unless otherwise specifically stated, the direction in which layers are stacked relative to the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Furthermore, such upper and lower directions are set for convenience within this specification, and in actual embodiments, the "up" direction in this specification may differ from the vertical upward direction.

[0044] In this specification, unless otherwise specified, a composition may include two or more compounds corresponding to each component included in the composition. Also, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to that component.

[0045] In this specification, unless specifically described otherwise, the temperature is 23℃, the pressure is 101,325 Pa (1 atm), and the relative humidity is 50%RH.

[0046] In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0047] (Resin composition)

[0048] A resin composition according to the first embodiment of the present invention comprises at least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polyamideimide precursor, a polyamideimide, and a polyamide, and a solvent, wherein the respective contents of N-methylpyrrolidone ("N-methyl-2-pyrrolidone," also referred to as "NMP") and γ-butyrolactone ("GBL") are each 0.1 mass% or less relative to the total mass of the resin composition.

[0049] A resin composition according to a second aspect of the present invention comprises at least one resin selected from the group consisting of a polyimide precursor, polyimide, a polyamideimide precursor, polyamideimide, and polyamide, and γ-valerolactone (GVL).

[0050] In the present invention, unless specifically limited, the resin composition according to the first embodiment and the resin composition according to the second embodiment are collectively referred to simply as the "resin composition."

[0051] The resin composition of the present invention is preferably used to form a photosensitive film provided for exposure and development, and is preferably used to form a film provided for exposure and development using a developer solution containing an organic solvent.

[0052] The resin composition of the present invention can be used, for example, to form an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.

[0053] In addition, the resin composition of the present invention is preferably used to form a photosensitive film provided for negative type development.

[0054] In the present invention, negative-type development refers to a phenomenon in which a non-exposed area is removed by development during exposure and development, and positive-type development refers to a phenomenon in which an exposed area is removed by development.

[0055] As the above-mentioned method of exposure, the above-mentioned developer, and the above-mentioned method of development, for example, the exposure method described in the exposure process and the developer and development method described in the development process in the description of the method for manufacturing a cured product described later are used.

[0056] The resin composition of the present invention has excellent stability over time.

[0057] The mechanism by which the above effect is obtained is unclear, but it is speculated as follows.

[0058] Since NMP and GBL have high polarity, they also have high solubility in resins, and compositions using these solvents tend to become low in viscosity. Due to this low-viscosity behavior, it is believed that because the polymer chains of the resin are in a loosened or non-aggregated state in the solution, when a portion of the resin's main chain (such as amide bonds) decomposes within the composition, the main chain becomes more susceptible to decompositional attack from basic decomposition products (decomposition products containing amino groups). As such, since the chain of decomposition reactions is accelerated in resin compositions containing solvents like NMP and GBL, it is presumed that resin compositions containing these solvents have low stability over time.

[0059] In the present invention, it is presumed that the stability of the composition over time is improved because the decomposition chain of the resin is suppressed by adopting a composition with low content of NMP and GBL, or a composition including GVL as a solvent.

[0060] Furthermore, particularly when a resin composition contains a thermobase generator, the decomposition of the thermobase generator is accelerated in highly polar solvents, and there are cases where the resin is decomposed by the base generated from the thermobase generator. It is believed that by adopting the above-described configuration, the resin composition of the present invention suppresses such decomposition of the resin caused by the thermobase generator.

[0061] Furthermore, for example, when a composition contains organic titanium compounds, the composition may thicken due to the formation of titanoxane bonds. It was found that while such thickening is prone to occur in highly polar solvents such as NMP and GBL, it is suppressed by using GVL. This is presumed to be because organic titanium compounds have high stability in low-polarity solvents, making them difficult to decompose.

[0062] In addition, when ketoxime initiators (such as Irgacure OXE01 described later) and oxime initiators (such as Irgacure OXE02 described later) are used as photopolymerization initiators, it was found that these initiators also undergo hydrolysis in the presence of water and bases. By the composition of the resin composition of the present invention, the decomposition of these initiators is suppressed, and effects such as increased exposure sensitivity are obtained.

[0063] Here, Patent Document 1 does not describe a composition that employs the configuration described above for the solvent.

[0064] Hereinafter, the components included in the composition of the present invention will be described in detail.

[0065] <At least one resin selected from the group consisting of polyimide precursors, polyimide, polyamideimide precursors, polyamideimide, and polyamide>

[0066] The resin composition of the present invention comprises at least one resin selected from the group consisting of a polyimide precursor, polyimide, a polyamideimide precursor, polyamideimide, and polyamide (hereinafter also referred to as a "specific resin").

[0067] A polyimide precursor refers to a resin that becomes polyimide by causing a change in its chemical structure due to external stimuli; a resin that becomes polyimide by causing a change in its chemical structure due to heat is preferred, and a resin that becomes polyimide by causing a ring-closing reaction due to heat to form a ring structure is more preferred.

[0068] Polyimide is a resin containing multiple imide bonds (*-C(=O)-N(-*)-C(=O)-*) in its main chain, and it is preferable that the resin contains multiple repeating units having imide bonds.

[0069] A polyamideimide precursor refers to a resin that becomes polyamideimide by causing a change in its chemical structure due to external stimuli; a resin that becomes polyamideimide by causing a change in its chemical structure due to heat is preferred, and a resin that becomes polyamideimide by causing a ring-closing reaction due to heat to form a ring structure is more preferred.

[0070] Polyamideimide refers to a material in which imide bonds (-C(=O)-N(-*)-C(=O)-*) and amide bonds (-NR) are present in the main chain. N It is a resin containing multiple -C(=O)-) groups, and preferably a resin containing multiple repeating units having imide and amide bonds. The above R N It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and particularly preferably a hydrogen atom.

[0071] Polyamide refers to amide bonds (-NR) in the main chain. N It is a resin having multiple -C(=O)-) groups, and preferably a resin containing multiple repeating units having amide bonds. The above R N It is as described above.

[0072] In the present invention, "main chain" refers to the relatively longest bonding chain among the resin molecules, and "side chain" refers to any other bonding chain.

[0073] Among these, the resin composition preferably comprises a polyimide or a polyimide precursor as a specific resin, and more preferably comprises a polyimide precursor.

[0074] It is desirable for a specific resin to have a polymerizable group, and it is more desirable to include a radical polymerizable group.

[0075] When a specific resin has radical polymerizable groups, the resin composition of the present invention preferably includes a radical polymerization initiator, and more preferably includes a radical crosslinking agent. Additionally, if necessary, a sensitizer may be included. With such a resin composition, for example, a negative-type photosensitive film is formed.

[0076] In addition, certain resins may have polarity converters such as acid-degradable groups.

[0077] When a specific resin has acid-degradable groups, it is preferable that the resin composition include a photogenerator. With such a resin composition, for example, a chemically amplified positive photosensitive film or a negative photosensitive film is formed.

[0078] [Polyimide Precursor]

[0079] The polyimide precursor used in the present invention is not particularly limited in type, but it is preferable to include a repeating unit represented by the following formula (2).

[0080] [Chemical Formula 1]

[0081]

[0082] Among equation (2), A 1 and A 2 are, respectively, oxygen atoms or -NR z- indicates, R 111 Silver represents a divalent organic group, and R 115 represents a tetravalent organic group, and R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, and R z represents a hydrogen atom or a monovalent organic group.

[0083] A in Equation (2) 1 and A 2 are, respectively, oxygen atoms or -NR z - indicates, and oxygen atoms are desirable.

[0084] R z represents a hydrogen atom or a monovalent organic group, and a hydrogen atom is preferred.

[0085] R in Equation (2) 111 Silver represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups; a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferred, and a group including an aromatic group having 6 to 20 carbon atoms is more preferred. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group containing a heteroatom in the chain, and the cyclic aliphatic group and aromatic group may be substituted with a reduced hydrocarbon group containing a heteroatom. R in Formula (2). 111Examples of such groups include -Ar- and -Ar-L-Ar-, and the group represented by -Ar-L-Ar- is preferred. provided that Ar is, independently, an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a single bond or a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. The preferred ranges thereof are as described above.

[0086] R 111 It is preferable that the diamine be derived from a diamine. Examples of diamines used in the preparation of polyimide precursors include straight-chain or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

[0087] Specifically, R 111 It is preferable that the diamine comprises a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and it is more preferable that the diamine comprises an aromatic group having 6 to 20 carbon atoms. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group containing a heteroatom in the chain, and the cyclic aliphatic group and the aromatic group may be substituted with a reducing hydrocarbon group containing a heteroatom. Examples of groups comprising an aromatic group include the following.

[0088] [Chemical Formula 2]

[0089]

[0090] In the formula, A represents a single bond or a divalent linker, and is preferably a group selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a combination thereof, more preferably a group selected from an alkylene group having 1 to 3 carbon atoms that may be substituted with a single bond or a fluorine atom, -O-, -C(=O)-, -S-, or -SO2-, and more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0091] In the formula, * indicates a binding site with another structure.

[0092] As a diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane;

[0093] 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine;

[0094] m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenylsulfone, 4,4'- or 3,3'-diaminodiphenylsulfide, 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'-Diaminoparaterphenyl, 4,4'-Bis(4-aminophenoxy)biphenyl, Bis[4-(4-aminophenoxy)phenyl]sulfone, Bis[4-(3-aminophenoxy)phenyl]sulfone, Bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-Bis(4-aminophenoxy)benzene, 9,10-Bis(4-aminophenyl)anthracene, 3,3'-Dimethyl-4,4'-Diaminodiphenylsulfone, 1,3-Bis(4-aminophenoxy)benzene, 1,3-Bis(3-aminophenoxy)benzene, 1,3-Bis(4-aminophenyl)benzene, 3,3'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diaminooctafluorobiphenyl, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-Bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3'-dihydroxy-4,4'-Diaminobiphenyl, 9,9'-Bis(4-aminophenyl)fluorene, 4,4'-Dimethyl-3,3'-Diaminodiphenylsulfone, 3,3',5,5'-Tetramethyl-4,4'-Diaminodiphenylmethane, 2,4- or 2,5-Diaminocumene, 2,5-Dimethyl-p-phenylenediamine, Acetoguanamin, 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, Ester 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, From 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)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 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'-hexafluorotolidine and 4,4'-diaminoquaternphenyl At least one type of diamine selected can be cited.

[0095] In addition, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0096] In addition, a diamine having two or more alkylene glycol units in its main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 is also preferably used.

[0097] R 111 In terms of the flexibility of the resulting organic film, it is preferable for it to be represented as -Ar-L-Ar-. provided that Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon having 1 or 2 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0098] Also, R 111 In terms of i-line transmittance, it is preferable that the material be a divalent organic group represented by the following formula (51) or formula (61). In particular, in terms of i-line transmittance and ease of availability, it is more preferable that the material be a divalent organic group represented by formula (61).

[0099] Equation (51)

[0100] [Chemical Formula 3]

[0101]

[0102] In equation (51), R 50 ~R 57 Each is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with a nitrogen atom in Formula (2).

[0103] R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), etc.

[0104] [Chemical Formula 4]

[0105]

[0106] In equation (61), R 58 and R 59 Each is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with a nitrogen atom in formula (2).

[0107] Examples of diamines that impart the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One or more of these may be used in combination.

[0108] R in Equation (2) 115 represents a tetravalent organic group. As for the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred.

[0109] In Equation (5) or Equation (6), * represents a site of connection with another structure, each independently.

[0110] [Chemical Formula 5]

[0111]

[0112] In Equation (5), R 112It is a single bond or a divalent linker, preferably a carbon aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a single bond or a fluorine atom, -O-, -CO-, -S-, -SO2-, and -NHCO-, and combinations thereof, more preferably a carbon aliphatic hydrocarbon group having 1 to 3 carbon atoms that may be substituted with a single bond or a fluorine atom, selected from -O-, -CO-, -S-, and -SO2-, and more preferably a divalent linker selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0113] R 115 Specifically, examples include tetracarboxylic acid residues remaining after the removal of an anhydride group from a tetracarboxylic acid dianhydride. The polyimide precursor is R 115 As a structure corresponding to, it may include only one tetracarboxylic acid dianhydride residue or two or more.

[0114] It is preferable that the tetracarboxylic acid dianhydride be represented by the following formula (O).

[0115] [Chemical Formula 6]

[0116]

[0117] In formula (O), R 115 represents a tetravalent organic group. R 115 is R in Equation (2) 115 It has the same meaning as, and the desirable range is also the same.

[0118] Specific examples of tetracarboxylic acid dianhydrides include pyromellitic acid dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic acid dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, and 4,4'-oxydiphthalic acid. Anhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid 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 acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, Examples include 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 1,8,9,10-phenanthrene tetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzene tetracarboxylic acid dianhydride, and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0119] In addition, tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be cited as preferred examples.

[0120] In Equation (2), R 111 and R 115 It is also possible for at least one of them to have an OH group. More specifically, R111 As such, a residue of a bisaminophenol derivative can be cited.

[0121] R in Equation (2) 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, it is preferable to include a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. In addition, R 113 and R 114 It is preferable that at least one of them includes a polymerizable group, and it is more preferable that both include a polymerizable group. R 113 and R 114 It is also desirable that at least one of the groups comprises two or more polymerizable groups. As a polymerizable group, it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferred. Specific examples of polymerizable groups include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazoleyl group, a block isocyanate group, and an amino group. As a radical polymerizable group having a polyimide precursor, a group having an ethylenically unsaturated bond is preferred.

[0122] Groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl groups, etc.), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), and the group represented by the following formula (III) is preferred.

[0123] [Chemical Formula 7]

[0124]

[0125] In Equation (III), R 200 It represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and a hydrogen atom or a methyl group is preferred.

[0126] In formula (III), * indicates a binding site with another structure.

[0127] In Equation (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group.

[0128] Suitable R 201 Examples include alkylene groups such as ethylene groups, propylene groups, trimethylene groups, tetramethylene groups, pentamethylene groups, hexamethylene groups, octamethylene groups, and dodecamethylene groups, 1,2-butanediyl groups, 1,3-butanediyl groups, -CH2CH(OH)CH2-, and polyalkyleneoxy groups; alkylene groups such as ethylene groups and propylene groups, -CH2CH(OH)CH2-, cyclohexyl groups, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene groups and propylene groups, or polyalkyleneoxy groups are more preferred.

[0129] In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups among the plurality of alkyleneoxy groups included in the polyalkyleneoxy group may each be the same or different.

[0130] When a polyalkyleneoxy group comprises multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having a pattern such as alternation.

[0131] The number of carbon atoms of the above alkylene group (including the number of carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, more preferably 2 to 5, even more preferably 2 to 4, more preferably 2 or 3, and particularly preferably 2.

[0132] In addition, the above alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms, etc.

[0133] In addition, the number of alkylene oxygen groups included in the polyalkylene oxygen group (number of repetitions of polyalkylene oxygen groups) is preferably 2 to 20, more preferably 2 to 10, and more preferably 2 to 6.

[0134] As for the polyalkylene oxygen group, from the perspective of solvent solubility and solvent resistance, a polyethylene oxygen group, a polypropylene oxygen group, a polytrimethylene oxygen group, a polytetramethylene oxygen group, or a group in which a plurality of ethylene oxygen groups and a plurality of propylene oxygen groups are combined is preferred, a polyethylene oxygen group or a polypropylene oxygen group is more preferred, and a polyethylene oxygen group is even more preferred. In the group in which a plurality of ethylene oxygen groups and a plurality of propylene oxygen groups are combined, the ethylene oxygen groups and propylene oxygen groups may be arranged randomly, arranged to form blocks, or arranged in a pattern such as alternation. Preferred embodiments of the number of repetitions of ethylene oxygen groups, etc. in these groups are as described above.

[0135] In Equation (2), R 113 In the case of this hydrogen atom, or, R 114 When the atom is a hydrogen atom, the polyimide precursor may form a countersalt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0136] In Equation (2), R 113 and R 114At least one of them may be a polarity converter such as an acid-degradable group. As for the acid-degradable group, it is not particularly limited as long as it decomposes under the action of acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. are preferred, and from the perspective of exposure sensitivity, acetal groups or ketal groups are more preferred.

[0137] Specific examples of acid-degradable groups include tert-butoxycarbonyl groups, isopropoxycarbonyl groups, tetrahydropyranyl groups, tetrahydrofuranyl groups, ethoxyethyl groups, methoxyethyl groups, ethoxymethyl groups, trimethylsilyl groups, tert-butoxycarbonylmethyl groups, trimethylsilyl ether groups, etc. From the perspective of exposure sensitivity, ethoxyethyl groups or tetrahydrofuranyl groups are preferred.

[0138] It is also desirable for the polyimide precursor to have fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less.

[0139] In addition, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine.

[0140] The repeating unit represented by Equation (2) is preferably the repeating unit represented by Equation (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having the repeating unit represented by Equation (2-A). By including the repeating unit represented by Equation (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude.

[0141] Equation (2-A)

[0142] [Chemical Formula 8]

[0143]

[0144] In Equation (2-A), A 1 and A 2 represents an oxygen atom, and R 111 and R 112 Each independently represents a divalent organic group, and R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, and R 113 and R 114 At least one of them is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

[0145] In this specification, the structure bonded to the side of the ring structure indicates that any hydrogen atom among the hydrogen atoms directly bonded to the reduction of the ring structure may be substituted.

[0146] In this specification, "direct coupling" means coupling without interposing a connector.

[0147] A 1 , A 2 , R 111 , R 113 and R 114 A in Equation (2), independently of each 1 , A 2 , R 111 , R 113 and R 114 It has the same meaning as, and the desirable range is also the same. R 112 is R in Equation (5) 112 It has the same meaning as, and the desirable range is also the same.

[0148] The polyimide precursor may include one type of repeating unit represented by Formula (2), but may include two or more types. In addition, it may include a structural isomer of the repeating unit represented by Formula (2). The polyimide precursor may also include other types of repeating units in addition to the repeating unit of Formula (2).

[0149] As one embodiment of the polyimide precursor in the present invention, an embodiment in which the content of the repeating unit represented by Formula (2) is 50 mol% or more of the total repeating unit may be provided. The total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably greater than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor, excluding the ends, may be repeating units represented by Formula (2).

[0150] 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 more 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 more preferably 4,000 to 20,000.

[0151] The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and more preferably 2.0 or higher. Although the upper limit of the degree of dispersion of the molecular weight of the polyimide precursor is not specifically determined, for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and more preferably 6.0 or lower.

[0152] In this specification, the degree of dispersion of molecular weight is a value calculated by weight-average molecular weight / number-average molecular weight.

[0153] When a resin composition includes multiple types of polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyimide precursor are within the above range. In addition, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by combining the multiple types of polyimide precursors as a single resin are each within the above range.

[0154] [Polyimide]

[0155] The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide that is soluble in a developer solution having an organic solvent as the main component.

[0156] In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at least 0.1g at 23°C in 100g of a 2.38 mass% aqueous tetramethylammonium solution, and from the perspective of pattern-forming properties, it is preferable that the polyimide dissolves at least 0.5g, and more preferable that the polyimide dissolves at least 1.0g. The upper limit of the dissolved amount is not particularly limited, but it is preferable that it be 100g or less.

[0157] From the perspective of the film strength and insulation properties of the resulting organic film, it is preferable that the polyimide be a polyimide having multiple imide structures in the main chain.

[0158] -Fluorine atom-

[0159] From the perspective of the film strength of the resulting organic film, it is also desirable for the polyimide to have fluorine atoms.

[0160] The fluorine atom is, for example, R in the repeating unit represented by the following equation (4). 132 , or, R in the repeating unit represented by the equation (4) described later 131 It is desirable to include R in the repeating unit represented by the equation (4) described later. 132, or, R in the repeating unit represented by the equation (4) described later 131 It is more preferable to include it as a fluorinated alkyl group.

[0161] The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5 mass% or more, and also preferably 20 mass% or less.

[0162] -Silicon Atom-

[0163] From the perspective of the film strength of the organic film obtained, it is also desirable for the polyimide to have silicon atoms.

[0164] The silicon atom, for example, R in the repeating unit represented by Equation (4) described later 131 It is desirable to include R in the repeating unit represented by the equation (4) described later. 131 It is more preferable to include the organically modified (poly)siloxane structure described below.

[0165] The above silicon atom or the above organically modified (poly)siloxane structure may be included in the side chain of the polyimide, but it is preferable that it be included in the main chain of the polyimide.

[0166] The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass% or more, and more preferably 20 mass% or less.

[0167] -Ethylene unsaturated bond-

[0168] From the perspective of the film strength of the organic film obtained, it is desirable for the polyimide to have ethylenically unsaturated bonds.

[0169] Polyimide may have ethylenically unsaturated bonds at the ends of the main chain or at the side chains, but it is preferable to have them at the side chains.

[0170] It is desirable that the above ethylenically unsaturated bond has radical polymerization capability.

[0171] The ethylenically unsaturated bond is R in the repeating unit represented by the formula (4) described later. 132 or R 131 It is desirable to include in, and R 132 or R 131 It is more preferable to include a group having an ethylenically unsaturated bond.

[0172] Among these, the ethylenically unsaturated bond is R in the repeating unit represented by the equation (4) described later. 131 It is desirable to include in, and R 131 It is more preferable to include a group having an ethylenically unsaturated bond.

[0173] Examples of groups having ethylenically unsaturated bonds include a vinyl group, an allyl group, a vinylphenyl group, a group having a vinyl group that may be substituted and is directly bonded to an aromatic ring, (meth)acrylamide group, (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0174] [Chemical Formula 9]

[0175]

[0176] In Equation (IV), R 20 It represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and a hydrogen atom or a methyl group is preferred.

[0177] In Equation (IV), R 21 It represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3. 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 formed by combining two or more of these.

[0178] The above alkylene group having 2 to 12 carbon atoms may be any of the straight-chain, branched-chain, cyclic, or combinations thereof alkylene groups.

[0179] As for the above alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferred, and an alkylene group having 2 to 4 carbon atoms is more preferred.

[0180] Among these, R 21 It is preferable that the cause be represented by any one of the following equations (R1) to (R3), and it is more preferable that the cause be represented by equation (R1).

[0181] [Chemical Formula 10]

[0182]

[0183] In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group formed by the combination of two or more of these; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). 21 This indicates the bonding site with the oxygen atom.

[0184] In Formulas 1(R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L is R of Formula (IV). 21 It is identical to a preferred embodiment of an alkylene group having 2 to 12 carbon atoms, or a (poly)alkyleneoxy group having 2 to 30 carbon atoms.

[0185] In formula (R1), it is preferable that X be an oxygen atom.

[0186] In equations (R1) through (R3), * has the same meaning as * in equation (IV), and the preferred mode is also the same.

[0187] The structure represented by formula (R1) is obtained by reacting a polyimide having a hydroxyl group, such as a phenolic hydroxyl group, with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.).

[0188] The structure represented by formula (R2) is obtained by reacting, for example, a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate, etc.).

[0189] The structure represented by formula (R3) is obtained by reacting a polyimide having a hydroxyl group, such as a phenolic hydroxyl group, with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.).

[0190] In formula (IV), * indicates a bonding site with another structure, and it is preferable that it be a bonding site with the main chain of the polyimide.

[0191] The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0192] -Polymerizable groups other than those having ethylenically unsaturated bonds-

[0193] Polyimide may have polymerizable groups other than those having ethylenically unsaturated bonds.

[0194] Examples of polymerizable groups other than those having ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups.

[0195] Polymerizable groups other than those having ethylenically unsaturated bonds are, for example, R in the repeating unit represented by Equation (4) described later. 131 It is desirable to include it.

[0196] The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0197] -Polarity Converter-

[0198] The polyimide may have a polarity converter such as an acid-degradable group. The acid-degradable group in the polyimide is R in the above-described formula (2). 113 and R 114 It is identical to the acid-degradable group described in [the example], and the preferred embodiment is also identical.

[0199] The polarity converter is, for example, R in the repeating unit represented by Equation (4) described later. 131 , R 132 , included in the ends of polyimide, etc.

[0200] -Sanga-

[0201] When polyimide is provided for alkali development, from the perspective of improving developability, the acid value of the polyimide is preferably 30 mgKOH / g or higher, more preferably 50 mgKOH / g or higher, and even more preferably 70 mgKOH / g or higher.

[0202] The above acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0203] When polyimide is provided for development using a developer solution having an organic solvent as the main component (e.g., the “solvent development”) described below, the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and more preferably 5 to 20 mg KOH / g.

[0204] The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0205] As for the acid groups included in the polyimide, acid groups with a pKa of 0 to 10 are preferred from the perspective of compatibility between storage stability and developmentability, and acid groups with a pKa of 3 to 8 are more preferred.

[0206] pKa is a value representing the equilibrium constant Ka in the dissociation reaction in which hydrogen ions are released from an acid, expressed as the negative common logarithm of that constant, pKa. In this specification, pKa is a value calculated by ACD / ChemSketch (registered trademark) unless otherwise specifically stated. For pKa, the values ​​published in the "Fiveth Revised Edition of the Handbook of Chemistry" edited by the Japan Chemical Society may be referenced.

[0207] In the case where the acid group is a polyvalent acid such as phosphoric acid, for example, the above pKa is the first dissociation constant.

[0208] As such an acid group, the polyimide preferably comprises at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably comprises a phenolic hydroxyl group.

[0209] -Phenolic hydroxyl group-

[0210] From the perspective of making the development speed by the alkaline developer appropriate, it is desirable for the polyimide to have a phenolic hydroxyl group.

[0211] Polyimide may have phenolic hydroxyl groups at the ends of the main chain or on the side chains.

[0212] The phenolic hydroxyl group is, for example, R in the repeating unit represented by Formula (4) described below. 132 or R 131 It is desirable to include it.

[0213] The amount of phenolic hydroxyl groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0214] As for the polyimide used in the present invention, there are no particular limitations on which it is a polymer compound having an imide structure, but it is preferable that it includes a repeating unit represented by the following formula (4).

[0215] [Chemical Formula 11]

[0216]

[0217] In Equation (4), R 131 Silver represents a divalent organic group, and R 132 represents a tetravalent organic group.

[0218] In the case where it has a polymerizable group, the polymerizable group is R 131 and R 132 It may be located at least one of the two, or it may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0219] Equation (4-1)

[0220] [Chemical Formula 12]

[0221]

[0222] In Equation (4-1), R 133 is a polymerizable group, and other groups have the same meaning as in Equation (4).

[0223] Equation (4-2)

[0224] [Chemical Formula 13]

[0225]

[0226] R 134 and R 135 At least one of them is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group has the same meaning as in formula (4).

[0227] As polymerizable groups, a group including the aforementioned ethylenically unsaturated bond, or a crosslinking group other than the group having the aforementioned ethylenically unsaturated bond, may be used.

[0228] R 131represents a divalent organic group. As a divalent organic group, R in Equation (2) 111 Examples identical to the above are provided, and the desirable range is also the same.

[0229] R 131 Examples include diamine residues remaining after the removal of the amino group of the diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R in Formula (2) of the polyimide precursor. 111 Examples of this can be given.

[0230] R 131 It is preferable that the diamine residue has at least two alkylene glycol units in the main chain, as this more effectively suppresses the occurrence of warping during firing. More preferably, it is a diamine residue containing two or more of either one or both of an ethylene glycol chain or a propylene glycol chain in one molecule, and even more preferably, it is the diamine and is a diamine residue that does not contain an aromatic ring.

[0231] Examples of diamines containing two or more of either one or both of an ethylene glycol chain or a propylene glycol chain in one molecule include Zepamin (registered trademark), KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Inc.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but are not limited to these.

[0232] R 132 represents a tetravalent organic group. As a tetravalent organic group, R in Equation (2) 115 An example identical to that is provided, and the desirable range is also the same.

[0233] For example, R 115The four bonds of the tetravalent organic group exemplified as such combine with the four -C(=O)- parts of the above formula (4) to form a condensed ring.

[0234] R 132 Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from the tetracarboxylic acid dianhydride. As a specific example, R in Formula (2) of the polyimide precursor 115 An example of this can be given. In terms of the strength of the organic film, R 132 It is preferable that it be an aromatic diamine residue having 1 to 4 aromatic rings.

[0235] R 131 and R 132 It is also desirable to have an OH group on at least one of them. More specifically, R 131 As such, 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, and the above (DA-1) to (DA-18) can be cited as preferred examples, and R 132 As such, the above (DAA-1) to (DAA-5) can be cited as more desirable examples.

[0236] It is also desirable for the polyimide to have fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10 mass% or more, and more preferably 20 mass% or less.

[0237] For the purpose of improving adhesion to a substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as a diamine component, examples include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc.

[0238] To improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide be sealed with end sealants such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Among these, it is more preferable to use a monoamine, and preferred compounds of the monoamine include aniline, 2-ethyleneilaniline, 3-ethyleneilaniline, 4-ethyleneilaniline, 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, Examples include 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end sealants.

[0239] -Imide conversion rate (closing rate)-

[0240] The imidization rate (also called "closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more, from the perspective of the film strength and insulation properties of the organic film obtained.

[0241] The upper limit of the above imidization rate is not specifically limited and must be 100% or less.

[0242] The above imidization rate is measured, for example, by the following method.

[0243] By measuring the infrared absorption spectrum of polyimide, the absorption peak at 1377 cm⁻¹, which originates from the imide structure, -1 The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum is measured again at 1377 cm⁻¹. -1 The peak intensity P2 in the vicinity is determined. Using the obtained peak intensities P1 and P2, the imidation rate of the polyimide can be calculated based on the following formula.

[0244] Imidization Rate (%) = (Peak Intensity P1 / Peak Intensity P2) × 100

[0245] Polyimide, in which all repeating units are R 131 and R 132 The combination of may include a repeating unit represented by the same equation (4) above, and R 131 and R 132 The combination may include a repeating unit represented by the above formula (4) comprising two or more different types. The polyimide may include other types of repeating units in addition to the repeating unit represented by the above formula (4). Examples of other types of repeating units include, for instance, the repeating unit represented by the above formula (2).

[0246] Polyimide is obtained by using methods such as, for example, reacting a tetracarboxylic acid dianhydride with a diamine (partially substituted with a monoamine terminal sealant) at low temperature; reacting a tetracarboxylic acid dianhydride (partially substituted with an acid anhydride, a monoacid chloride compound, or a monoactive ester compound terminal sealant) with a diamine at low temperature; obtaining a diester by reacting a tetracarboxylic acid dianhydride with an alcohol and then reacting it with a diamine (partially substituted with a monoamine terminal sealant) in the presence of a condensation agent; obtaining a diester by reacting a tetracarboxylic acid dianhydride with an alcohol and then acid-chlorinating the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine terminal sealant), thereby obtaining a polyimide precursor, and then completely imidizing this using a known imidization reaction method, or stopping the imidization reaction midway to introduce a partial imide structure, and furthermore, completely It can be synthesized by using a method that introduces some imide structures by blending an imidized polymer with its polyimide precursor. In addition, other known methods for synthesizing polyimides may also be applied.

[0247] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and more preferably 15,000 to 40,000. By making the weight-average molecular weight 5,000 or higher, the bending resistance of the film after curing 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 higher.

[0248] The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and more preferably 4,000 to 20,000.

[0249] The degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and more preferably 2.0 or higher. Although the upper limit of the degree of dispersion of the molecular weight of the polyimide is not specifically determined, for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and more preferably 6.0 or lower.

[0250] When a resin composition includes multiple types of polyimides as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by combining the multiple types of polyimides as a single resin are each within the above range.

[0251] [Polyamideimide Precursor]

[0252] The polyamideimide precursor preferably comprises a repeating unit represented by the following formula (PAI-2).

[0253] [Chemical Formula 14]

[0254]

[0255] In equation (PAI-2), R 117 represents a trivalent organic group, and R 111 represents a divalent organic group, and A 2 represents an oxygen atom or -NH-, and R 113 It represents a hydrogen atom or a monovalent organic group.

[0256] In equation (PAI-2), R 117Examples include straight or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, complex aromatic groups, or groups formed by connecting two or more of these by single bonds or linkers, and a straight aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these by single bonds or linkers is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linkers is more preferred.

[0257] As the above linker, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene group, alkylene halide group, arylene group, or a linker formed by combining two or more of these is preferred, and -O-, -S-, alkylene group, alkylene halide group, arylene group, or a linker formed by combining two or more of these is more preferred.

[0258] As for the above alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is more preferred.

[0259] As for the above alkylene halogen group, an alkylene halogen group having 1 to 20 carbon atoms is preferred, an alkylene halogen group having 1 to 10 carbon atoms is more preferred, and an alkylene halogen group having 1 to 4 carbon atoms is more preferred. In addition, as for the halogen atoms in the above alkylene halogen group, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., may be examples, and fluorine atoms are preferred. The above alkylene halogen group may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkylene halogen groups include (ditrifluoromethyl)methylene groups, etc.

[0260] As for the above arylene group, a phenylene group or a naphthylene group is preferred, a phenylene group is more preferred, and a 1,3-phenylene group or a 1,4-phenylene group is more preferred.

[0261] Also, R 117 It is preferable that it be derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As for the halogenation, chlorination is preferred.

[0262] In the present invention, a compound having three carboxyl groups is called a tricarboxylic acid compound.

[0263] Two of the three carboxyl groups of the above tricarboxylic acid compound may be acid anhydrides.

[0264] Examples of tricarboxylic acid compounds that may be halogenated and used in the manufacture of polyamideimide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0265] These tricarboxylic acid compounds may be used as a single type or as two or more types.

[0266] Specifically, as a tricarboxylic acid compound, it is preferable to have a tricarboxylic acid compound comprising a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these by a single bond or a linker, and it is more preferable to have a tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by a single bond or a linker.

[0267] In addition, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are connected by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or phenylene group, etc.

[0268] These compounds may be compounds in which two carboxyl groups are anhydridated (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride chloride).

[0269] In equation (PAI-2), R 111 , A 2 , R 113 Each is R in the above-described formula (2). 111 , A 2 , R 113 It has the same meaning as, and the desirable mode is also the same.

[0270] Polyamideimide precursors may include additional repeating units.

[0271] Other repetition units include the repetition unit represented by the above-mentioned equation (2) and the repetition unit represented by the following equation (PAI-1).

[0272] [Chemical Formula 15]

[0273]

[0274] In equation (PAI-1), R 116 represents a divalent organic group, and R 111 It represents a divalent organic group.

[0275] In equation (PAI-1), R 116Examples include straight or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, complex aromatic groups, or groups formed by connecting two or more of these by single bonds or linkers, and a straight aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these by single bonds or linkers is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linkers is more preferred.

[0276] As the above linker, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene group, alkylene halide group, arylene group, or a linker formed by combining two or more of these is preferred, and -O-, -S-, alkylene group, alkylene halide group, arylene group, or a linker formed by combining two or more of these is more preferred.

[0277] As for the above alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is more preferred.

[0278] As for the above alkylene halogen group, an alkylene halogen group having 1 to 20 carbon atoms is preferred, an alkylene halogen group having 1 to 10 carbon atoms is more preferred, and an alkylene halogen group having 1 to 4 carbon atoms is more preferred. In addition, as for the halogen atoms in the above alkylene halogen group, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., may be examples, and fluorine atoms are preferred. The above alkylene halogen group may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkylene halogen groups include (ditrifluoromethyl)methylene groups, etc.

[0279] As for the above arylene group, a phenylene group or a naphthylene group is preferred, a phenylene group is more preferred, and a 1,3-phenylene group or a 1,4-phenylene group is more preferred.

[0280] Also, R 116 It is preferable that it be derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.

[0281] In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound.

[0282] The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, but, for example, it is preferable that it be chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

[0283] Examples of dicarboxylic acid compounds or dicarboxylic acid dihalide compounds that may be halogenated and used in the preparation of polyamideimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds.

[0284] These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used in isolation, or in two or more.

[0285] Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, it is preferable to have a dicarboxylic acid compound or a dicarboxylic acid dihalide compound comprising a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these by a single bond or a linker, and it is more preferable to have a dicarboxylic acid compound or a dicarboxylic acid dihalide compound comprising an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by a single bond or a linker.

[0286] In addition, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, souveric acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonaneinic acid, Dodecane diacid, tridecane diacid, tetradecane diacid, pentadecaine diacid, hexadecane diacid, heptadecaine diacid, octadecaine diacid, nonadecaine diacid, eicosane diacid, hen-eicosane diacid, docosane diacid, tricosane diacid, tetracosane diacid, pentacosane diacid, hexacosane diacid, heptacosane diacid, octacosane diacid, nonacosane diacid, triacontein diacid, hen-triacontein diacid, do-triacontein diacid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, Examples include benzophenone-4,4'-dicarboxylic acid.

[0287] Specific examples of dicarboxylic acid dihalide compounds include compounds having a structure in which two carboxyl groups in the specific examples of the dicarboxylic acid compounds are halogenated.

[0288] In equation (PAI-1), R 111 is R in the above-described formula (2). 111 It has the same meaning as, and the desirable mode is also the same.

[0289] In addition, it is preferable that the polyamideimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyamideimide precursor is preferably 10 mass% or more, and also preferably 20 mass% or less.

[0290] In addition, for the purpose of improving adhesion to the substrate, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine component.

[0291] As an embodiment of the polyamideimide precursor in the present invention, an embodiment comprising a repeating unit represented by Formula (PAI-2), a repeating unit represented by Formula (PAI-1), and a repeating unit represented by Formula (2) may be provided. The total content of the repeating units is preferably 50 mol% or more of the total repeating units, more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably greater than 90 mol%. The upper limit of the total content is not particularly limited and is 100 mol% or less. All repeating units in the polyamideimide precursor excluding the terminals may be any one of the repeating unit represented by Formula (PAI-2), the repeating unit represented by Formula (PAI-1), and the repeating unit represented by Formula (2).

[0292] In addition, as another embodiment of the polyamideimide precursor in the present invention, an embodiment comprising a repeating unit represented by Formula (PAI-2) and a repeating unit represented by Formula (PAI-1) may be cited. The total content of the repeating units is preferably 50 mol% or more of the total repeating units, more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably greater than 90 mol%. The upper limit of the total content is not particularly limited and is 100 mol% or less. All repeating units in the polyamideimide precursor excluding the terminals may be either the repeating unit represented by Formula (PAI-2) or the repeating unit represented by Formula (PAI-1).

[0293] The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and more preferably 4,000 to 25,000.

[0294] The degree of dispersion of the molecular weight of the polyamideimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and more preferably 2.0 or higher. Although the upper limit of the degree of dispersion of the molecular weight of the polyamideimide precursor is not specifically determined, for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and more preferably 6.0 or lower. When the resin composition includes multiple types of polyamideimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyamideimide precursor are within the above ranges. Furthermore, it is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by combining the multiple types of polyamideimide precursors as a single resin are each within the above ranges.

[0295] [Polyamideimide]

[0296] The polyamideimide used in the present invention may be an alkali-soluble polyamideimide, or a polyamideimide that is soluble in a developer solution having an organic solvent as the main component.

[0297] In this specification, alkali-soluble polyamideimide refers to a polyamideimide that dissolves at least 0.1g at 23°C in 100g of a 2.38 mass% aqueous tetramethylammonium solution, and from the perspective of pattern-forming properties, it is preferable that the polyamideimide dissolves at least 0.5g, and more preferable that the polyamideimide dissolves at least 1.0g. The upper limit of the dissolved amount is not particularly limited, but it is preferable that it be 100g or less.

[0298] In addition, from the perspective of the film strength and insulation properties of the resulting organic film, it is preferable that the polyamideimide be a polyamideimide having multiple amide bonds and multiple imide structures in the main chain.

[0299] -Fluorine atom-

[0300] From the perspective of the film strength of the resulting organic film, it is desirable for the polyamideimide to have fluorine atoms.

[0301] The fluorine atom, for example, R in the repeating unit represented by the formula (PAI-3) described below 117 , or, R 111 It is desirable to include R in the repeating unit represented by the equation (PAI-3) described below. 117 , or, R 111 It is more preferable to include it as a fluorinated alkyl group.

[0302] The amount of fluorine atoms relative to the total mass of the polyamideimide is preferably 5 mass% or more, and also preferably 20 mass% or less.

[0303] -Ethylene unsaturated bond-

[0304] From the perspective of the film strength of the organic film obtained, the polyamideimide may have ethylenically unsaturated bonds.

[0305] Polyamideimide may have ethylenically unsaturated bonds at the ends of the main chain or at the side chains, but it is preferable to have them at the side chains.

[0306] It is desirable that the above ethylenically unsaturated bond has radical polymerization capability.

[0307] The ethylenically unsaturated bond is R in the repeating unit represented by the formula (PAI-3) described below. 117 , or, R 111 It is desirable to include R in the repeating unit represented by the equation (PAI-3) described below. 117 , or, R 111 It is more preferable to include a group having an ethylenically unsaturated bond.

[0308] A preferred embodiment of a group having an ethylenically unsaturated bond is the same as a preferred embodiment of a group having an ethylenically unsaturated bond in the polyimide described above.

[0309] The amount of ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0310] -Polymerizable groups other than ethylenically unsaturated bonds-

[0311] Polyamideimide may have polymerizable groups other than ethylenically unsaturated bonds.

[0312] As polymerizable groups other than ethylenically unsaturated bonds in polyamideimide, groups identical to polymerizable groups other than ethylenically unsaturated bonds in the polyimide described above may be cited.

[0313] Polymerizable groups other than ethylenically unsaturated bonds are, for example, R in the repeating unit represented by the formula (PAI-3) described below. 111 It is desirable to include it.

[0314] The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g.

[0315] -Polarity Converter-

[0316] The polyamideimide may have a polarity converter such as an acid-degradable group. The acid-degradable group in the polyamideimide is R in the above-described formula (2). 113 and R 114 It is identical to the acid-degradable group described in [the example], and the preferred embodiment is also identical.

[0317] -Sanga-

[0318] When polyamideimide is provided for alkaline development, from the perspective of improving developability, the acid value of the polyamideimide is preferably 30 mgKOH / g or higher, more preferably 50 mgKOH / g or higher, and even more preferably 70 mgKOH / g or higher.

[0319] In addition, the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0320] In addition, when polyamideimide is provided for development using a developer solution having an organic solvent as the main component (e.g., the "solvent development" described below), the acid value of the polyamideimide is preferably 2 to 35 mg KOH / g, more preferably 3 to 30 mg KOH / g, and more preferably 5 to 20 mg KOH / g.

[0321] The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0322] In addition, as for the acid groups included in the polyamideimide, the same groups as the acid groups in the polyimide described above can be cited, and the preferred embodiment is also the same.

[0323] -Phenolic hydroxyl group-

[0324] From the perspective of making the development speed by the alkaline developer appropriate, it is desirable for the polyamideimide to have a phenolic hydroxyl group.

[0325] Polyamideimide may have a phenolic hydroxyl group at the end of the main chain or on the side chain.

[0326] The phenolic hydroxyl group is, for example, R in the repeating unit represented by the formula (PAI-3) described below. 117 , or, R 111 It is desirable to include it.

[0327] The amount of phenolic hydroxyl groups relative to the total mass of the polyamideimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0328] As for the polyamide imide used in the present invention, any polymer compound having an imide structure and an amide bond is not particularly limited, but it is preferable to include a repeating unit represented by the following formula (PAI-3).

[0329] [Chemical Formula 16]

[0330]

[0331] In equation (PAI-3), R 111 and R 117 are respectively, R in Equation (PAI-2). 111 and R 117 It has the same meaning as, and the desirable mode is also the same.

[0332] In the case where it has a polymerizable group, the polymerizable group is R 111 and R 117 It may be located at least on one side, or at the end of the polyamideimide.

[0333] In addition, to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyamideimide with a terminal sealant such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. A preferred embodiment of the terminal sealant is the same as a preferred embodiment of the terminal sealant in the polyimide described above.

[0334] -Imide conversion rate (closing rate)-

[0335] The imidization rate (also called "closure rate") of the polyamide imide is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more, from the perspective of the film strength and insulation properties of the organic film obtained.

[0336] The upper limit of the above imidization rate is not specifically limited and must be 100% or less.

[0337] The above imidization rate is measured by the same method as the polyimide closure rate described above.

[0338] Polyamideimide is, R 111 and R 117 The combination of may include a repeating unit represented by the same above-mentioned equation (PAI-3), and R 111 and R 117 The combination may include repeating units represented by the above formula (PAI-3), which includes two or more different types. In addition, the polyamideimide may include repeating units of other types in addition to the repeating units represented by the above formula (PAI-3). Examples of other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0339] Polyamideimide can be synthesized by, for example, by obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or by stopping the imidization reaction midway and introducing a partial imide structure, or furthermore, by blending a completely imidized polymer with the polyamideimide precursor to introduce a partial imide structure.

[0340] The weight-average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and more preferably 10,000 to 30,000. By making the weight-average molecular weight 5,000 or higher, the bending resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or higher.

[0341] In addition, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and more preferably 4,000 to 25,000.

[0342] The degree of dispersion of the molecular weight of the polyamideimide is preferably 1.5 or higher, more preferably 1.8 or higher, and more preferably 2.0 or higher. Although the upper limit of the degree of dispersion of the molecular weight of the polyamideimide is not specifically determined, for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and more preferably 6.0 or lower.

[0343] In addition, when the resin composition includes multiple types of polyamideimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide are within the above ranges. In addition, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by treating the multiple types of polyamideimides as a single resin are each within the above ranges.

[0344] [Polyamide]

[0345] It is preferable that the polyamide contains repeating units represented by the formula (PAI-1) described above.

[0346] A preferred embodiment of the repeating unit represented by formula (PAI-1) included in the polyamide is the same as a preferred embodiment of the repeating unit represented by formula (PAI-1) included in the polyamideimide precursor.

[0347] In addition, it is also desirable for the polyamide to include repeating units represented by the following formula (PA-1).

[0348] [Chemical Formula 17]

[0349]

[0350] In equation (PA-1), R 118 is a trivalent organic group, and R 119 is a divalent organic group, and R 120 It represents a hydrogen atom or a monovalent organic group.

[0351] In equation (PA-1), R 118 As such, R in the above-described formula (PAI-2) 117 A group identical to the one shown can be cited. Additionally, the following structures are particularly preferred. Among the following structures, * represents a bonding site with two carboxyl groups and a nitrogen atom in the formula (PA-1), respectively.

[0352] [Chemical Formula 18]

[0353]

[0354] In equation (PA-1), R 119 As such, R in the above-described formula (PAI-2) 111 Examples of groups identical to those shown below may be provided. Additionally, the following structures may be particularly preferred. In the following structures, * indicates a bonding site with two nitrogen atoms in the formula (PA-1). Furthermore, hydrogen atoms in the ring structure of the following structures may be substituted. Examples of substituents include alkyl groups (preferably methyl, ethyl, propyl, isopropyl, butyl, or isobutyl groups), hydroxyl groups, etc.

[0355] [Chemical Formula 19]

[0356]

[0357] Among the above structures, X 1 ~X 8 Each represents independently a single bond, -O-, -C(=O)-, -S(=O)2-, -CH2-, -C(CH3)2-, -C(CF3)2-, -C(CH3)(Ph)-, or a 1,1-cyclohexanediyl group. Also, Ph represents a phenyl group.

[0358] X 2 , X 3 , X 4 , X 5 , X 6 and X 8 It is desirable that it be -O-.

[0359] X 7 It is preferable that the bond be a single bond, -O-, -S(=O)2-, -C(CH3)2-, or -C(CF3)2-.

[0360] Also, R 119 It is also desirable that it has the following structure. Among the following structures, R P1 Each represents independently a single bond or an alkylene group, and * represents, respectively, a bonding site with two nitrogen atoms in formula (PA-1). R P1Each is independently a single bond or an alkylene group having 2 to 6 carbon atoms is more preferable. In addition, hydrogen atoms in the ring structure among the following structures may be substituted. Examples of substituents include alkyl groups (preferably methyl, ethyl, propyl, isopropyl, butyl, or isobutyl groups, etc.).

[0361] [Chemical Formula 20]

[0362]

[0363] Also, R 119 It is also desirable that it has the following structure. Among the following structures, R P2 Each independently represents an alkylene group, and R P3 Each independently represents an alkylene group, n1 represents an integer from 1 to 10, and R P4 represents an alkylene group, and R P5 Each independently represents an alkylene group, and R P6 Each represents an alkyl group or a phenyl group independently, n2 represents an integer from 1 to 40, and * represents a bonding site with two nitrogen atoms in formula (PA-1).

[0364] R P2 Each is independently an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 2 to 12 carbon atoms.

[0365] R P3 Each is independently an alkylene group having 2 to 6 carbon atoms is preferred, an ethylene group or a propylene group is more preferred, and an ethylene group is more preferred.

[0366] It is preferable that n1 be an integer from 1 to 5, and more preferable that it be an integer from 1 to 3.

[0367] R P4 Each is independently an alkylene group having 2 to 6 carbon atoms is preferred, an ethylene group or a propylene group is more preferred, and an ethylene group is more preferred.

[0368] R P5Each is independently an alkylene group having 2 to 10 carbon atoms is preferred, an alkylene group having 2 to 6 carbon atoms is more preferred, an ethylene group, a propylene group, or a trimethylene group is more preferred, and a trimethylene group is particularly preferred.

[0369] R P6 Each is independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a methyl group or a phenyl group.

[0370] It is more preferable that n2 be an integer between 1 and 20.

[0371] [Chemical Formula 21]

[0372]

[0373] In equation (PA-1), R 120 It is preferable that the group be a monovalent organic group, more preferable that the group be one containing a radical polymerizable group, and more preferable that the group be one represented by the following formula (PR-1).

[0374] R 120 As for the radical polymerizable group included therein, a group having an ethylenically unsaturated bond is preferred, and a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group, etc.), a (meth)acrylamide group, or a (meth)acryloyloxy group is more preferred, and a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is more preferred.

[0375] [Chemical Formula 22]

[0376]

[0377] In formula (PR-1), R P represents a group having a radical polymerizable group, and * represents a bonding site with a nitrogen atom in formula (PA-1).

[0378] In addition, to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyamide with a terminal sealant such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. A preferred embodiment of the terminal sealant is the same as a preferred embodiment of the terminal sealant in the polyimide described above.

[0379] Polyamide is, R 118 , R 119 and R 120 The combination of may include a repeating unit represented by the same above-mentioned equation (PA-1), and R 118 , R 119 and R 120 The combination may include repeating units represented by the above formula (PA-1), which includes two or more different types. In addition, the polyamide may include repeating units of other types in addition to the repeating units represented by the above formula (PA-1). Examples of other types of repeating units include repeating units represented by the above formula (PAI-1).

[0380] Polyamides are synthesized, for example, by the following method, but the synthesis method is not limited thereto.

[0381] A divalent carboxylic acid substituted with an amino group is reacted with a compound that reacts with an amino group to obtain a compound (hereinafter also referred to as a "sealing body") in which the amino group in the divalent carboxylic acid is sealed by an organic group (preferably a group having a radical polymerizable group).

[0382] Examples of compounds that react with the above amino group include acid chlorides, isocyanates, or epoxy compounds. That is, by using these compounds having radical polymerizable groups as compounds that react with the above amino group, a sealant having radical polymerizable groups can be obtained.

[0383] Subsequently, a polyamide can be obtained by polycondensing the above sealant with a diamine. As the diamine, R in the formula (PA-1) described above 119 Compounds in which amino groups are bonded to both ends can be used.

[0384] The weight-average molecular weight (Mw) of the polyamide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight-average molecular weight 5,000 or higher, the bending resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or higher.

[0385] In addition, the number average molecular weight (Mn) of the polyamide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and more preferably 4,000 to 25,000.

[0386] The degree of dispersion of the molecular weight of the polyamide is preferably 1.5 or higher, more preferably 1.8 or higher, and more preferably 2.0 or higher. Although the upper limit of the degree of dispersion of the molecular weight of the polyamide is not specifically determined, for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and more preferably 6.0 or lower.

[0387] In addition, when the resin composition includes multiple types of polyamides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamide are within the above ranges. In addition, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by combining the multiple types of polyamides as a single resin are each within the above ranges.

[0388] [Method for manufacturing polyimide precursors, etc.]

[0389] Polyimide precursors, etc., can be obtained by methods such as, for example, reacting a tetracarboxylic acid dianhydride with a diamine at low temperature; reacting a tetracarboxylic acid dianhydride with a diamine at low temperature to obtain a polyamic acid and then esterifying it using a condensing agent or an alkylating agent; obtaining a diester by a tetracarboxylic acid dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent; or obtaining a diester by a tetracarboxylic acid dianhydride with an alcohol and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent and reacting it with a diamine. Among the above manufacturing methods, the method of obtaining a diester by a tetracarboxylic acid dianhydride with an alcohol and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent and reacting it with a diamine is more preferable.

[0390] Examples of the above condensation agents include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-diosuccinimidylcarbonate, trifluoroacetic anhydride, etc.

[0391] Examples of the above alkylating agents include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, triethyl orthoformate, etc.

[0392] Examples of the above-mentioned halogenating agents include thionyl chloride, oxalyl chloride, oxyphosphorus chloride, etc.

[0393] In the method for manufacturing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types.

[0394] As for organic solvents, they can be appropriately determined depending on the raw material, but examples include pyridine, diethylene glycol dimethyl ether (diglaim), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0395] In a method for manufacturing polyimide precursors, etc., it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.

[0396] Basic compounds can be appropriately determined depending on the raw material, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undes-7-ene, N,N-dimethyl-4-aminopyridine.

[0397] -Terminal Sealant-

[0398] In a method for manufacturing polyimide precursors, etc., it is desirable to seal carboxylic acid anhydrides, acid anhydride derivatives, or amino groups remaining at the resin ends of polyimide precursors, etc., in order to further improve storage stability. When sealing carboxylic acid anhydrides and acid anhydride derivatives remaining at the resin ends, examples of end sealants include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more desirable to use monoalcohols, phenols, or monoamines due to reactivity and membrane stability. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.In addition, as preferred compounds of monoamine, aniline, 2-ethyleneilaniline, 3-ethyleneilaniline, 4-ethyleneilaniline, 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-6-aminonaphthalene. Examples include 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end sealants.

[0399] In addition, when sealing the amino group at the end of the resin, it is possible to seal it with a compound having a functional group capable of reacting with the amino group. Preferred sealants for the amino group include carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, etc., and carboxylic acid anhydride and carboxylic acid chloride are more preferred. Preferred compounds of carboxylic acid anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, etc. In addition, preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexane carbonyl chloride, 2-ethylhexane oil chloride, cinnamoyl chloride, 1-adamanthene carbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, etc.

[0400] -Solid Precipitation-

[0401] A method for manufacturing polyimide precursors, etc., may include a process for precipitating a solid. Specifically, the absorption byproduct of the dehydration condensation agent coexisting in the reaction solution may be filtered and separated as necessary, and the obtained polymer component may be added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component may be precipitated as a solid and dried to obtain the polyimide precursor, etc. To improve the degree of purification, operations such as redissolving, redepositioning, and drying of the polyimide precursor, etc. may be repeated. Additionally, the method may include a process for removing ionic impurities using an ion exchange resin.

[0402] 〔content〕

[0403] In the resin composition of the present invention, the content of a specific resin is preferably 20 mass% or more with respect to the total solid content of the resin composition, more preferably 30 mass% or more, more preferably 40 mass% or more, and even more preferably 50 mass% or more. Furthermore, in the resin composition of the present invention, the content of the resin is preferably 99.5 mass% or less with respect to the total solid content of the resin composition, more preferably 99 mass% or less, more preferably 98 mass% or less, even more preferably 97 mass% or less, and even more preferably 95 mass% or less.

[0404] The resin composition of the present invention may include only one specific resin or two or more resins. When two or more resins are included, it is preferable that the total amount be within the above range.

[0405] The resin composition of the present invention may also preferably include at least two types of resins.

[0406] Specifically, the resin composition of the present invention may include a specific resin and two or more other resins described below, and may include two or more specific resins, but it is preferable to include two or more specific resins.

[0407] When the resin composition of the present invention comprises two or more specific resins, for example, as a polyimide precursor, a structure derived from a dianhydride (R referred to in formula (2) above) 115 It is preferable that ) includes two or more different types of polyimide precursors.

[0408] Another Suzy

[0409] The resin composition of the present invention may include the specific resin described above and another resin different from the specific resin (hereinafter simply referred to as "another resin").

[0410] Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, uretane resin, butyral resin, styryl resin, polyether resin, polyester resin, etc.

[0411] For example, by additionally adding (meth)acrylic resin, a resin composition with excellent coating properties is obtained, and a pattern (cured product) with excellent solvent resistance is obtained.

[0412] For example, instead of the polymerizable compound described below, or in addition to the polymerizable compound described below, a polymerizable group having a weight-average molecular weight of 20,000 or less and a high polymerizable group number (for example, the molar amount of the polymerizable group contained in 1 g of resin is 1 × 10⁻⁶ -3 By adding a (meth)acrylic resin (at a mol / g or higher) to the resin composition, the applicability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.

[0413] When the resin composition of the present invention includes other resins, the content of the other resin is preferably 0.01 mass% or more with respect to the total solid content of the resin composition, more preferably 0.05 mass% or more, more preferably 1 mass% or more, even more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more.

[0414] In the resin composition of the present invention, the content of another resin is preferably 80 mass% or less with respect to the total solid content of the resin composition, more preferably 75 mass% or less, more preferably 70 mass% or less, even more preferably 60 mass% or less, and even more preferably 50 mass% or less.

[0415] As a preferred embodiment of the resin composition of the present invention, the content of another resin may be low. In the above embodiment, the content of the other resin is preferably 20 mass% or less with respect to the total solid content of the resin composition, more preferably 15 mass% or less, more preferably 10 mass% or less, even more preferably 5 mass% or less, and even more preferably 1 mass% or less. The lower limit of the content is not particularly limited and may be 0 mass% or more.

[0416] The resin composition of the present invention may include only one type of other resin, or may include two or more types. When two or more types are included, it is preferable that the total amount be within the above range.

[0417] Solvent

[0418] The resin composition of the present invention includes a solvent.

[0419] Here, in the first embodiment of the present invention, the respective contents of N-methylpyrrolidone and γ-butyrolactone relative to the total mass of the resin composition are both 0.1 mass% or less.

[0420] In the second aspect of the present invention, it is preferable that the respective contents of N-methylpyrrolidone and γ-butyrolactone relative to the total mass of the resin composition are both 0.1 mass% or less.

[0421] The content of N-methylpyrrolidone relative to the total mass of the resin composition of the present invention is preferably 0.05 mass% or less, and more preferably 0.01 mass% or less. The lower limit of the content is not particularly limited and may be 0 mass% or more.

[0422] The content of γ-butyrolactone relative to the total mass of the resin composition of the present invention is preferably 0.05 mass% or less, and more preferably 0.01 mass% or less. The lower limit of the content is not particularly limited and may be 0 mass% or more.

[0423] In the first embodiment of the present invention, the resin composition preferably comprises γ-valerolactone as the solvent.

[0424] In a second aspect of the present invention, the resin composition comprises γ-valerolactone as the solvent.

[0425] The content of γ-valerolactone relative to the total mass of the solvent included in the resin composition of the present invention is preferably 50 mass% or more, more preferably 60 mass% or more, more preferably 70 mass% or more, particularly preferably 75 mass% or more, and most preferably 80 mass% or more. The upper limit of the above content is not particularly limited and may be 100 mass% or less. In addition, considering the solubility of the component included in the resin composition, such as a specific resin, it may be 90 mass% or less.

[0426] An embodiment further comprising dimethyl sulfoxide as a solvent is also one of the preferred embodiments of the present invention.

[0427] In some cases, the solubility of a component included in a resin composition, such as a specific resin, can be increased by including dimethyl sulfoxide.

[0428] The content of dimethyl sulfoxide relative to the total mass of the solvent included in the resin composition of the present invention is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more. As an upper limit, for example, 50 mass% or less is preferred, 40 mass% or less is more preferred, 30 mass% or less is more preferred, 25 mass% or less is even more preferred, and 20 mass% or less is particularly preferred.

[0429] In addition, when the resin composition of the present invention comprises γ-valerolactone and dimethyl sulfoxide, the content of γ-valerolactone relative to the total amount of γ-valerolactone and dimethyl sulfoxide is preferably 50 to 95 mass%, and more preferably 70 to 90 mass%.

[0430] When the resin composition of the present invention comprises γ-valerolactone and dimethyl sulfoxide, the total amount of γ-valerolactone and dimethyl sulfoxide relative to the total mass of the solvent included in the resin composition is preferably 80 mass% or more, and more preferably 90 mass% or more. The upper limit of the above content is not particularly limited and may be 100 mass% or less.

[0431] In addition, the resin composition of the present invention may further include other solvents different from the γ-valerolactone and dimethyl sulfoxide described above.

[0432] Other solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0433] As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionate esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 3-methyl ethoxypropionate, 3-ethyl ethoxypropionate, etc.), alkyl esters of 2-alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), Suitable examples include methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-methyl oxobutanate, 2-ethyl oxobutanate, ethyl hexanoate, ethyl heptanoate, dimethyl malonicate, diethyl malonicate, etc.

[0434] As 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, Suitable examples include diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc.

[0435] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone.

[0436] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0437] Suitable amides include N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc.

[0438] Suitable examples of ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc.

[0439] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0440] From the perspective of coating properties, the solvent content is preferably an amount such that the total solid content concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that it is 5 to 75 mass%, even more preferably an amount such that it is 10 to 70 mass%, and even more preferably an amount such that it is 20 to 70 mass%. The solvent content can be adjusted according to the desired thickness of the coating film and the coating method. When two or more types of solvents are contained, it is preferable that their total amount falls within the above range.

[0441] <Polymerizable Compounds and Photopolymerization Initiators>

[0442] The resin composition of the present invention preferably comprises a polymerizable compound and a photopolymerization initiator.

[0443] According to such an embodiment, for example, it becomes possible to use the resin composition of the present invention as a negative-type photosensitive resin composition.

[0444] Details of preferred embodiments for each compound are described below.

[0445] Polymerizable Compounds

[0446] The resin composition of the present invention preferably includes a polymerizable compound.

[0447] Examples of polymerizable compounds include radical crosslinkers or other crosslinkers.

[0448] [Radical Crosslinking Agent]

[0449] The resin composition of the present invention preferably includes a radical crosslinking agent.

[0450] A radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferred. Examples of the group containing the ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, etc.

[0451] Among these, (meth)acryloyl groups, (meth)acrylamide groups, and vinylphenyl groups are preferred, and from the perspective of reactivity, (meth)acryloyl groups are more preferred.

[0452] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

[0453] Among the compounds having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 bonds is even more preferred.

[0454] In terms of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0455] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0456] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, unsaturated carboxylic acid esters or amides having nucleogenic substituents such as hydroxyl groups, amino groups, or sulfanyl groups, addition products of monofunctional or polyfunctional isocyanates or epoxys, or dehydration condensation products of monofunctional or polyfunctional carboxylic acids are also suitably used. In addition, addition products of monofunctional or polyfunctional alcohols, amines, and thiols with unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups, and substitution products of monofunctional or polyfunctional alcohols, amines, and thiols with unsaturated carboxylic acid esters or amides having leaching substituents such as halogen groups or tosyloxy groups are also suitable. Furthermore, as another example, it is possible to use a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc., instead of the above unsaturated carboxylic acid. For specific examples, reference may be made to paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0457] For the radical crosslinking agent, compounds having a boiling point of 100°C or higher under atmospheric pressure are also preferred. Examples of compounds having a boiling point of 100°C or higher under atmospheric pressure include compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0458] Preferred radical crosslinking agents other than those described above include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0459] As radical crosslinking agents, a structure in which the (meth)acryloyl groups thereof are bonded via an ethylene glycol residue or a propylene glycol residue is preferred, such as dipentaerythritol triacrylate (commercially available KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.)), A-TMMT (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), A-DPH (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.)), and the (meth)acryloyl groups thereof are bonded via an ethylene glycol residue or a propylene glycol residue. Their oligomer types can also be used.

[0460] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Satomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (all manufactured by Nippon Kagaku Co., Ltd.); UAS-10 and UAB-140, uretane oligomers (all manufactured by Nippon Seishi Co., Ltd.); NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.), Examples include the DPHA-40H (manufactured by Nippon Kagaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoei Co., Ltd.), and the Blemmer PME400 (manufactured by Nichiyu Co., Ltd.).

[0461] As radical crosslinking agents, uretain acrylates as described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. Sho 51-037193, Japanese Patent Publication No. Hei 02-032293, and Japanese Patent Publication No. Hei 02-016765, or uretain compounds having an ethylene oxide-based framework as described in Japanese Patent Publication No. Sho 58-049860, Japanese Patent Publication No. Sho 56-017654, Japanese Patent Publication No. Sho 62-039417, and Japanese Patent Publication No. Sho 62-039418 are also suitable. As a radical crosslinking agent, compounds having an amino structure or a sulfide structure within the molecule, as described in Japanese Patent Publication No. Sho 63-277653, Japanese Patent Publication No. Sho 63-260909, and Japanese Patent Publication No. Hei 01-105238, may also be used.

[0462] The radical crosslinking agent may be a radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. The radical crosslinking agent having acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a radical crosslinking agent in which acid groups are formed by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride is more preferable. Particularly preferably, in the radical crosslinking agent in which acid groups are formed by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, the aliphatic polyhydroxy compound is a compound in which pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid modified acrylic oligomers manufactured by Doa Kosei Co., Ltd., such as M-510 and M-520.

[0463] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, the handling properties during manufacturing and the developability are excellent. In addition, the polymerization properties are good. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0464] As a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and uretain bonds (hereinafter also referred to as "crosslinking agent U") is also preferred.

[0465] In the present invention, a urea bond refers to *-NR N -C(=O)-NR N It is a combination represented by -*, and R N Each represents independently a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom.

[0466] In the present invention, the uretane bond refers to *-OC(=O)-NR N It is a combination represented by -*, and R N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom, respectively.

[0467] In some cases, the resin composition may have improved chemical resistance, resolving properties, etc. by including the crosslinking agent U.

[0468] Although the mechanism by which the above effect is obtained is unclear, for example, it is thought that when curing by heating, a portion of the crosslinking agent U is thermally decomposed, thereby generating amines, and that said amines promote the cyclization of the precursor of the cyclized resin, such as the polyimide precursor.

[0469] Crosslinking agent U may have only one urea bond or uretane bond, may have one or more urea bonds and one or more uretane bonds, may have two or more urea bonds without uretane bonds, or may have two or more uretane bonds without urea bonds.

[0470] The total number of urea bonds and uretane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and more preferably 1 or 2.

[0471] When crosslinking agent U does not have uretain bonds, the number of urea bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and more preferably 1 or 2.

[0472] When crosslinking agent U does not have urea bonds, the number of uretain bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and more preferably 1 or 2.

[0473] The radical polymerizable group in crosslinking agent U is not particularly limited, but may include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, etc., and a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.

[0474] When crosslinking agent U has two or more radical polymerization groups, the structure of each radical polymerization group may be the same or different.

[0475] The number of radical polymerizable groups in the crosslinking agent U may be one or two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0476] In the crosslinking agent U, the radical polymerizable group (mass of compound per mole of radical polymerizable group) is preferably 150 to 400 g / mol.

[0477] The lower limit of the above radical polymerizable group is more preferably 200 g / mol or more, more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more, from the perspective of the chemical resistance of the cured product.

[0478] The upper limit of the above radical polymerizable group is more preferably 350 g / mol or less from the perspective of development, more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less.

[0479] Among them, the polymerizable group value of the crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0480] It is preferable that the crosslinking agent U has a structure represented by, for example, the following formula (U-1).

[0481] [Chemical Formula 23]

[0482]

[0483] In equation (U-1), R U1 is a hydrogen atom or a monovalent organic group, and A is -O- or -NR N -is, R N is a hydrogen atom or a monovalent organic group, and Z U1 is an organic group of the m-valence, and Z U2 is an organic group of n+1, X is a radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 1.

[0484] R U1 A hydrogen atom, an alkyl group, or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[0485] R N A hydrogen atom, an alkyl group, or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[0486] Z U1 Hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N -, or, a group formed by the combination of two or more of these is preferred, and is a hydrocarbon group, or, a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O)2-, and -NR NA group combined with at least one type of group selected from the group consisting of - is more preferable.

[0487] As the above hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is more preferred. Examples of the above hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups formed by the combination thereof. R N It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.

[0488] Z U2 - is a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N -, or, a group formed by the combination of two or more of these is preferred, and is a hydrocarbon group, or, a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O)2-, and -NR N A group combined with at least one type of group selected from the group consisting of - is more preferable.

[0489] As the above hydrocarbon group, Z U1 The same as those mentioned in [this] can be cited, and the desirable mode is also the same.

[0490] X is not particularly limited, but may include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, etc., and a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.

[0491] It is preferable that n be an integer from 1 to 10, more preferable that n be an integer from 1 to 4, more preferable that n be 1 or 2, and particularly preferable that n be 1.

[0492] It is preferable that m be an integer from 1 to 10, more preferable that m be an integer from 1 to 4, and more preferable that m be 1 or 2.

[0493] It is also preferable that the crosslinking agent U has at least one of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group.

[0494] From the perspective of the chemical resistance of the resulting cured film, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but it is preferable that it be an alcoholic hydroxyl group.

[0495] In terms of the chemical resistance of the resulting cured film, as for the alkyleneoxy group, an alkyleneoxy group having 2 to 20 carbon atoms is preferred, an alkyleneoxy group having 2 to 10 carbon atoms is more preferred, an alkyleneoxy group having 2 to 4 carbon atoms is more preferred, an ethylene group or a propylene group is more preferred, and an ethylene group is particularly preferred.

[0496] The alkyleneoxy group may be included in the crosslinking agent U as a polyalkyleneoxy group. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0497] The amide group is -C(=O)-NR N Performs a combination that appears through -. R N ...is as described above. When crosslinking agent U has an amide group, crosslinking agent U is, for example, RC(=O)-NR N The form appearing as -*, or *-C(=O)-NR N It may be included as a group represented by -R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.

[0498] The crosslinking agent U may have two or more structures selected from the group consisting of a hydroxyl group, an alkyleneoxy group (provided that if it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group), an amide group, and a cyano group within the molecule, but an embodiment having only one structure within the molecule is also preferred.

[0499] The above hydroxyl group, alkyleneoxy group, amide group, and cyano group may be present at any position in the crosslinking agent U, but from the perspective of chemical resistance, it is also preferable that the crosslinking agent U is connected to at least one selected from the group consisting of the above hydroxyl group, alkyleneoxy group, amide group, and cyano group, and at least one radical polymerizable group included in the crosslinking agent U by a linker comprising a urea bond or a uretain bond (hereinafter also referred to as "linker L2-1").

[0500] In particular, when the crosslinking agent U contains only one radical polymerizable group, it is preferable that the radical polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group are connected by a linker comprising a urea bond or a uretain bond (hereinafter also referred to as "linker L2-2").

[0501] When the crosslinking agent U comprises an alkyleneoxy group (provided that if it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and also has the linker L2-1 or the linker L2-2, the structure bonded to the side opposite to the linker L2-1 or the linker L2-2 of the alkyleneoxy group (provided that if it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) is not particularly limited, but a hydrocarbon group, a radical polymerizable group, or a combination thereof is preferred. As for the hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is more preferred. Examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by the combination thereof. In addition, a preferred embodiment of the radical polymerizable group is the same as the preferred embodiment of the radical polymerizable group in the crosslinking agent U described above.

[0502] When the crosslinking agent U includes an amide group and also has the linker L2-1 or the linker L2-2, the structure formed on the side opposite to the linker L2-1 or the linker L2-2 of the amide group is not particularly limited, but a hydrocarbon group, a radical polymerizable group, or a combination thereof is preferred. As for the hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is more preferred. In addition, examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by the combination thereof. A preferred embodiment of the radical polymerizable group is the same as the preferred embodiment of the radical polymerizable group in the crosslinking agent U described above. In addition, in the above embodiment, the carbon atom side of the amide group may be bonded to linker L2-1 or linker L2-2, and the nitrogen atom side of the amide group may be bonded to linker L2-1 or linker L2-2.

[0503] Among these, from the perspective of adhesion to the substrate, chemical resistance, and Cu void inhibition, it is desirable for the crosslinking agent U to have a hydroxyl group.

[0504] It is desirable for the crosslinking agent U to include an aromatic group in terms of compatibility with a specific resin.

[0505] It is preferable that the above aromatic group directly bonds to a urea bond or a uretain bond included in the crosslinking agent U. If the crosslinking agent U contains two or more urea bonds or uretain bonds, it is preferable that the aromatic group directly bonds to one of the urea bonds or uretain bonds.

[0506] The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and may have a structure in which they form a condensed ring, but it is preferable that it be an aromatic hydrocarbon group.

[0507] As for the above aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferred, and a group having 2 or more hydrogen atoms removed from a benzene ring structure is even more preferred.

[0508] As the above aromatic heterogroup, a 5-membered or 6-membered aromatic heterogroup is preferred. Examples of aromatic heterogroups in such aromatic heterogroups include pyrrole, imidazole, triazole, tetrazole, pyrazol, furan, thiophene, oxazole, isooxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may further condense with other rings, such as indole and benzimidazole.

[0509] As heteroatoms included in the above aromatic heterocyclic group, nitrogen atoms, oxygen atoms, or sulfur atoms are preferred.

[0510] The above aromatic group is preferably included in a linker that connects, for example, two or more radical polymerizable groups and includes a urea bond or a uretain bond, or a linker that connects at least one radical polymerizable group included in the crosslinking agent U with at least one selected from the group consisting of the above-mentioned hydroxyl group, alkyleneoxy group, amide group, and cyano group.

[0511] The number of atoms (linking chain length) between the urea bond or uretane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and more preferably 2 to 10.

[0512] If the crosslinking agent U contains a total of 2 or more urea bonds or uretane bonds, or contains 2 or more radical polymerizable groups, or contains 2 or more urea bonds or uretane bonds and also contains 2 or more radical polymerizable groups, the minimum of the number of atoms (link chain length) between the urea bonds or uretane bonds and the radical polymerizable groups must be within the above range.

[0513] In this specification, "number of atoms (linking chain length) between a urea bond or uretane bond and a polymerizable group" refers to connecting two atoms or groups of atoms of a connection target in the shortest possible (minimum number of atoms) among the atomic chains on the path connecting these connection targets. For example, in a structure represented by the following formula, the number of atoms (linking chain length) between a urea bond and a radical polymerizable group (methacryloyloxy group) is 2.

[0514] [Chemical Formula 24]

[0515]

[0516] [Axis of Symmetry]

[0517] It is also desirable that the crosslinking agent U be a compound with a structure that does not have a symmetry axis.

[0518] The statement that crosslinking agent U does not have an axis of symmetry means that it is a compound that is left-right asymmetric and does not have an axis that produces a molecule identical to the original molecule by rotating the entire compound. In addition, when the structural formula of crosslinking agent U is written on paper, the statement that crosslinking agent U does not have an axis of symmetry means that the structural formula of crosslinking agent U cannot be written in a form that has an axis of symmetry.

[0519] It is believed that since crosslinking agent U does not have a symmetry axis, aggregation of crosslinking agent Us within the composition film is suppressed.

[0520] [Molecular Weight]

[0521] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0522] The method for manufacturing crosslinking agent U is not particularly limited, but, for example, it can be obtained by reacting a radical polymerizable compound with a compound having an isocyanate group and a compound having at least one of a hydroxyl group or an amino group.

[0523] Specific examples of crosslinking agent U are shown below, but crosslinking agent U is not limited thereto.

[0524] [Chemical Formula 25]

[0525]

[0526] [Chemical Formula 26]

[0527]

[0528] [Chemical Formula 27]

[0529]

[0530] For the resin composition, it is preferable to use a difunctional methacrylate or acrylate in terms of pattern resolution and film elasticity.

[0531] Specific compounds include 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-tricyclodecaine diacrylate, dimethylol-tricyclodecaine dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified diacrylate of isocyanuric acid, isocyanuric acid-modified dimethacrylate, other difunctional acrylates having uretane bonds, and difunctional methacrylates having uretane bonds may be used. If necessary, two or more of these may be mixed and used.

[0532] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate, in which the formula quantity of polyethylene glycol chains is about 200.

[0533] In the resin composition of the present invention, a monofunctional radical crosslinking agent may preferably be used as a radical crosslinking agent in terms of inhibiting the bending of the pattern (cured product). As monofunctional radical crosslinking agents, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, and polypropylene glycol mono (meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinyl caprolactam, and allylglycidyl ether are preferably used. As a monofunctional radical crosslinking agent, a compound having a boiling point of 100°C or higher under atmospheric pressure is also preferred in order to suppress volatilization before exposure.

[0534] In addition, as radical crosslinking agents with two or more functions, allyl compounds such as diallyl phthalate and triallyl trimellitate can be cited.

[0535] When a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably greater than 0 mass% and less than or equal to 60 mass% with respect to the total solid content of the resin composition. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and more preferably 30 mass% or less.

[0536] Radical crosslinking agents may be used as a single type, but two or more types may be used in combination. When two or more types are used in combination, it is desirable that the total amount be within the above range.

[0537] [Other crosslinking agents]

[0538] The resin composition of the present invention may also include a different crosslinking agent, which is different from the radical crosslinking agent described above.

[0539] Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and it is preferable that the compound has multiple groups within its molecule that promote the reaction of forming a covalent bond with another compound in the composition or the reaction product thereof by photosensitization of the photogenerator or photobase generator described above, and it is preferable that the compound has multiple groups within its molecule that promote the reaction of forming a covalent bond with another compound in the composition or the reaction product thereof by the action of an acid or a base.

[0540] The above acid or base is preferably an acid or base generated from a photogenerator or a photobase generator in the photolithography process.

[0541] As other crosslinking agents, a compound having at least one group selected from the group consisting of acyloxymethyl, methylol, ethylol, and alkoxymethyl groups is preferred, and a compound having a structure in which at least one group selected from the group consisting of acyloxymethyl, methylol, ethylol, and alkoxymethyl groups is directly bonded to a nitrogen atom is more preferred.

[0542] Other crosslinking agents include, for example, compounds having a structure in which a hydrogen atom of an amino group is substituted with an acyloxymethyl group, a methylol group, an ethylol group, or an alkoxymethyl group by reacting an amino group-containing compound, such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine, with formaldehyde or an alcohol. The method of preparing these compounds is not particularly limited, and any compound having the same structure as the compound prepared by the above method is sufficient. It may also be an oligomer formed by the self-condensation of the methylol groups of these compounds.

[0543] Among the above amino group-containing compounds, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluryl, urea, or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.

[0544] Among these, the resin composition of the present invention preferably comprises at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably comprises at least one compound selected from the group consisting of glycoluryl-based crosslinking agents and melamine-based crosslinking agents described below.

[0545] As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, an example of a structural example may be a compound in which the alkoxymethyl group or the acyloxymethyl group is substituted directly onto an aromatic group or a nitrogen atom of the following urea structure, or onto a triazine.

[0546] The alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.

[0547] The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0548] The molecular weight of the above compound is preferably 1500 or less, and more preferably 180 to 1200.

[0549] [Chemical Formula 28]

[0550]

[0551] R 100 It represents an alkyl group or an acyl group.

[0552] R 101 and R 102Each of them independently represents a monovalent organic group and may be combined with each other to form a ring.

[0553] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include compounds of the following general formula.

[0554] [Chemical Formula 29]

[0555]

[0556] In the formula, X represents a single bond or a divalent organic group, and individual R 104 Each independently represents an alkyl group or an acyl group, and R 103 Silver, hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, or, groups that decompose by the action of an acid to produce alkali-soluble groups (e.g., groups detached by the action of an acid, -C(R 4 )2COOR 5 The energy appearing as (R 4 Each independently represents a hydrogen atom or a C1- to C4 alkyl group, and R 5 represents the energy that is defused by the action of acid.))

[0557] R 105 Each independently represents an alkyl group or an alkeneyl group, a, b, and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

[0558] A group that decomposes by the action of acid to generate an alkali-soluble group, a group that is detached by the action of acid, -C(R 4 )2COOR 5 R in the group represented as 5 Regarding this, for example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR39 ), -C(R 01 )(R 02 )(OR 39 Examples include ) etc.

[0559] During the meal, R 36 ~R 39 represents, respectively, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkeneyl group. 36 and R 37 Silver may combine with each other to form rings.

[0560] As for the above alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

[0561] The above alkyl group may be either a straight chain or a branched chain.

[0562] As for the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is more preferred.

[0563] The above cycloalkyl group may have a single-ring structure or a polycyclic structure such as a condensed ring.

[0564] The above aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.

[0565] As for the above aracle group, an aracle group having 7 to 20 carbon atoms is preferred, and an aracle group having 7 to 16 carbon atoms is more preferred.

[0566] The above aryl group is intended to be an aryl group substituted by an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.

[0567] The above alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

[0568] These groups may have additional known substituents.

[0569] R01 and R 02 Each represents, independently, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkeneyl group.

[0570] The group that decomposes by the action of an acid to generate an alkali-soluble group, or the group that is detached by the action of an acid, is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.

[0571] In addition, among the compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, ethylol groups, and alkoxymethyl groups, a compound having at least one group selected from the group consisting of urea bonds and uretain bonds is also preferred. A preferred embodiment of the above compound is identical to a preferred embodiment of the crosslinking agent U described above, except that the polymerizable group is at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, ethylol groups, and alkoxymethyl groups, which is not a radical polymerizable group.

[0572] Specifically, the following structures may be cited as compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and ethylol groups. Compounds having an acyloxymethyl group may be compounds in which the alkoxymethyl group of the following compounds is changed to an acyloxymethyl group. Compounds having an alkoxymethyl group or an acyloxymethyl group within a molecule may be cited as compounds such as the following, but are not limited thereto.

[0573] [Chemical Formula 30]

[0574]

[0575] [Chemical Formula 31]

[0576]

[0577] [Chemical Formula 32]

[0578]

[0579] A compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available one or a one synthesized by a known method.

[0580] From the perspective of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0581] Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, etc.

[0582] Specific examples of urea-based crosslinking agents include, for example, monohydroxymethylated glycolyl, dihydroxymethylated glycolyl, trihydroxymethylated glycolyl, tetrahydroxymethylated glycolyl, monomethoxymethylated glycolyl, dimethoxymethylated glycolyl, trimethoxymethylated glycolyl, tetramethoxymethylated glycolyl, monoethoxymethylated glycolyl, diethoxymethylated glycolyl, triethoxymethylated glycolyl, tetraethoxymethylated glycolyl, monopropoxymethylated glycolyl, dipropoxymethylated glycolyl, tripropoxymethylated glycolyl, tetrapropoxymethylated glycolyl, monobutoxymethylated glycolyl, dibutoxymethylated glycolyl, tributoxymethylated glycolyl. Or, glycoluryl-based crosslinking agents such as tetrabutoxymethylated glycoluryl,

[0583] Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea, etc.

[0584] Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or, ethylene urea-based crosslinking agents such as dibutoxymethylated ethylene urea,

[0585] Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or, propylene urea-based crosslinking agents such as dibutoxymethylated propylene urea,

[0586] Examples include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0587] Specific examples of benzoguanamine-based crosslinking agents include, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine. Examples include dibutoxymethylated benzoguanamine, tribubutoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

[0588] In addition, as a compound having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups, a compound in which at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring) is also suitably used.

[0589] Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl of hydroxymethylbenzoic acid, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl of methoxymethylbenzoic acid, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], Examples include 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0590] Commercially available products may be used as other crosslinking agents, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Yukizai High School), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, Examples include TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Kagaku High School), NikaRac (registered trademark, hereinafter the same), MX-290, NikaRac MX-280, NikaRac MX-270, NikaRac MX-279, NikaRac MW-100LM, NikaRac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

[0591] The resin composition of the present invention also preferably comprises at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[0592] -Epoxy compound (compound having an epoxy group)-

[0593] As for the epoxy compound, it is preferable to have a compound having two or more epoxy groups in one molecule. The epoxy groups undergo a crosslinking reaction at 200°C or lower, and since a dehydration reaction resulting from crosslinking does not occur, film shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective for low-temperature curing and suppression of warping of the resin composition.

[0594] It is preferable that the epoxy compound contains polyethylene oxide groups. This lowers the elastic modulus, thereby suppressing bending. The polyethylene oxide groups refer to a repeating unit of ethylene oxide being 2 or more, and it is preferable that the repeating unit is 2 to 15.

[0595] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin or polyhydric alcohol hydrocarbon type epoxy resin such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicone such as polymethyl(glycidyloxypropyl)siloxane.Specifically, Epiclon (registered trademark, hereinafter the same) 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon HP-4770, Epiclon EXA-830LVP, Epiclon EXA-8183, Epiclon EXA-8169, Epiclon N-660, Epiclon N-665-EXP-S, Epiclon N-740 (all product names, manufactured by DIC Co., Ltd.), Ricaresin (registered trademark, hereinafter the same) BEO-20E, Ricaresin BEO-60E, Ricaresin HBE-100, Ricaresin DME-100, Ricaresin L-200 (all product names, manufactured by Shin Nippon Rica Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all product names, manufactured by ADEKA Co., Ltd.), Celoxide (registered trademark, same applies hereinafter) 2021P, Celoxide 2081, Celoxide 2000, EHPE3150, Epolid (registered trademark, same applies hereinafter) GT401, Epolid PB4700, Epolid PB3600 (all product names, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, Examples include EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). In addition, the following compounds are also suitably used.

[0596] [Chemical Formula 33]

[0597]

[0598] In the expression, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0599] Among the above structures, in order to achieve both heat resistance and improved elongation, it is preferable that n be 1 to 2 and m be 3 to 7.

[0600] -Oxetane compounds (compounds having an oxetane group)-

[0601] Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As specific examples, the Aaron oxetane series manufactured by Doa Kosei Co., Ltd. (e.g., OXT-121, OXT-221) can be suitably used, and these may be used alone or a mixture of two or more types.

[0602] -Benzoxazine compounds (compounds having a benzoxazole group-

[0603] Benzoxazine compounds are desirable because, due to the cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and also, thermal shrinkage is small, thereby suppressing the occurrence of warping.

[0604] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (both trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolak-type dihydrobenzoxazine compounds. These may be used alone or mixed in combination of two or more types.

[0605] The content of other crosslinking agents is preferably 0.1 to 30 mass% with respect to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. The other crosslinking agents may be contained in only one type or in two or more types. When two or more other crosslinking agents are contained, the total amount thereof is preferably within the above range.

[0606] [Polymerization Initiator]

[0607] The resin composition of the present invention preferably includes a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.

[0608] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet to visible range is preferred. In addition, it may be an activator that interacts with a photo-excited sensitizer to generate an active radical.

[0609] The photoradical polymerization initiator is at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). -1 ·cm -1 It is preferable to contain at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using known methods. For example, it is preferable to measure at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with an ethyl acetate solvent.

[0610] As a photoradical polymerization initiator, known compounds may be optionally used. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine backbone, compounds having an oxadiazole backbone, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details regarding these, reference may be made to paragraphs 0165–0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138–0151 of International Patent Publication No. 2015 / 199219, the contents of which are incorporated herein by reference. Additionally, paragraphs 0065–0111 of Japanese Patent Publication No. 2014-130173, the compound described in Japanese Patent Publication No. 6301489, MATERIAL STAGE pp. 37–60, vol. 19, No. Examples include the peroxide-based photopolymerization initiator described in 3, 2019, the photopolymerization initiator described in International Publication No. 2018 / 221177, the photopolymerization initiator described in International Publication No. 2018 / 110179, the photopolymerization initiator described in Japanese Published Patent Application No. 2019-043864, the photopolymerization initiator described in Japanese Published Patent Application No. 2019-044030, and the peroxide-based initiator described in Japanese Published Patent Application No. 2019-167313, the contents of which are incorporated herein by reference.

[0611] As for ketone compounds, for example, the compound described in paragraph 0087 of Japanese Patent Publication No. 2015-087611 is exemplified, and this content is incorporated herein by reference. As for commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0612] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds may be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Publication No. Hei 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent Publication No. 4225898 may be used, and the contents thereof are incorporated herein by reference.

[0613] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCURE 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) may be used.

[0614] As α-aminoketone-based initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) may be used.

[0615] As aminoacetophenone-based initiators, acylphosphine oxide-based initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 may be suitably used. This content is incorporated herein by reference.

[0616] As a photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it becomes possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a photocuring promoter.

[0617] Specific examples of oxime compounds include the compound described in Japanese Published Patent Application No. 2001-233842, the compound described in Japanese Published Patent Application No. 2000-080068, the compound described in Japanese Published Patent Application No. 2006-342166, the compound described in JCS Perkin II (1979, pp. 1653-1660), the compound described in JCS Perkin II (1979, pp. 156-162), the compound described in the Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compound described in Japanese Published Patent Application No. 2000-066385, the compound described in Japanese Published Patent Application No. 2004-534797, the compound described in Japanese Published Patent Application No. 2017-019766, and Japanese Patent Publication Examples include compounds described in No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, etc., which are incorporated herein by reference.

[0618] Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. Oxime compounds used as photoradical polymerization initiators have a >C=NOC(=O)- linker within the molecule.

[0619] [Chemical Formula 34]

[0620]

[0621] Examples of commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), ADEKA Optomer N-1919 (manufactured by ADEKA Inc., photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA Arcles NCI-730, NCI-831, and ADEKA Arcles NCI-930 (manufactured by ADEKA Inc.), DFI-091 (manufactured by Daito Chemics Inc.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, oxime compounds of the following structure may also be used.

[0622] [Chemical Formula 35]

[0623]

[0624] As a photoradical polymerization initiator, for example, an oxime compound having a fluorene ring as described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189, an oxime compound having a backbone in which at least one benzene ring among the carbazole rings becomes a naphthalene ring, or an oxime compound having a fluorine atom may be used.

[0625] Additionally, oxime compounds having a nitro group, oxime compounds having a benzofuran backbone, and oxime compounds having a hydroxyl group substituent attached to a carbazole backbone, as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, may also be used. These contents are incorporated herein by reference.

[0626] As a photopolymerization initiator, an aromatic ring Ar in which an electron-requiring group is introduced to the aromatic ring is used. OX1 An oxime compound having (hereinafter also referred to as oxime compound OX) may be used. The above aromatic group Ar OX1 Examples of the electron-attracting groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfeneyl groups, arylsulfeneyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups; acyl groups and nitro groups are preferred, and acyl groups are more preferred because they facilitate the formation of a film with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have a substituent. As a substituent, it is preferable that it be a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkeneyl group, an alkylsulfaneyl group, an arylsulfaneyl group, an acyl group, or an amino group, more preferable that it be an alkyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylsulfaneyl group, an arylsulfaneyl group, or an amino group, and even more preferable that it be an alkoxy group, an alkylsulfaneyl group, or an amino group.

[0627] The oxime compound OX is preferably at least one selected from the compound represented by formula (OX1) and the compound represented by formula (OX2), and more preferably is the compound represented by formula (OX2).

[0628] [Chemical Formula 36]

[0629]

[0630] During the meal, R X1 Representing silver, alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfaneyl group, arylsulfaneyl group, alkylsulfeneyl group, arylsulfeneyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group,

[0631] R X2 ...represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfaneyl group, an arylsulfaneyl group, an alkylsulfeneyl group, an arylsulfeneyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group,

[0632] R X3 ~R X14 Each represents a hydrogen atom or a substituent independently.

[0633] However, R X10 ~R X14 At least one of them is an electronic spheroid.

[0634] In the above formula, R X12 ga is an electronic incubator, and R X10 , R X11 , R X13 , R X14 It is preferable that it be a hydrogen atom.

[0635] Specific examples of oxime compounds OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent Publication No. 4600600, and the contents thereof are incorporated herein by reference.

[0636] Particularly desirable oxime compounds include oxime compounds having specific substituents as described in Japanese Patent Publication No. 2007-269779, or oxime compounds having thioryl groups as described in Japanese Patent Publication No. 2009-191061, and these contents are incorporated herein by reference.

[0637] In terms of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiasol compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0638] In addition, the photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, and an acetophenone compound; more preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable.

[0639] As photoradical polymerization initiators, compounds described in paragraphs 0175–0179 of International Publication No. 2021 / 020359 and compounds described in paragraphs 0048–0055 of International Publication No. 2015 / 125469 may be used, and this is incorporated herein by reference.

[0640] As a photoradical polymerization initiator, a photoradical polymerization initiator with two or more functional groups may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity is obtained. In addition, when a compound with an asymmetric structure is used, crystallinity is reduced, solubility in solvents, etc. is improved, and it becomes difficult to precipitate over time, thereby improving the stability of the resin composition over time. Specific examples of photoradical polymerization initiators having two or more functions are: dimers of oxime compounds described in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407–0412 of Japanese Patent Publication No. 2016-532675, and paragraphs 0039–0055 of International Publication No. 2017 / 033680; compounds (E) and (G) described in Japanese Patent Publication No. 2013-522445; Cmpd 1–7 described in International Publication No. 2016 / 034963; and paragraph No. Examples include the oxime ester photoinitiator described in 0007, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 2017-167399, the photopolymerization initiator described in paragraphs 0017 to 0026 of Japanese Patent Publication No. 2017-151342 (A), and the oxime ester photoinitiator described in Japanese Patent Publication No. 6469669, and the contents thereof are incorporated by reference into this specification.

[0641] When the resin composition includes a photopolymerization initiator, the content thereof is preferably 0.1 to 30 mass% with respect to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and more preferably 1.0 to 10 mass%. The photopolymerization initiator may be contained in only one type or in two or more types. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range.

[0642] In addition, since photopolymerization initiators can also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator can be further advanced by heating with an oven or hot plate.

[0643] [Increase / Decrease System]

[0644] The resin composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes electron-excited. The electron-excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and actions such as electron transfer, energy transfer, and exothermic reaction occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and decompose to generate radicals, acids, or bases.

[0645] As usable sensitizers, compounds such as benzophenone-based, mihiller ketone-based, coumarin-based, pyrazolazo-based, anilinoazo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazoleazo-based, pyridonazo-based, cyanine-based, phenothiazine-based, pyrrolopyrazolazomethine-based, xanthen-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds may be used.

[0646] As sensitizers, for example, mihiller ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazol, 2-(p-dimethylaminophenylvinylene)benzothiazol, 2-(p-dimethylaminophenylvinylene)isonaphthothiazol, 1,3-Bis(4'-Dimethylaminobenzal)acetone, 1,3-Bis(4'-Diethylaminobenzal)acetone, 3,3'-Carbonyl-Bis(7-Diethylaminocoumarin), 3-Acetyl-7-Dimethylaminocoumarin, 3-Ethoxycarbonyl-7-Dimethylaminocoumarin, 3-Benzyloxycarbonyl-7-Dimethylaminocoumarin, 3-Methoxycarbonyl-7-Diethylaminocoumarin, 3-Ethoxycarbonyl-7-Diethylaminocoumarin(7-(Diethylamino)Coumarin-3-EthylCarboxylate), N-Phenyl-N'-Ethylethanolamine, N-Phenyldiethanolamine, Np-Tolyldiethanolamine, N-Phenylethanolamine, 4-Mopolinobenzophenone, Dimethylaminobenzoic acid Examples include isoamyl, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc.

[0647] In addition, other sensitizing dyes may be used.

[0648] For details regarding the sensitizing pigment, reference may be made to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, and this content is incorporated herein by reference.

[0649] When the resin composition includes a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass% with respect to the total solid content of the resin composition, more preferably 0.1 to 15 mass%, and even more preferably 0.5 to 10 mass%. The sensitizer may be used alone or in combination of two or more types.

[0650] [Chain Movement System]

[0651] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in pages 683-684 of the Polymer Dictionary, 3rd Edition (edited by the Polymer Society, 2005). As chain transfer agents, for example, a group of compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH within the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having thiocarbonylthio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization are used. These can generate radicals by donating hydrogen to low-activity radicals or by deprotonating after oxidation. In particular, thiol compounds may be preferably used.

[0652] Additionally, the chain transfer agent may use compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219, and this is incorporated herein by reference.

[0653] When the resin composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be of only one type or two or more types. If there are two or more types of chain transfer agents, it is preferable that their total amount falls within the above range.

[0654] Base generator

[0655] The resin composition of the present invention may include a base generating agent. Here, a base generating agent is a compound capable of generating a base through physical or chemical action. Preferred base generating agents include thermobase generating agents and photobase generating agents.

[0656] In particular, when the resin composition includes a precursor of a cyclization resin, it is preferable that the resin composition include a base generating agent. By including a thermobase generating agent in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, thereby improving the mechanical properties and chemical resistance of the cured product, and, for example, improving performance as an interlayer insulating film for a redistribution layer included in a semiconductor package.

[0657] As a base generator, it may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines.

[0658] The base generating agent is not particularly limited, and known base generating agents may be used. Examples of known base generating agents include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, etc.

[0659] Specific compounds of nonionic base generators include compounds represented by formula (B1), formula (B2), or formula (B3).

[0660] [Chemical Formula 37]

[0661]

[0662] Among Equations (B1) and (B2), Rb 1 , Rb 2 and Rb 3 Each is independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure. However, Rb 1 and Rb 2 There is no case where it simultaneously becomes a hydrogen atom. Also, Rb 1 , Rb 2 and Rb 3 There are no cases where all of them have carboxyl groups. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonding hands of a trivalent nitrogen atom are covalently bonded to carbon atoms of a hydrocarbon group. Therefore, if the carbon atom bonded to the trivalent nitrogen atom is a carbon atom constituting a carbonyl group, that is, if it forms an amide group together with the nitrogen atom, it is not a tertiary amine structure.

[0663] Among Equations (B1) and (B2), Rb 1 , Rb 2 and Rb 3 It is preferable that at least one of these includes a cyclic structure, and more preferable that at least two include a cyclic structure. As for the cyclic structure, it may be either a single ring or a condensed ring, and a single ring or a condensed ring formed by the condensation of two single rings is preferred. The single ring is preferably a five-membered ring or a six-membered ring, and a six-membered ring is more preferred. The single ring is preferably a cyclohexane ring and a benzene ring, and a cyclohexane ring is more preferred.

[0664] More specifically, Rb 1 and Rb 2It is preferable that the atom is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). These groups may have substituents. Rb 1 and Rb 2 They may be combined to form a ring. As for the ring formed, a nitrogen-containing heterocyclic ring of 4 to 7 groups is preferred. Rb 1 and Rb 2 It is preferable that the alkyl group be a straight-chain, branched, or cyclic alkyl group that may have a substituent (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group that may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), and more preferably a cyclohexyl group that may have a substituent.

[0665] Rb 3As, alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and more preferably 6 to 10), alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12, and more preferably 2 to 6), arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and more preferably 7 to 12), arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20, and more preferably 8 to 16), alkoxyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12), aryloxy group (preferably 6 to 22 carbon atoms, and more preferably 6 to 18), Examples include 6 to 12 carbon atoms, or arylalkyloxy groups (7 to 23 carbon atoms are preferred, 7 to 19 are more preferred, and 7 to 12 are more preferred). Among these, cycloalkyl groups (3 to 24 carbon atoms are preferred, 3 to 18 are more preferred, and 3 to 12 are more preferred), arylalkenyl groups, and arylalkyloxy groups are preferred. Rb 3 It may have additional substituents.

[0666] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0667] [Chemical Formula 38]

[0668]

[0669] In the food, Rb 11 and Rb 12 , and, Rb 31 and Rb 32 are, respectively, Rb in Equation (B1). 1 and Rb 2 It is the same as.

[0670] Rb 13It is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), and may have substituents. Among these, Rb 13 An arylalkyl group is preferred.

[0671] Rb 33 and Rb 34 Each is independently a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0672] Rb 35 The group is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), and an aryl alkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), and the aryl group is preferred.

[0673] The compound represented by formula (B1-1) is preferably the compound represented by formula (B1-1a).

[0674] [Chemical Formula 39]

[0675]

[0676] Rb 11 and Rb 12 is Rb in Equation (B1-1) 11 and Rb 12 It has the same meaning as

[0677] Rb 15 and Rb 16 The hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), and a hydrogen atom or a methyl group is preferred.

[0678] Rb 17 The group is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), and among these, an aryl group is preferred.

[0679] [Chemical Formula 40]

[0680]

[0681] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group along the path of a linking chain connecting adjacent oxygen and carbon atoms, wherein the number of atoms along the linking chain path is 3 or more. Also, R N1 and R N2 Each represents a monovalent organic group independently.

[0682] In this specification, "linking chain" refers to the shortest (minimum number of atoms) connection of two atoms or groups of atoms in a path connecting the two atoms or groups of atoms to be connected. For example, in a compound represented by the following formula, L is composed of a phenylethylene group and has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms in the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4.

[0683] [Chemical Formula 41]

[0684]

[0685] In formula (B3), the number of carbon atoms in L (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the perspective of rapidly proceeding the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for base generating agents include, for example, compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0686] In addition, it is also desirable for the base generator to include a compound represented by the following formula (N1).

[0687] [Chemical Formula 42]

[0688]

[0689] In equation (N1), R N1 and R N2 Each represents a monovalent organic group independently, and R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linker.

[0690] L is a divalent linker, and it is preferable that it be a divalent organic group. The linker chain length is preferably 1 or more, and more preferably 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and more preferably 5 or less. The linker chain length is the number of atoms in the atomic arrangement that is the shortest path between the two carbonyl groups in the formula.

[0691] In equation (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and more preferably 1 to 10 carbon atoms). Specifically, examples include an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and more preferably 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. R N1 and R N2 As such, using an aliphatic hydrocarbon group is desirable because the basicity of the resulting base is high. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have substituents, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have oxygen atoms in the aliphatic hydrocarbon chain, the aromatic ring, or the substituents. In particular, an embodiment in which the aliphatic hydrocarbon group has oxygen atoms in the hydrocarbon chain is exemplified.

[0692] R N1 and R N2 Examples of aliphatic hydrocarbon groups constituting the group include straight-chain or branched chain alkyl groups, cyclic alkyl groups, groups comprising a combination of chain alkyl groups and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. The straight-chain or branched chain alkyl groups preferably have 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms. Examples of straight-chain or branched chain alkyl groups include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, isopropyl groups, isobutyl groups, secondary butyl groups, tertiary butyl groups, isopentyl groups, neopentyl groups, tertiary pentyl groups, isohexyl groups, etc.

[0693] The cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of cyclic alkyl groups include cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cyclooctyl groups, etc.

[0694] The group comprising a combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and more preferably 4 to 12 carbon atoms. Examples of the group comprising a combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group, etc.

[0695] The alkyl group having oxygen atoms in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. The alkyl group having oxygen atoms in the chain may be chain-shaped or cyclic, and may be straight-chain or branched.

[0696] In particular, from the perspective of raising the boiling point of the decomposition-product bases described later, R N1 and R N2An alkyl group having 5 to 12 carbon atoms is preferred. However, in formulations where adhesion is important when laminated with a layer of metal (e.g., copper), it is preferred to be a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms.

[0697] R N1 and R N2 They may be connected to each other to form a ring structure. The ring structure may contain oxygen atoms, etc., within the chain. Also, R N1 and R N2 The cyclic structure formed by the ring may be a single ring or a condensed ring, but a single ring is preferred. As for the cyclic structure formed, a five-membered or six-membered ring containing a nitrogen atom in formula (N1) is preferred, and examples include a pyrrole ring, an imidazole ring, a pyrazol ring, a pyrroline ring, a pyrrolidine ring, an imidazolidin ring, a pyrazolidin ring, a piperidine ring, a piperazine ring, a morpholine ring, etc., and pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring are preferred.

[0698] R C1 Silver represents a hydrogen atom or a protecting group, and a hydrogen atom is preferred.

[0699] As for the protecting group, a protecting group that decomposes by the action of an acid or a base is preferred, and a protecting group that decomposes by an acid is preferred.

[0700] Specific examples of the protecting group include chain- or cyclic alkyl groups or chain- or cyclic alkyl groups having an oxygen atom in the chain. Examples of chain- or cyclic alkyl groups include methyl groups, ethyl groups, isopropyl groups, tert-butyl groups, cyclohexyl groups, etc. Examples of chain-type alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and methyloxymethyl (MOM) groups, ethyloxyethyl (EE) groups, etc. are preferred. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy groups, glycidyl groups, oxetanyl groups, tetrahydrofuranyl groups, tetrahydropyranyl (THP) groups, etc.

[0701] In formula (N1), the divalent linker constituting L is not particularly limited, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have a substituent, or may have an atom other than a carbon atom in the hydrocarbon chain. The divalent linker is more preferably a divalent hydrocarbon linker that may have an oxygen atom in the chain, and is more preferably a group including a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and is more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom.

[0702] The divalent hydrocarbon linker preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and more preferably 6 to 10. A group comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., an arylenealkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and more preferably 7 to 10.

[0703] Specifically, the linker L is preferably a straight or branched chain alkylene group, a cyclic alkylene group, a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a straight or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylenealkylene group.

[0704] The straight or branched chain-shaped alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.

[0705] The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.

[0706] The group comprising a combination of chain-like alkylene groups and cyclic alkylene groups preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and more preferably 4 to 6 carbon atoms.

[0707] The alkylene group having an oxygen atom in the chain may be chain-shaped or cyclic, and may be straight-chain or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0708] The straight or branched alkene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and more preferably 2 to 3. The straight or branched alkene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and more preferably 1 to 3.

[0709] The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6. The number of C=C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and more preferably 1 to 2.

[0710] The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms.

[0711] The arylenealkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.

[0712] Among these, chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, and arylenealkylene groups are preferred, and 1,2-ethylene groups, propanediyl groups (particularly 1,3-propanediyl groups), cyclohexanediyl groups (particularly 1,2-cyclohexanediyl groups), vinylene groups (particularly cis-vinylene groups), phenylene groups (1,2-phenylene groups), phenylenemethylene groups (particularly 1,2-phenylenemethylene groups), and ethyleneoxyethylene groups (particularly 1,2-ethyleneoxy-1,2-ethylene groups) are more preferred.

[0713] Examples of base-generating agents include the following compounds, but are not limited to them.

[0714] [Chemical Formula 43]

[0715]

[0716] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and more preferably 300 or more.

[0717] Specific preferred compounds of ionic base generators include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0718] Specific examples of ammonium salts include the following compounds, but are not limited thereto.

[0719] [Chemical Formula 44]

[0720]

[0721] Specific examples of aluminum salts include the following compounds, but are not limited thereto.

[0722] [Chemical Formula 45]

[0723]

[0724] When the resin composition includes a base generating agent, the content of the base generating agent is preferably 0.1 to 50 parts by mass per 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 more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.

[0725] One or more base generating agents may be used. When two or more are used, it is preferable that the total amount be within the above range.

[0726] Metal Adhesion Improver

[0727] The resin composition of the present invention preferably includes a metal adhesion modifier in order to improve adhesion to metal materials used for electrodes or wiring. Examples of metal adhesion modifiers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphate derivative compounds, β-keto ester compounds, amino compounds, etc.

[0728] [Silain Coupling Agent]

[0729] Examples of silane coupling agents include the compound described in paragraph 0316 of International Publication No. 2021 / 112189 and the compound described in paragraphs 0067 to 0078 of Japanese Patent Publication No. 2018-173573, the contents of which are incorporated herein by reference. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. It is also preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. In addition, R below may be a structure derived from a blocking agent in a block isocyanate group. As for the blocking agent, it may be selected according to the detachment temperature, but examples include alcohol compounds, phenol compounds, pyrazol compounds, triazole compounds, lactam compounds, active methylene compounds, etc. For example, from the perspective of wanting the extraction temperature to be 160 to 180°C, caprolactam, etc. is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0730] [Chemical Formula 46]

[0731]

[0732] Other silane coupling agents include, for example, vinyl trimethoxysilane, vinyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, Examples include N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used individually or in combination of two or more.

[0733] In addition, as a silane coupling agent, an oligomer-type compound having multiple alkoxysilyl groups may also be used.

[0734] Examples of such oligomer-type compounds include compounds containing repeating units represented by the following formula (S-1).

[0735] [Chemical Formula 47]

[0736]

[0737] In equation (S-1), R S1 represents a monovalent organic group, and R S2represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer from 0 to 2.

[0738] R S1 It is preferable that the structure includes a polymerizable group. Examples of polymerizable groups include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazoleyl group, a blocked isocyanate group, an amino group, etc. Examples of groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, etc., and the vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group are preferred, the vinylphenyl group or a (meth)acryloyloxy group is more preferred, and the (meth)acryloyloxy group is more preferred.

[0739] R S2 It is preferable that it be an alkoxy group, and more preferable that it be a methoxy group or an ethoxy group.

[0740] n represents an integer from 0 to 2, and it is preferable that it be 1.

[0741] Here, the structures of the repeating units represented by multiple formulas (S-1) included in the oligomer-type compound may each be identical.

[0742] Here, among the repeating units represented by a plurality of formulas (S-1) included in the oligomer type compound, it is preferable that at least one has n of 1 or 2, more preferable that at least two have n of 1 or 2, and even more preferable that at least two have n of 1.

[0743] As such, commercially available oligomer-type compounds can be used, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.).

[0744] [Aluminum-based adhesive preparations]

[0745] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetoacetate), aluminum tris(acetylacetonate), ethyl acetoacetate aluminum diisopropylate, etc.

[0746] Other metal adhesion modifiers may include compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and sulfide-based compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, and the contents thereof are incorporated herein by reference.

[0747] The content of the metal adhesion modifier is preferably 0.01 to 30 parts by mass per 100 parts by mass of a specific resin, more preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass. By making the content above the lower limit value, the adhesion between the pattern and the metal layer is improved, and by making the content below the upper limit value, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion modifier may be of only one type or two or more types. When two or more types are used, it is preferable that their total amount falls within the above range.

[0748] Migration Inhibitor

[0749] The resin composition of the present invention preferably further comprises a migration inhibitor. By including 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 originating from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0750] Examples of migration inhibitors include, although not specifically limited, compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazol ring, iso-oxazole ring, isothiazol 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), thiourea groups and compounds having a sulfanyl group, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0751] As a migration inhibitor, an ion trapping agent that captures anions such as halogen ions may also be used.

[0752] Other migration inhibitors may be used, for example, as other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Publication No. 2012-194520, the compounds described in paragraph 0166 of International Patent Publication No. 2015 / 199219, etc., and the contents thereof are incorporated by reference into this specification.

[0753] Specific examples of migration inhibitors include the following compounds.

[0754] [Chemical Formula 48]

[0755]

[0756] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass% with respect to the total solid content of the resin composition, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%.

[0757] There may be only one type of migration inhibitor, or two or more types. If there are two or more types of migration inhibitors, it is preferable that the total is within the above range.

[0758] Polymerization Inhibitor

[0759] The resin composition of the present invention preferably includes a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds, etc.

[0760] Specific compounds of polymerization inhibitors include the compound described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-en-N,N-dioxide, etc. These are incorporated herein by reference.

[0761] When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass% with respect to the total solid content of the resin composition, more preferably 0.02 to 15 mass% or less, and even more preferably 0.05 to 10 mass% or less.

[0762] There may be only one type of polymerization inhibitor or two or more types. If there are two or more types of polymerization inhibitors, it is preferable that the total amount is within the above range.

[0763] Other Additives

[0764] The resin composition of the present invention may, as necessary, include various additives, for example, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers and other additives (for example, defoaming agents, flame retardants, etc.), compounds having a pyridine ring, urea compounds such as dicyclohexyl urea and diisopropyl urea, etc., within the range in which the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components may be described by referring, for example, to paragraph no. 0183 onwards of Japanese Patent Publication No. 2012-003225 (paragraph no. 0237 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), and paragraph no. 0101 to 0104, 0107 to 0109 of Japanese Patent Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are incorporated, it is preferable that the total content be 3 mass% or less of the solid content of the resin composition of the present invention.

[0765] [Surfactant]

[0766] Various surfactants, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants, can be used as surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0767] By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid characteristics (particularly fluidity) when preparing the coating solution composition are further improved, thereby further enhancing the uniformity of the coating thickness and liquid reduction. That is, when a film is formed using a coating solution containing a surfactant, the interfacial tension between the surface to be coated and the coating solution is reduced, improving wettability to the surface to be coated and enhancing coating performance. Consequently, the formation of a uniform film with minimal thickness non-uniformity can be performed more effectively.

[0768] Examples of fluorine-based surfactants include compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which are incorporated herein by reference.

[0769] As a fluorine-based surfactant, a fluorine-containing polymer compound comprising a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) may also be preferably used, and examples include the following compounds.

[0770] [Chemical Formula 49]

[0771]

[0772] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.

[0773] As for the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain may be used as the fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Publication No. 2010-164965, which are incorporated herein by reference. In addition, commercially available products include, for example, MegaPac RS-101, RS-102, RS-718K, etc., manufactured by DIC Inc.

[0774] The fluorine content in the fluorine-based surfactant is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and particularly preferably 7 to 25 mass%. Fluorine-based surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid reduction, and also have good solubility in the composition.

[0775] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include compounds described in paragraphs 0329 to 0334 of International Publication No. 2021 / 112189, respectively, and this content is incorporated herein by reference.

[0776] Surfactants may be used in the form of only one type, or two or more types may be combined.

[0777] The content of the surfactant is preferably 0.001 to 2.0 mass% with respect to the total solid content of the composition, and more preferably 0.005 to 1.0 mass%.

[0778] [Higher Fatty Acid Derivatives]

[0779] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may have a higher fatty acid derivative, such as behenic acid or behenic acid amide, added and distributed on the surface of the resin composition of the present invention during the drying process after application.

[0780] In addition, higher fatty acid derivatives may use compounds described in paragraph 0155 of International Publication No. 2015 / 199219, and this is incorporated herein by reference.

[0781] When the resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% with respect to the total solid content of the resin composition. The higher fatty acid derivative may be one type or two or more types. If there are two or more types of higher fatty acid derivatives, the total amount thereof is preferably within the above range.

[0782] [Thermal Polymerization Initiator]

[0783] Examples of thermal polymerization initiators include thermal radical polymerization initiators. A thermal radical polymerization initiator is a compound that generates radicals through thermal energy to initiate or promote the polymerization reaction of a polymerizable compound. Since the polymerization reaction of resins and polymerizable compounds can be advanced by adding a thermal radical polymerization initiator, solvent resistance can be further improved. Additionally, photopolymerization initiators may also have the function of initiating polymerization by heat and may be added as thermal polymerization initiators.

[0784] As a thermal radical polymerization initiator, specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Publication No. 2008-063554 may be cited, and the contents thereof are incorporated herein by reference.

[0785] When a thermal polymerization initiator is included, the content thereof is preferably 0.1 to 30 mass% with respect to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. The thermal polymerization initiator may be included as a single type or as two or more types. When two or more types of thermal polymerization initiators are included, the total amount is preferably within the above range.

[0786] [Inorganic Particles]

[0787] Specifically, as inorganic particles, examples include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0788] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[0789] The above average particle size of the inorganic particle is the primary particle size and also the volume average particle size. The volume average particle size can be measured, for example, by dynamic light scattering using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).

[0790] If the above measurement is difficult, it may also be measured by centrifugal sedimentation light transmission, X-ray transmission, or laser diffraction and scattering.

[0791] [UV absorber]

[0792] Examples of ultraviolet absorbers include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers.

[0793] Specific examples of ultraviolet absorbers include compounds described in paragraphs 0341 to 0342 of International Publication No. 2021 / 112189, which are incorporated herein by reference.

[0794] One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.

[0795] When the resin composition includes an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 mass% or more and 1 mass% or less with respect to the total solid mass of the resin composition, and more preferably 0.01 mass% or more and 0.1 mass% or less.

[0796] [Organic Titanium Compounds]

[0797] By containing an organic titanium compound, a resin layer with excellent chemical resistance can be formed even when cured at a low temperature.

[0798] Examples of usable organic titanium compounds include those in which an organic group is bonded to a titanium atom through covalent or ionic bonds.

[0799] Specific examples of organic titanium compounds are denoted as I) to VII) below:

[0800] I) Titanium chelate compound: A titanium chelate compound having two or more alkoxy groups is more preferred in that it provides good storage stability of the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanethionate), titanium diisopropoxide bis(2,4-pentanethionate), titanium diisopropoxide bis(tetramethylheptanethionate), titanium diisopropoxide bis(ethylacetoacetate), etc.

[0801] II) Tetraalkoxytitanium compounds: e.g., titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyl oxide, titanium tetrakis[bis{2,2-(aryloxymethyl)butoxide}], etc.

[0802] III) Titanocene compounds: for example, pentamethylcyclopentadieneyl titanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0803] IV) Monoalkoxytitanium compounds: Examples include titanium tris(dioctyl phosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, etc.

[0804] V) Titanium oxide compounds: Examples include titanium oxide bis(pentanethionate), titanium oxide bis(tetramethylheptanethionate), phthalocyanine titanium oxide, etc.

[0805] VI) Titanium tetraacetylacetonate compounds: e.g., titanium tetraacetylacetonate, etc.

[0806] VII) Titanate coupling agents: e.g., isopropyltridodecylbenzenesulfonyl titanate, etc.

[0807] Among these, as an organic titanium compound, it is preferable to have at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, in terms of better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0808] In addition, it is also desirable to include a compound represented by the following formula (T-1) as an organic titanium compound, or instead of an organic titanium compound.

[0809] [Chemical Formula 50]

[0810]

[0811] In Equation (T-1), M is titanium, zirconium, or hafnium, l1 is an integer from 0 to 2, l2 is 0 or 1, l1+l2×2 is an integer from 0 to 2, m is an integer from 0 to 4, n is an integer from 0 to 2, l1+l2+m+n×2=4, and R 11 Each is independently a substituted or unsubstituted cyclopentadieneyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group, and R 12 is a substituted or unsubstituted hydrocarbon group, and R 2 are each independently groups containing a structure represented by the following equation (T-2), and R 3 Each is independently a group containing a structure represented by the following equation (T-2), and X A Each is independently an oxygen atom or a sulfur atom.

[0812] [Chemical Formula 51]

[0813]

[0814] In equation (T-2), X 1 ~X 3 Each represents -C(-*)= or -N= independently, * represents a bonding site with a different structure, and # represents a bonding site with a metal atom.

[0815] In formula (T-1), from the perspective of preservation stability of the composition, it is preferable that M be titanium.

[0816] An embodiment in which l1 and l2 are 0 in Equation (T-1) is also one of the preferred embodiments of the present invention.

[0817] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0818] In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1.

[0819] Here, in Equation (T-1), l1 and l2 are 0, and m is 0, 2, or 4.

[0820] In Equation (T-1), from the perspective of the stability of a specific metal complex, R 11 A substituted or unsubstituted cyclopentadienyl ligand is preferred.

[0821] Also, R 11 The cyclopentadieneyl group, alkoxy group, and phenoxy group in the above may be substituted, but an unsubstituted form is also one of the preferred forms of the present invention.

[0822] In equation (T-1), R 12 It is preferable that it be a hydrocarbon group having 1 to 20 carbon atoms, and more preferable that it be a hydrocarbon group having 2 to 10 carbon atoms.

[0823] R 12 As for the hydrocarbon group, it may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred.

[0824] As for the aliphatic hydrocarbon group, it may be a saturated aliphatic hydrocarbon or an unsaturated aliphatic hydrocarbon, but a saturated aliphatic hydrocarbon group is preferred.

[0825] As for the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, an aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferred, and a phenylene group is more preferred.

[0826] R 12 As for the substituents in , monovalent substituents are preferred, and examples include halogen atoms. Also, R 12 If it is an aromatic hydrocarbon group, it may have an alkyl group as a substituent.

[0827] Among these, in Equation (T-1), R 12 It is preferable that is an unsubstituted phenylene group. Also, R 12 In this case, it is preferable that the phenylene group be a 1,2-phenylene group.

[0828] In Equation (T-1), m is greater than or equal to 2, and R 2 If 2 or more are included, those 2 or more R 2 The structures of each may be identical or different.

[0829] In Equation (T-1), n ​​is greater than or equal to 2, and R 3 If 2 or more are included, those 2 or more R 3 The structures of each may be identical or different.

[0830] In equation (T-2), X 1 ~X 3 Each represents -C(-*)= or -N= independently, and it is preferable that at least one represents -C(-*)=, and more preferable that at least two represent -C(-*)=.

[0831] Specific examples of the compound represented by formula (T-1) include compounds having the following structure, but are not limited thereto.

[0832] [Chemical Formula 52]

[0833]

[0834] When an organic titanium compound is included, the content is preferably 0.05 to 10 parts by mass per 100 parts by mass of a specific resin, and more preferably 0.1 to 2 parts by mass. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0835] [Antioxidant]

[0836] By including an antioxidant as an additive, the elongation characteristics of the film after curing and the adhesion to the metal material can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, thioether compounds, etc. Specific examples of antioxidants include compounds described in paragraphs 0348 to 0357 of International Publication No. 2021 / 112189, which are incorporated herein by reference.

[0837] The content of the antioxidant is preferably 0.1 to 10 parts by mass per 100 parts by mass of a specific resin, and more preferably 0.5 to 5 parts by mass. By adding an amount of 0.1 parts by mass or more, it is easy to obtain effects such as improved elongation characteristics or adhesion to metal materials even under high temperature and high humidity environments, and by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with a photosensitive agent. Only one type of antioxidant may be used, or two or more types may be used. If two or more types are used, it is preferable that their total amount be within the above range.

[0838] [Inhibitor]

[0839] Examples of anti-coagulant agents include sodium polyacrylate.

[0840] Anti-coagulant may be used as a single type or in combination of two or more types.

[0841] When the resin composition includes an anti-aggregation agent, the content of the anti-aggregation agent is preferably 0.01 mass% or more and 10 mass% or less with respect to the total solid mass of the resin composition, and more preferably 0.02 mass% or more and 5 mass% or less.

[0842] [Phenol compounds]

[0843] Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenethris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Kagaku Kogyo Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Yukizai Co., Ltd.).

[0844] Phenolic compounds may be used as a single type or in combination of two or more types.

[0845] When the resin composition includes a phenolic compound, the content of the phenolic compound is preferably 0.01 mass% or more and 30 mass% or less with respect to the total solid mass of the resin composition, and more preferably 0.02 mass% or more and 20 mass% or less.

[0846] [Other polymer compounds]

[0847] Other polymer compounds include siloxane resin, (meth)acrylic polymer copolymerized with (meth)acrylic acid, novolak resin, resol resin, polyhydroxystyrene resin and copolymers thereof. Other polymer compounds may be modified materials in which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0848] Other polymer compounds may be used individually or in combination of two or more types.

[0849] When the resin composition includes other polymer compounds, the content of the other polymer compounds is preferably 0.01 mass% or more and 30 mass% or less with respect to the total solid mass of the resin composition, and more preferably 0.02 mass% or more and 20 mass% or less.

[0850] [Compounds having a pyridine ring]

[0851] The resin composition may further include a compound having a pyridine ring.

[0852] Compounds having a pyridine ring include pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetylpyridine, 3-acetylpyridine, 4-acetylpyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine, 4-(aminomethyl)pyridine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, Examples include 2,4,6-trimethylpyridine, 2-mercaptopyridine, 3-mercaptopyridine, 4-mercaptopyridine, etc., but are not limited to these.

[0853] Compounds having a pyridine ring may be used alone or in combination of two or more.

[0854] When the resin composition includes a compound having a pyridine ring, the content of other polymer compounds is preferably 0.01 mass% or more and 30 mass% or less with respect to the total solid mass of the resin composition, and more preferably 0.02 mass% or more and 20 mass% or less.

[0855] Characteristics of the Resin Composition

[0856] The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. In terms of coating film thickness, 1,000 mm 2 / s~12,000mm 2 / s is preferable, and 2,000mm 2 / s~10,000mm 2 / s is more preferable, and 2,500mm 2 / s~8,000mm 2 / s is more preferable. Within the above range, it becomes easier to obtain a coating film with high uniformity. 1,000mm 2 If it is greater than / s, for example, it is easy to apply to a film thickness required as an insulating film for redistribution, and 12,000mm 2 If / s or less, a coating film with excellent surface finish is obtained.

[0857] <Limitations on materials contained in resin compositions>

[0858] The moisture content of the resin composition of the present invention is preferably less than 2.0 mass%, more preferably less than 1.5 mass%, and more preferably less than 1.0 mass%. If it is less than 2.0%, the storage stability of the resin composition is improved.

[0859] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container during storage.

[0860] The metal content of the resin composition of the present invention is preferably less than 5 parts per million (mass ppm) from the perspective of insulation properties, more preferably less than 1 part per million (mass ppm), and more preferably less than 0.5 parts per million (mass ppm). Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals included as complexes of organic compounds and metals are excluded. When multiple metals are included, it is preferable that the total of these metals falls within the above range.

[0861] In addition, methods for reducing metal impurities unintentionally included in the resin composition of the present invention may include selecting a raw material with a low metal content as a raw material constituting the resin composition of the present invention, performing filter filtration on the raw material constituting the resin composition of the present invention, or performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene, etc.

[0862] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably less than 200 mass ppm from the perspective of wiring corrosion resistance. Among these, the content existing in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the sum of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, each fall within the above ranges.

[0863] As a method for controlling the content of halogen atoms, ion exchange treatment is preferably cited.

[0864] Conventionally known receiving containers may be used as receiving containers for the resin composition of the present invention. As a receiving container, for the purpose of suppressing the incorporation of impurities into the raw material or the resin composition of the present invention, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of six types of six layers of resin, or a bottle in which six types of resin are arranged in a seven-layer structure. Examples of such containers include the container described in Japanese Patent Publication No. 2015-123351.

[0865] <Curated product of resin composition>

[0866] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0867] The cured product of the present invention is a cured product formed by curing a resin composition.

[0868] It is preferable that the curing of the resin composition be carried out by heating, and the heating temperature is more preferably 120°C to 400°C, more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, it is preferable that the cured product be in the form of a film. By pattern processing of the resin composition, the shape of the cured product may be selected according to the application, such as forming a protective film on a wall surface, forming a bias hole for conductivity, adjusting impedance, capacitance, or internal stress, or providing a heat dissipation function. It is preferable that the film thickness of the cured product (a film formed from the cured product) be 0.5 μm or more and 150 μm or less.

[0869] The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and more preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after curing of the resin composition and can be calculated from the following formula.

[0870] Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0871] Characteristics of the Cured Product of the Resin Composition

[0872] The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.

[0873] The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and more preferably 50% or more.

[0874] The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and more preferably 230°C or higher.

[0875] <Preparation of Resin Composition>

[0876] The resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited and can be carried out using conventionally known methods.

[0877] Mixing methods include mixing by stirring blades, mixing by ball mills, and mixing by rotating a tank.

[0878] The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

[0879] For the purpose of removing foreign substances, such as dust or fine particles, from the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore diameter is, for example, preferably 5 μm or less, more preferably 1 μm or less, more preferably 0.5 μm or less, and more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. If the filter material is polyethylene, it is more preferable to use HDPE (high-density polyethylene). The filter may be used after being pre-cleaned with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore diameters or materials may be combined. As an example of a connection mode, an HDPE filter with a pore diameter of 1 μm is connected in series as the first stage, and an HDPE filter with a pore diameter of 0.2 μm is connected as the second stage. In addition, various materials may be filtered multiple times. When filtering multiple times, recirculating filtration may be performed. In addition, filtration may be performed by applying pressure. When filtration is performed by applying pressure, the pressure applied is preferably, for example, 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and more preferably 0.05 MPa or more and 0.5 MPa or less.

[0880] In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. A combination of filter filtration and impurity removal treatment using an adsorbent may also be performed. As for the adsorbent, known adsorbents may be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[0881] After filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure and a degassing process may be performed.

[0882] (Method for manufacturing a hardened material)

[0883] The method for manufacturing a cured product of the present invention preferably includes a film-forming process in which a resin composition is applied to a substrate to form a film.

[0884] A method for manufacturing a cured product more preferably comprises a film forming process, an exposure process for selectively exposing the film formed by the film forming process, and a development process for forming a pattern by developing the film exposed by the exposure process using a developer.

[0885] A method for manufacturing a cured product is particularly preferably composed of at least one of the film forming process, the exposure process, the development process, and a heating process for heating a pattern obtained by the development process and a post-development exposure process for exposing a pattern obtained by the development process.

[0886] In addition, the method for manufacturing the cured product may also include the film forming process and the process of heating the film.

[0887] The details of each process are explained below.

[0888] Film formation process

[0889] The resin composition of the present invention can be used in a film-forming process that forms a film by applying it to a substrate.

[0890] The method for manufacturing a cured product of the present invention preferably includes a film-forming process in which a resin composition is applied to a substrate to form a film.

[0891] 〔write〕

[0892] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical film, ceramic material, deposited film, magnetic film, reflective film; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any of a substrate formed from metal and a substrate in which a metal layer is formed, for example, by plating or deposition); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrate; mold substrate; and electrode plate of a plasma display panel (PDP). Semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[0893] These materials may have a layer such as an adhesion layer or an oxide layer formed by hexamethyldisilase (HMDS) or the like provided on the surface.

[0894] The shape of the material is not particularly limited and may be circular or rectangular.

[0895] If the size of the substrate is circular, for example, the diameter is preferably 100 to 450 mm, and more preferably 200 to 450 mm. If the substrate is rectangular, for example, the length of the short side is preferably 100 to 1000 mm, and more preferably 200 to 700 mm.

[0896] As a substrate, for example, a plate-shaped, preferably panel-shaped substrate (substrate) is used.

[0897] In cases where a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer made of a cured material) or a metal layer, the resin layer or the metal layer serves as the substrate.

[0898] As a means of applying the resin composition onto a substrate, coating is preferred.

[0899] Specifically, the means of application include the dip coat method, air knife coat method, curtain coat method, wire bar coat method, gravure coat method, extrusion coat method, spray coat method, spin coat method, slit coat method, inkjet method, etc. From the perspective of film thickness uniformity, the spin coat method, slit coat method, spray coat method, or inkjet method is preferred, and from the perspective of film thickness uniformity and productivity, the spin coat method and slit coat method are more preferred. By adjusting the solid content concentration of the resin composition or the coating conditions according to the means of application, a film of a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate; for circular substrates such as wafers, the spin coat method, spray coat method, inkjet method, etc. are preferred, and for rectangular substrates, the slit coat method, spray coat method, inkjet method, etc. are preferred. In the case of the spin coat method, for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.

[0900] In addition, a method of transferring a coating film formed by applying it in advance on a provisional support according to the above application method onto a substrate may also be applied.

[0901] Regarding the transfer method, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592 may be suitably used.

[0902] In addition, a process for removing excess film at the end of the substrate may be performed. Examples of such processes include edge bead rinse (EBR) and back rinse.

[0903] A pre-wet process may be adopted in which various solvents are applied to the substrate before applying the resin composition to improve the wettability of the substrate, and then the resin composition is applied.

[0904] Drying Process

[0905] The above film may be provided to a drying process (drying process) for drying the formed film (layer) to remove the solvent after the film formation process (layer formation process).

[0906] That is, the method for manufacturing a cured product of the present invention may include a drying process for drying a film formed by a film forming process.

[0907] It is preferable that the above drying process be performed after the film formation process and before the photolithography process.

[0908] In the drying process, the drying temperature of the film is preferably 50 to 150°C, more preferably 70°C to 130°C, and more preferably 90°C to 110°C. Additionally, drying may be performed under reduced pressure. As for the drying time, 30 seconds to 20 minutes is exemplified, 1 minute to 10 minutes is preferable, and 2 minutes to 7 minutes is more preferable.

[0909] Photolithography Process

[0910] The above film may be provided to an exposure process that selectively exposes the film.

[0911] A method for manufacturing a cured product may include an exposure process for selectively exposing a film formed by a film formation process.

[0912] Selective exposure means exposing a portion of the film. Furthermore, through selective exposure, an exposed area (exposed region) and an unexposed area (unexposed region) are formed in the film.

[0913] The exposure amount is not particularly limited as long as it can cure the resin composition of the present invention, but, for example, 50 to 10,000 mJ / cm² in terms of exposure energy at a wavelength of 365 nm. 2 It is desirable, and 200~8,000 mJ / cm² 2 It is more desirable.

[0914] The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, and 240 to 550 nm is preferred.

[0915] Exposure wavelengths, in relation to the light source, include (1) semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-lines (wavelength 436 nm), h-lines (wavelength 405 nm), i-lines (wavelength 365 nm), broad (three wavelengths of g, h, and i lines), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, and (7) the second harmonic of a YAG laser at 532 nm and the third harmonic at 355 nm. For the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-line is more preferred from the perspective of exposure sensitivity.

[0916] The method of exposure is not particularly limited and may be any method in which at least a portion of the film made of the resin composition of the present invention is exposed, such as exposure using a photomask or exposure by a laser direct imaging method.

[0917] Post-exposure heating process

[0918] The above film may be provided in a heating process after exposure (heating process after exposure).

[0919] That is, the method for manufacturing a cured product of the present invention may include a post-exposure heating process for heating a film exposed by a photolithography process.

[0920] The post-exposure heating process can be performed after the exposure process and before the development process.

[0921] In the heating process after exposure, the heating temperature is preferably 50℃ to 140℃, and more preferably 60℃ to 120℃.

[0922] In the heating process after exposure, the heating time is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes.

[0923] In the heating process after exposure, the heating rate from the starting temperature to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and more preferably 3 to 10°C / min.

[0924] In addition, the heating rate may be appropriately changed during heating.

[0925] As a heating means for the heating process after exposure, there are no particular limitations, and known hot plates, ovens, infrared heaters, etc., can be used.

[0926] In addition, it is also desirable to perform the process under an atmosphere of low oxygen concentration by flowing inert gases such as nitrogen, helium, or argon during heating.

[0927] <Development Process>

[0928] The above film after exposure may be provided to a development process that forms a pattern by developing it using a developer solution.

[0929] That is, the method for manufacturing a cured product of the present invention may include a developing process in which a film exposed by a photolithography process is developed using a developer to form a pattern.

[0930] By performing the development, one of the exposed and unexposed parts of the film is removed, and a pattern is formed.

[0931] Here, the phenomenon in which the non-exposed portion of the film is removed by the development process is called negative-type development, and the phenomenon in which the exposed portion of the film is removed by the development process is called positive-type development.

[0932] 〔developer〕

[0933] Examples of developers used in the development process include alkaline aqueous solutions or developers containing organic solvents.

[0934] When the developer is an alkaline aqueous solution, basic compounds that may be included in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, and TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, Methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and more preferably TMAH. The content of the basic compound in the developer is preferably 0.01 to 10 mass% of the total mass of the developer, more preferably 0.1 to 5 mass%, and even more preferably 0.3 to 3 mass%.

[0935] In cases where the developer contains an organic solvent, the compound described in paragraph 0387 of International Publication No. 2021 / 112189 may be used as the organic solvent. This content is incorporated herein by reference. In addition, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. may also be suitable examples.

[0936] When the developer includes an organic solvent, one or more types of organic solvents may be used in combination. In the present invention, a developer is particularly preferred that includes at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone, a developer is more preferred that includes at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide, and a developer containing cyclopentanone is particularly preferred.

[0937] When the developer solution contains an organic solvent, the content of the organic solvent relative to the total mass of the developer solution is preferably 50 mass% or more, more preferably 70 mass% or more, more preferably 80 mass% or more, and particularly preferably 90 mass% or more. In addition, the content may be 100 mass%.

[0938] If the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generating agent. In some cases, performance such as the elongation at break of the pattern may be improved by at least one of the basic compound and the base generating agent in the developer penetrating into the pattern.

[0939] As for the basic compound, organic bases are preferred from the perspective of reliability when remaining on the film after curing (adhesion to the substrate when the cured product is further heated).

[0940] As for the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, but to promote the imidation reaction, primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines, or ammonium salts are more preferred, secondary amines or tertiary amines are even more preferred, and tertiary amines are particularly preferred.

[0941] Regarding the basic compound, from the perspective of the mechanical properties (elongation at break) of the cured product, it is desirable that it is difficult to remain in the cured film (the resulting cured product), and from the perspective of promoting cyclization, it is desirable that the amount remaining before heating is difficult to decrease due to vaporization, etc.

[0942] Accordingly, the boiling point of the basic compound is preferably 30°C to 350°C at atmospheric pressure (101,325 Pa), more preferably 80°C to 270°C, and more preferably 100°C to 230°C.

[0943] It is preferable that the boiling point of the basic compound be higher than the boiling point of the organic solvent contained in the developer by subtracting 20°C, and more preferable that it be higher than the boiling point of the organic solvent contained in the developer.

[0944] For example, when the boiling point of an organic solvent is 100°C, the basic compound used preferably has a boiling point of 80°C or higher, and more preferably has a boiling point of 100°C or higher.

[0945] The developer may contain only one basic compound, or two or more.

[0946] Specific examples of basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianylinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propanediamine, N-[3-(dimethylamino)propyl]acetamide, N-[3-(dimethylamino)propyl]acrylamide, Examples include N-[3-(dimethylamino)propyl]methacrylamide, N-methyl-N-(2-methylaminopropyl)acetamide, etc.

[0947] A preferred embodiment of the base generating agent is the same as a preferred embodiment of the base generating agent included in the composition described above. In particular, it is preferable that the base generating agent be a thermobase generating agent.

[0948] When the developer comprises at least one of a basic compound and a base generating agent, the content of the basic compound or base generating agent is preferably 10 mass% or less with respect to the total mass of the developer, and more preferably 5 mass% or less. The lower limit of the content is not particularly limited, but, for example, 0.1 mass% or more is preferred.

[0949] When a basic compound or base generator is a solid in the environment where the developer is used, it is also preferable that the content of the basic compound or base generator be 70 to 100 mass% with respect to the total solid content of the developer.

[0950] The developer may contain only one of the basic compound and the base generating agent, or may contain two or more. If there are two or more of the basic compound and the base generating agent, it is preferable that the total amount is within the above range.

[0951] The developer may contain additional components.

[0952] Other ingredients include, for example, known surfactants or known antifoaming agents.

[0953] [Method of supplying developing solution]

[0954] The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and includes a method of immersing a substrate with a formed film in the developer, puddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, and spray nozzles.

[0955] From the perspective of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying it through a spray nozzle is preferred, and from the perspective of developer penetration into the image area, the method of supplying it through a spray nozzle is more preferred.

[0956] In addition, a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied through a straight nozzle again, and the substrate is spun to remove the developer from the substrate, and this process may be repeated multiple times.

[0957] Methods for supplying the developer solution in the development process include a process in which the developer solution is continuously supplied to the substrate, a process in which the developer solution is maintained in a roughly stationary state on the substrate, a process in which the developer solution is vibrated on the substrate using ultrasound or the like, and a combination of the same.

[0958] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not specifically determined, but is preferably 10 to 45°C, and more preferably 18°C ​​to 30°C.

[0959] In the development process, after treatment with the developer, cleaning (rinsing) of the pattern with a rinsing solution may be further performed. In addition, methods such as supplying the rinsing solution before the developer in contact with the pattern is completely dried may be adopted.

[0960] [Rinse Solution]

[0961] When the developer is an alkaline aqueous solution, water, for example, can be used as the rinsing solution. When the developer is a developer containing an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0962] As for the organic solvent in the case where the rinse solution contains an organic solvent, the same organic solvent as the organic solvent exemplified in the case where the above-described developer solution contains an organic solvent can be cited.

[0963] It is preferable that the organic solvent included in the rinse solution be an organic solvent different from the organic solvent included in the developer solution, and it is more preferable that the organic solvent has a lower solubility of the pattern than the organic solvent included in the developer solution.

[0964] When the rinse solution contains an organic solvent, one type of organic solvent or a mixture of two or more types may be used. The organic solvents are preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, and more preferably cyclohexanone and PGMEA.

[0965] When the rinse solution contains an organic solvent, the organic solvent is preferably 50 mass% or more, more preferably 70 mass% or more, and more preferably 90 mass% or more with respect to the total mass of the rinse solution. In addition, the organic solvent may be 100 mass% with respect to the total mass of the rinse solution.

[0966] The rinse solution may contain at least one of a basic compound and a base generating agent.

[0967] Although not specifically limited, an embodiment in which the developer solution contains an organic solvent, and the rinsing solution contains at least one of an organic solvent, a basic compound, and a base generating agent is also one of the preferred embodiments of the present invention.

[0968] As basic compounds and base generating agents included in the rinse solution, examples of basic compounds and base generating agents that may be included when the above-described developer solution contains an organic solvent may be cited, and preferred embodiments are the same.

[0969] Basic compounds and base-generating agents included in the rinse solution can be selected by considering the solubility of the solvent in the rinse solution, etc.

[0970] When the rinse solution comprises at least one of a basic compound and a base generating agent, the content of the basic compound or base generating agent is preferably 10 mass% or less with respect to the total mass of the rinse solution, and more preferably 5 mass% or less. The lower limit of the above content is not particularly limited, but, for example, 0.1 mass% or more is preferred.

[0971] When the basic compound or base generator is solid in the environment where the rinse liquid is used, it is also preferable that the content of the basic compound or base generator be 70 to 100 mass% with respect to the total solid content of the rinse liquid.

[0972] When the rinse solution contains at least one of a basic compound and a base generating agent, the rinse solution may contain only one of the basic compound and base generating agent, or two or more. When at least one of the basic compound and base generating agent is two or more, it is preferable that the total amount is within the above range.

[0973] The rinse solution may contain additional ingredients.

[0974] Other ingredients include, for example, known surfactants or known antifoaming agents.

[0975] [Method of supplying rinse solution]

[0976] There are no particular restrictions on the method of supplying the rinse solution as long as a desired pattern can be formed, and methods include immersing the substrate in the rinse solution, supplying the rinse solution to the substrate by liquid rising, supplying the rinse solution to the substrate by showering, and continuously supplying the rinse solution onto the substrate by means such as a straight nozzle.

[0977] From the perspective of the penetration of the rinse solution, the removal of non-burned areas, and manufacturing efficiency, there are methods of supplying the rinse solution through a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of supplying it continuously through a spray nozzle is preferred, and from the perspective of the penetration of the rinse solution into the burned area, a method of supplying it through a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include a straight nozzle, a shower nozzle, a spray nozzle, etc.

[0978] That is, the rinsing process is preferably a process of supplying the rinsing liquid to the film after exposure by means of a straight nozzle or continuously supplying it, and more preferably a process of supplying the rinsing liquid by means of a spray nozzle.

[0979] As a method for supplying the rinse liquid in the rinsing process, a process in which the rinse liquid is continuously supplied to the substrate, a process in which the rinse liquid is maintained in a roughly stationary state on the substrate, a process in which the rinse liquid on the substrate is vibrated with ultrasound or the like, and a combination of the same can be employed.

[0980] As for the rinsing time, 10 seconds to 10 minutes is preferable, and 20 seconds to 5 minutes is more preferable. The temperature of the rinsing solution during rinsing is not specifically determined, but 10 to 45°C is preferable, and 18°C ​​to 30°C is more preferable.

[0981] In the developing process, a process of bringing the treatment solution into contact with the pattern may be included after treatment with the developer solution or after cleaning the pattern with the rinse solution. Additionally, methods such as supplying the treatment solution while the developer solution or rinse solution in contact with the pattern is not completely dry may be adopted.

[0982] Examples of the above treatment solution include a treatment solution comprising at least one of water and an organic solvent, and at least one of a basic compound and a base generating agent.

[0983] A preferred embodiment of at least one of the above organic solvent, and, basic compound, and base generating agent is the same as a preferred embodiment of at least one of the organic solvent, and, basic compound, and base generating agent used in the rinse liquid described above.

[0984] The method of supplying the pattern of the treatment liquid can use the same method as the method of supplying the rinse liquid described above, and the preferred embodiment is also the same.

[0985] The content of the basic compound or base generating agent in the treatment solution is preferably 10 mass% or less with respect to the total mass of the treatment solution, and more preferably 5 mass% or less. The lower limit of the above content is not particularly limited, but, for example, it is preferably 0.1 mass% or more.

[0986] In addition, when the basic compound or base generating agent is a solid in the environment where the treatment solution is used, it is also preferable that the content of the basic compound or base generating agent be 70 to 100 mass% with respect to the total solid content of the treatment solution.

[0987] When the treatment solution contains at least one of a basic compound and a base generating agent, the treatment solution may contain only one of the basic compound and base generating agent, or two or more. When at least one of the basic compound and base generating agent is two or more, it is preferable that the total amount is within the above range.

[0988] Heating Process

[0989] The pattern obtained by the development process (or the pattern after rinsing in the case of performing a rinsing process) may be provided to a heating process that heats the pattern obtained by the development process.

[0990] That is, the method for manufacturing a cured product of the present invention may include a heating process for heating a pattern obtained by a developing process.

[0991] In addition, the method for manufacturing a cured product of the present invention may include a heating process for heating a pattern obtained by another method without performing a developing process, or a film obtained by a film forming process.

[0992] In the heating process, the resin, such as the polyimide precursor, is cyclized to become the polyimide resin.

[0993] In addition, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds.

[0994] As for the heating temperature (maximum heating temperature) in the heating process, 50 to 450°C is preferred, 150 to 350°C is more preferred, 150 to 250°C is more preferred, 160 to 250°C is even more preferred, and 160 to 230°C is particularly preferred.

[0995] The heating process is preferably a process that promotes the cyclization reaction of the polyimide precursor within the pattern by means of the action of a base, etc., generated from the base generating agent by heating.

[0996] In the heating process, it is preferable to perform heating at a heating rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The heating rate is more preferably 2 to 10°C / min, and more preferably 3 to 10°C / min. By increasing the heating rate to 1°C / min or higher, productivity can be ensured while preventing excessive volatilization of the acid or solvent, and by increasing the heating rate to 12°C / min or lower, residual stress in the cured product can be relieved.

[0997] Additionally, in the case of a rapid heating oven, it is preferable to heat at a rate of 1 to 8°C / second from the temperature at the start of heating to the maximum heating temperature, more preferable at 2 to 7°C / second, and more preferable at 3 to 6°C / second.

[0998] The temperature at which heating is initiated is preferably 20°C to 150°C, more preferably 20°C to 130°C, and more preferably 25°C to 120°C. The temperature at which heating is initiated refers to the temperature at which the process of heating to the maximum heating temperature is initiated. For example, when the resin composition of the present invention is applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and, for example, it is preferable to increase the temperature starting from a temperature 30°C to 200°C lower than the boiling point of the solvent included in the resin composition.

[0999] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and more preferably 15 to 240 minutes.

[1000] In particular, when forming a multilayer laminate, from the perspective of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, more preferably 100°C or higher, and particularly preferably 120°C or higher.

[1001] The upper limit of the above heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and more preferably 240°C or lower.

[1002] Heating may be performed in stages. For example, a process such as increasing the temperature from 25°C to 120°C at a rate of 3°C / min, maintaining it at 120°C for 60 minutes, increasing the temperature from 120°C to 180°C at a rate of 2°C / min, and maintaining it at 180°C for 120 minutes may be performed. In addition, it is also desirable to treat while irradiating with ultraviolet light as described in U.S. Patent Publication No. 9159547. It is possible to improve the characteristics of the film through such a pretreatment process. It is preferable to perform the pretreatment process for a short period of about 10 seconds to 2 hours, and more preferable to perform it for 15 seconds to 30 minutes. The pretreatment process may be performed in two or more steps; for example, a first pretreatment process may be performed in the range of 100 to 150°C, and then a second pretreatment process may be performed in the range of 150 to 200°C.

[1003] In addition, it may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5°C / min.

[1004] From the perspective of preventing the decomposition of a specific resin, it is preferable to perform the heating process in an atmosphere of low oxygen concentration by flowing inert gases such as nitrogen, helium, or argon, or by performing it under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[1005] As for the heating means in the heating process, there are no particular limitations, but examples include a hot plate, an infrared furnace, an electric oven, a hot air oven, an infrared oven, etc.

[1006] Post-development exposure process

[1007] The pattern obtained by the development process (or the pattern after rinsing in the case of performing a rinsing process) may be provided to a post-development exposure process in which the pattern after the development process is exposed, instead of or in addition to the heating process.

[1008] That is, the method for manufacturing a cured product of the present invention may include a post-development exposure process for exposing a pattern obtained by a development process. The method for manufacturing a cured product of the present invention may include a heating process and a post-development exposure process, or it may include only one of the heating process and the post-development exposure process.

[1009] In the post-development exposure process, for example, reactions such as the cyclization of polyimide precursors by the photosensitive action of a photobase generator, or the detachment of acid-degradable groups by the photosensitive action of a photocatalytic agent, can be promoted.

[1010] In the exposure process after development, at least a portion of the pattern obtained in the development process needs to be exposed, but it is preferable that the entire pattern be exposed.

[1011] The exposure amount in the post-development exposure process is 50–20,000 mJ / cm², converted to exposure energy at the wavelength where the photosensitive compound is sensitive. 2 It is desirable, and 100~15,000 mJ / cm² 2 It is more desirable.

[1012] The exposure process after development can be performed, for example, using a light source in the exposure process described above, and it is preferable to use broadband light.

[1013] Metal layer formation process

[1014] A pattern obtained by a developing process (preferably provided in at least one of a heating process and a post-development exposure process) may be provided to a metal layer forming process for forming a metal layer on the pattern.

[1015] That is, the method for manufacturing a cured product of the present invention preferably includes a metal layer forming process for forming a metal layer on a pattern obtained by a developing process (preferably provided in at least one of a heating process and a post-development exposure process).

[1016] As for the metal layer, existing metal types may be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals are examples, copper and aluminum are more preferred, and copper is more preferred.

[1017] The method for forming the metal layer can be any existing method without particular limitation. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent Publication No. 7888181B2, and U.S. Patent Publication No. 9177926B2 may be used. Examples include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining the same. More specifically, sputtering, a patterning method combining photolithography and etching, and a patterning method combining photolithography and electroplating may be cited. A preferred embodiment of plating is electroplating using a copper sulfate or copper cyanide plating solution.

[1018] As for the thickness of the metal layer, in the thickest part, 0.01 to 50 μm is preferred, and 1 to 10 μm is more preferred.

[1019] <Uses>

[1020] Examples of the method for manufacturing the cured product of the present invention, or applicable fields of the cured product, include insulating films for electronic devices, interlayer insulating films for redistribution layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, interlayer insulating films), or forming patterns by etching on insulating films for mounting purposes as described above. For these applications, for example, one may refer to Science & Technology Co., Ltd., "High-performance Polyimide and Application Technology," April 2008, supervised by Masaaki Kakimoto, CMC Technical Library, "Fundamentals and Development of Polyimide Materials," published November 2011, and the Japan Polyimide and Aromatic Polymer Research Group, ed., "Fundamentals and Applications of Latest Polyimide," NTS, August 2010.

[1021] The method for manufacturing a cured product of the present invention, or the cured product of the present invention, may also be used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, for use as an etching of a molded part, and for manufacturing a protective lacquer and a dielectric layer in electronics, particularly in microelectronics.

[1022] (Laminated body, and, method of manufacturing the laminated body)

[1023] The laminate of the present invention refers to a structure having multiple layers of the cured material of the present invention.

[1024] The laminate is a laminate comprising two or more layers made of a cured material, and may also be a laminate with three or more layers stacked.

[1025] Among the layers comprising two or more layers of the cured material included in the above laminate, at least one is a layer comprising the cured material of the present invention, and from the perspective of suppressing shrinkage of the cured material or deformation of the cured material due to said shrinkage, it is also preferable that all layers comprising the cured material included in the above laminate are layers comprising the cured material of the present invention.

[1026] That is, the method for manufacturing a laminate of the present invention preferably includes the method for manufacturing a cured product of the present invention, and more preferably includes repeating the method for manufacturing a cured product of the present invention a plurality of times.

[1027] The laminate of the present invention preferably comprises two or more layers made of a cured material, and includes a metal layer between any one of the layers made of the cured material. The metal layer is preferably formed by the metal layer forming process.

[1028] That is, the method for manufacturing a laminate according to the present invention preferably further includes a metal layer forming process for forming a metal layer on a layer formed of a cured material between the multiple methods for manufacturing a cured material. A preferred embodiment of the metal layer forming process is as described above.

[1029] As for the above laminate, for example, a laminate comprising at least three layers stacked in this order, such as a layer made of a first hardened material, a metal layer, and a layer made of a second hardened material, can be cited as a preferred laminate.

[1030] Preferably, the layer formed by the first cured material and the layer formed by the second cured material are both layers formed by the cured material of the present invention. The resin composition of the present invention used to form the layer formed by the first cured material and the resin composition of the present invention used to form the layer formed by the second cured material may have the same composition or may have different compositions. The metal layer in the laminate of the present invention is preferably used as a metal wiring layer, such as a redistribution layer.

[1031] Additive manufacturing process

[1032] The method for manufacturing a laminate of the present invention preferably includes a lamination process.

[1033] The lamination process is a series of processes comprising, once again, performing at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, (d) a heating process, and a post-development exposure process on the surface of a pattern (resin layer) or a metal layer in this order. However, the method may be a form in which at least one of (a) the film formation process and (d) the heating process and the post-development exposure process is repeated. Furthermore, after at least one of (d) the heating process and the post-development exposure process, (e) a metal layer formation process may be included. It goes without saying that the lamination process may appropriately further include the above-mentioned drying process, etc.

[1034] If an additional stacking process is performed after the stacking process, a surface activation treatment process may be further performed after the photolithography process, after the heating process, or after the metal layer formation process. Plasma treatment is exemplified as a surface activation treatment. Details regarding the surface activation treatment will be described later.

[1035] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[1036] For example, a configuration having 2 to 20 layers of resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration having 2 to 9 layers is more preferred.

[1037] Each of the above layers may have the same composition, shape, film thickness, etc., or may differ.

[1038] In particular, in the present invention, after providing a metal layer, an embodiment is preferred in which a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, an embodiment may be provided in which the sequence of (a) film formation process, (b) exposure process, (c) development process, (d) at least one of a heating process and an exposure process after development, and (e) metal layer formation process is repeated, or an embodiment may be provided in which the sequence of (a) film formation process, (d) at least one of a heating process and an exposure process after development, and (e) metal layer formation process is repeated. By alternately performing a lamination process for laminating the resin composition layer (resin layer) of the present invention and a metal layer formation process, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

[1039] (Surface activation treatment process)

[1040] The method for manufacturing a laminate of the present invention preferably includes a surface activation treatment process for surface activating at least a portion of the metal layer and the resin composition layer.

[1041] The surface activation treatment process is typically performed after the metal layer formation process, but the metal layer formation process may be performed after the development process (preferably after at least one of the heating process and the post-development exposure process), and then after performing the surface activation treatment process on the resin composition layer.

[1042] Surface activation treatment may be performed only on at least a portion of the metal layer, only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. It is preferable to perform surface activation treatment on at least a portion of the metal layer, and it is preferable to perform surface activation treatment on a portion or all of the area in the metal layer where the resin composition layer is formed on the surface. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved.

[1043] It is preferable to perform surface activation treatment on part or all of the resin composition layer (resin layer) after exposure. By performing surface activation treatment on the surface of the resin composition layer in this way, adhesion to the metal layer or resin layer provided on the surface-activated surface can be improved. In particular, when the resin composition layer is cured, such as when performing negative type development, it is less susceptible to damage from the surface treatment, and adhesion is easily improved.

[1044] Surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This is incorporated herein by reference.

[1045] (Semiconductor device and method of manufacturing the same)

[1046] The present invention also discloses a semiconductor device comprising the cured material of the present invention or a laminate.

[1047] In addition, the present invention also discloses a method for manufacturing a semiconductor device comprising a method for manufacturing a cured product of the present invention or a method for manufacturing a laminate.

[1048] As a specific example of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a redistribution layer, reference may be made to paragraphs 0213 to 0218 of Japanese Patent Publication No. 2016-027357 and to the description of FIG. 1, the contents of which are incorporated herein by reference.

[1049] Examples

[1050] The present invention will be explained in more detail below with reference to examples. The materials, usage amounts, ratios, processing details, processing procedures, etc., shown in the following examples may be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[1051] Suzy's Synthesis

[1052] [Synthesization Example 1: Synthesis of Polymer P-1]

[1053] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at 60°C for 18 hours to prepare a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Subsequently, the obtained diester was chlorinated with SOCl2, and then a solution of 4,4'-diaminodiphenyl ether dissolved in N-methylpyrrolidone was added dropwise to the reaction mixture in the same manner as in Synthesis Example 2 described below, and then the obtained reaction mixture was purified and dried. The weight average molecular weight of this polyimide precursor (polymer P-1) was 18,000. Polymer P-1 is a resin with the following structure.

[1054] [Chemical Formula 53]

[1055]

[1056] [Synthesization Example 2: Synthesis of Polymer P-2]

[1057] 7.76 g (25 mmol) of 4,4'-Oxydiphthalic dianhydride (ODPA) and 6.23 g (25 mmol) of 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride were placed in a reaction vessel, and 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 7.91 g of pyridine while stirring at room temperature. After the exothermic reaction was completed, the mixture was cooled to room temperature and left to stand for 16 more hours.

[1058] Next, under ice cooling, a solution of 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 30 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes. Subsequently, a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone was added while stirring for 60 minutes.

[1059] Additionally, after stirring at room temperature for 2 hours, 3 ml of ethyl alcohol was added and stirred for 1 hour. Then, 100 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[1060] The obtained reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 3 liters of water to precipitate the polymer, and the obtained precipitate was filtered and then vacuum dried to obtain powdered polymer P-2.

[1061] The weight-average molecular weight (Mw) of this polymer was measured to be 23,000.

[1062] Polymer P-2 is a resin with the following structure.

[1063] [Chemical Fo...

Claims

Claim 1 delete Claim 2 delete Claim 3 A resin composition comprising at least one resin selected from the group consisting of a polyimide precursor, polyimide, a polyamideimide precursor, polyamideimide, and polyamide, and a solvent, wherein the solvent comprises γ-valerolactone, and the content of γ-valerolactone is 50 mass% or more based on the total mass of the solvent. Claim 4 A resin composition comprising at least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polyamideimide precursor, a polyamideimide, and a polyamide, and a solvent, wherein the solvent comprises γ-valerolactone and dimethyl sulfoxide, and the content of γ-valerolactone relative to the total amount of γ-valerolactone and dimethyl sulfoxide is 50 to 95 mass%. Claim 5 A resin composition according to claim 3 or claim 4, wherein the content of γ-valerolactone is 60 mass% or more with respect to the total mass of the solvent. Claim 6 A resin composition according to claim 3, further comprising dimethyl sulfoxide as the solvent. Claim 7 A resin composition according to claim 3 or claim 4, further comprising a polymerizable compound and a photopolymerization initiator. Claim 8 A resin composition used for forming an interlayer insulating film for a redistribution layer, in accordance with claim 3 or claim 4. Claim 9 A cured product formed by curing the resin composition described in claim 3 or claim 4. Claim 10 A laminate comprising two or more layers made of the cured material described in claim 9, and a metal layer between any one of the layers made of the cured material. Claim 11 A method for manufacturing a cured article, comprising a film-forming process of forming a film by applying the resin composition described in claim 3 or claim 4 onto a substrate. Claim 12 A method for manufacturing a cured article according to claim 11, comprising an exposure process for selectively exposing the film and a development process for developing the film using a developer to form a pattern. Claim 13 A method for manufacturing a cured product according to claim 11, comprising a heating process of heating the film at 50 to 450°C. Claim 14 A method for manufacturing a laminate comprising the method for manufacturing a cured product as described in claim 11. Claim 15 A method for manufacturing a semiconductor device comprising the method for manufacturing a cured product described in claim 11. Claim 16 A semiconductor device comprising the cured material described in claim 9.

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