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

Abstract

A resin composition, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the laminate, and a semiconductor device including the cured product or the laminate, the resin composition contains a solvent and at least one resin selected from the group consisting of polyimide precursors, polyimides, polyamideimide precursors, polyamideimides, and polyamides, and the contents of N-methylpyrrolidone and gamma-butyrolactone are each 0.1 mass% or less relative to the total mass of the resin composition.

Description

Technical Field

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

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

[0003] For example, polyimide is used in various applications due to its excellent heat resistance and insulation properties. The above-mentioned applications are not particularly limited, but if a semiconductor device for mounting is used as an example, it can be used as an insulating film, a sealing material, or a protective film. In addition, it can also be used as a base film, a cover layer, etc. of a flexible substrate.

[0004] For example, in the above-mentioned applications, polyimide is used in the form of a resin composition containing a polyimide precursor.

[0005] For example, such a resin composition is applied to a substrate by coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.

[0006] The polyimide precursor is cyclized by, for example, heating, and becomes a polyimide in a cured product.

[0007] The resin composition can be applied by a known coating method, etc., and therefore, it can be said that the resin composition has excellent manufacturing adaptability, such as high degree of freedom in designing the shape, size, and application position when applied. From the perspective of excellent manufacturing adaptability in addition to the high performance of polyimide, the expansion of industrial application of the resin composition is increasingly expected.

[0008] For example, Patent Document 1 describes a negative photosensitive resin composition, characterized in that it contains the following components: (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide and polyimide as polyimide precursors; (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 amount of the compounds in which n=1 to 5 among the compounds represented by the chemical formula (b1) in (B) is less than 0.01 parts by mass.

[0009] Previous technical literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2022-073737 Summary of the invention

[0012] Technical issues to be solved by the invention

[0013] The resin composition is required to have excellent stability during storage (stability over time). Specifically, for example, it is required that the viscosity of the composition does not easily change after being stored at room temperature for several weeks.

[0014] The object of the present invention is to provide a resin composition with excellent temporal stability, a cured product obtained by curing the above resin composition, a laminate comprising the above cured product, a method for manufacturing the cured product, a method for manufacturing a laminate, a method for manufacturing a semiconductor device including the method for manufacturing a laminate, and a semiconductor device comprising the above cured product or the above laminate.

[0015] Means for solving technical problems

[0016] Hereinafter, examples of representative embodiments of the present invention will be described.

[0017] <1> A resin composition comprising:

[0018] At least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polyamideimide precursor, a polyamideimide, and a polyamide; and

[0019] Solvents,

[0020] The content of each of N-methylpyrrolidone and γ-butyrolactone is 0.1% by mass or less relative to the total mass of the resin composition.

[0021] <2> according to <1> The resin composition contains γ-valerolactone as the solvent.

[0022] <3> A resin composition comprising:

[0023] At least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polyamideimide precursor, a polyamideimide, and a polyamide; and

[0024] γ-Valerolactone.

[0025] <4> according to <2> or <3> The resin composition, wherein

[0026] The content of the γ-valerolactone is 60% by mass or more based on the total mass of the solvent.

[0027] <5> according to <1> to <4> The resin composition described above further contains dimethyl sulfoxide as the solvent.

[0028] <6> according to <1> to <5> The resin composition described in any one of the above aspects further comprises a polymerizable compound and a photopolymerization initiator.

[0029] <7> according to <1> to <6> The resin composition described in any one of the above is used for forming an interlayer insulating film for a redistribution layer.

[0030] <8> A solidified material, which is <1> to <7> The resin composition described in any one of the above is cured.

[0031] <9> A laminate comprising two or more layers of <8> The layers are formed of the above-mentioned cured product, and a metal layer is included between any of the layers formed of the above-mentioned cured product.

[0032] <10> A method for producing a solidified product, comprising: <1> to <7> A film forming step of applying any one of the resin compositions to a substrate to form a film.

[0033] <11> according to <10> The method for producing the solidified material comprises:

[0034] An exposure step of selectively exposing the film; and

[0035] In the development step, the film is developed using a developer to form a pattern.

[0036] <12> according to <10> or <11> The method for producing the cured product comprises a heating step of heating the film at 50 to 450°C.

[0037] <13> A method for manufacturing a laminate, comprising: <10> to <12> The method for producing a cured product according to any one of the above.

[0038] <14> A method for manufacturing a semiconductor device, comprising: <10> to <12> The method for producing a cured product according to any one of the above.

[0039] <15> A semiconductor device comprising <8> The solidified material or <9> The laminated body.

[0040] Effects of the Invention

[0041] According to the present invention, there are provided a resin composition having excellent stability over time, a cured product obtained by curing the resin composition, a laminate comprising the cured product, a method for manufacturing the cured product, a method for manufacturing a laminate, a method for manufacturing a semiconductor device including the method for manufacturing a laminate, and a semiconductor device comprising the cured product or the laminate. DETAILED DESCRIPTION

[0042] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0043] In the present specification, a numerical range expressed using the symbol “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0044] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process can be achieved.

[0045] In the marking of groups (atomic groups) in this specification, the marking not indicating substitution and unsubstituted includes not only groups (atomic groups) without substitution but also groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0046] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include active light or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams.

[0047] In this specification, “(meth)acrylate” means both or either “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either “acrylic acid” and “methacrylic acid”, and “(meth)acryloyl” means both or either “acryloyl” and “methacryloyl”.

[0048] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0049] In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition. In addition, in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent relative to the total mass of the composition.

[0050] In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, for example, using HLC-8220GPC (manufactured by TOSOH CORPORATION), guard column HZ-L, TSKgel Super HZM-M, TSKgelSuper HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) are connected in series and used as tubing column, thus weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as eluent. Wherein, in the case where solubility is relatively low, in the case where THF is not suitable as elution liquid, NMP (N- methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specifically stated, detection in GPC measurement uses a UV ray (ultraviolet) detector having a wavelength of 254 nm.

[0051] In this specification, regarding the positional relationship of each layer constituting the laminate, when recorded as "up" or "down", other layers can be located on the upper side or lower side of the layer that becomes the benchmark in the multiple layers of interest. That is, the third layer or element can also be sandwiched between the layer that becomes the benchmark and the above-mentioned other layers, and the layer that becomes the benchmark does not need to contact the above-mentioned other layers. Unless otherwise specified, the direction of the substrate stacking layer is referred to as "up", or, when there is a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the setting of this up and down direction is for the convenience of explaining this specification, and in a practical manner, the "up" direction in this specification can also be different from the vertical upward direction.

[0052] In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to the component as each component contained 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 the component.

[0053] In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0054] In the present specification, a combination of preferred embodiments is a more preferred embodiment.

[0055] (Resin composition)

[0056] The resin composition of the first embodiment of the present invention contains: 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 content of each of N-methylpyrrolidone (also recorded as "N-methyl-2-pyrrolidone", "NMP") and γ-butyrolactone (also recorded as "GBL") is 0.1% by mass or less relative to the total mass of the resin composition.

[0057] The resin composition of the second aspect of the present invention contains: at least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polyamideimide precursor, a polyamideimide, and a polyamide; and γ-valerolactone (GVL).

[0058] In the present invention, unless otherwise specified, the resin composition of the first embodiment and the resin composition of the second embodiment are also collectively referred to as a "resin composition".

[0059] The resin composition of the present invention is preferably used to form a photosensitive film (subject to exposure and development), and is preferably used to form a film (subject to exposure and development using a developer containing an organic solvent).

[0060] The resin composition of the present invention can be used to form, for example, an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.

[0061] Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative-tone development.

[0062] In the present invention, among exposure and development, negative-tone development refers to development in which non-exposed areas are removed by development, and positive-tone development refers to development in which exposed areas are removed by development.

[0063] As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, and the developer and the development method described in the development step can be used.

[0064] The resin composition of the present invention is excellent in stability over time.

[0065] The mechanism by which the above effects are obtained is not clear, but is presumed as follows.

[0066] Since NMP and GBL have high polarity, their solubility in resin is also high, and compositions formed using these solvents tend to be easy to have low viscosity. From the above-mentioned changes in low viscosity, it is believed that since the polymer chain of the resin is in a loosened state or an unagglomerated state in the solution, when a part of the main chain (amide bond, etc.) of the resin in the composition is decomposed, it is more susceptible to the decomposition attack of the main chain by the alkaline decomposition product (decomposition product with amino group) as the decomposition product of the resin. In this way, in a resin composition containing solvents such as NMP and GBL, the decomposition reaction chain is promoted, so it is presumed that the time stability of the resin composition containing these solvents is low.

[0067] In the present invention, it is presumed that by adopting a structure in which the contents of NMP and GBL are low or a structure in which GVL is contained as a solvent, the decomposition chain of the above-mentioned resin is suppressed, and thus the temporal stability of the composition is improved.

[0068] Furthermore, in particular, when the resin composition contains a thermal base generator, the decomposition of the thermal base generator is also promoted in a highly polar solvent, and the resin may be decomposed by the base generated from the thermal base generator. It is believed that the resin composition of the present invention can also suppress the decomposition of the resin caused by the thermal base generator by adopting the above-mentioned structure.

[0069] Furthermore, for example, when the composition contains an organic titanium compound, the composition may thicken due to the formation of titanoxane bonds. It has been found that such thickening is also likely to occur in highly polar solvents such as NMP and GBL, but such thickening is suppressed by using GVL. It is presumed that the reason for this is that the organic titanium compound is highly stable and difficult to decompose in a low polar solvent.

[0070] In addition, it has been found that when a ketone oxime initiator (such as Irgacure OXE01 described below) or an oxime initiator (such as Irgacure OXE02 described below) is used as a photopolymerization initiator, these initiators are also hydrolyzed in the presence of water and a base. Depending on the structure of the resin composition of the present invention, the decomposition of these initiators may be suppressed, and effects such as an increase in exposure sensitivity may be obtained.

[0071] Here, Patent Document 1 does not describe a composition having such a structure as described above as a solvent.

[0072] Hereinafter, the components contained in the composition of the present invention will be described in detail.

[0073] <At least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polyamideimide precursor, a polyamideimide, and a polyamide>

[0074] The resin composition of the present invention contains at least one resin (hereinafter also referred to as “specific resin”) selected from the group consisting of a polyimide precursor, a polyimide, a polyamideimide precursor, a polyamideimide, and a polyamide.

[0075] The polyimide precursor is a resin that changes its chemical structure due to external stimulation to become a polyimide, preferably a resin that changes its chemical structure due to heat to become a polyimide, and more preferably a resin that forms a ring structure by a ring-closing reaction due to heat to become a polyimide.

[0076] Polyimide refers to a resin having a plurality of imide bonds (*-C(=O)-N(-*)-C(=O)-*) in the main chain, and is preferably a resin having a plurality of repeating units having imide bonds.

[0077] The polyamideimide precursor is a resin that changes its chemical structure due to external stimulation to become polyamideimide, preferably a resin that changes its chemical structure due to heat to become polyamideimide, and more preferably a resin that forms a ring structure by a ring-closing reaction due to heat to become polyamideimide.

[0078] Polyamide-imide refers to a polymer having multiple imide bonds (*-C(=O)-N(-*)-C(=O)-*) and amide bonds (-NR N The resin containing R-C(=O)-) is preferably a resin containing a plurality of repeating units having an imide bond and an amide bond. N represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, further preferably a hydrogen atom.

[0079] Polyamide refers to a polymer with multiple amide bonds (-NR N The resin containing R-C(=O)-) is preferably a resin containing a plurality of repeating units having an amide bond. N As mentioned above.

[0080] In the present invention, the "main chain" refers to the relatively longest connecting chain in the resin molecule, and the "side chain" refers to the connecting chains other than the main chain.

[0081] Among these, the resin composition preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.

[0082] The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0083] When the specific resin has a free radical polymerizable group, the resin composition of the present invention preferably contains a free radical polymerization initiator, more preferably contains a free radical polymerization initiator and a free radical crosslinking agent. In addition, a sensitizer can be contained as needed. This resin composition, for example, forms a negative photosensitive film.

[0084] Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group.

[0085] When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. This resin composition can be used to form, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film.

[0086] 〔Polyimide precursor〕

[0087] The polyimide precursor used in the present invention is not particularly limited in its type and the like, but preferably contains a repeating unit represented by the following formula (2).

[0088] [Chemical formula 1]

[0089]

[0090] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NR z -, R 111 Represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group.

[0091] A in formula (2) 1 and A 2 Each independently represents an oxygen atom or -NR z -, preferably an oxygen atom.

[0092] R z represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.

[0093] R in formula (2) 111represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group, preferably a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the cyclic hydrocarbon group of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. As R in formula (2) 111 Examples include groups represented by -Ar- and -Ar-L-Ar-, preferably groups represented by -Ar-L-Ar-. Ar is independently an aromatic group, L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges are as described above.

[0094] R 111 It is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cycloaliphatic or aromatic diamines. The diamine may be used alone or in combination of two or more.

[0095] Specifically, R 111 Preferred are diamines containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably diamines containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the cyclic hydrocarbon group of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. Examples of the group containing an aromatic group include the following groups.

[0096] [Chemical formula 2]

[0097]

[0098] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO- or a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S- or -SO2-, further preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0099] In the formula, * indicates the bonding site with other structures.

[0100] Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane;

[0101] 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;

[0102] m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2, 2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4' -dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, At least one diamine selected from 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine or 4,4'-diaminoquaterphenyl.

[0103] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0104] Furthermore, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 can also be preferably used.

[0105] From the viewpoint of the flexibility of the obtained organic film, R 111 Preferably, it is represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- or -SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.

[0106] Furthermore, from the perspective of i-ray transmittance, R 111 Preferred are divalent organic groups represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, divalent organic groups represented by formula (61) are more preferred.

[0107] Formula (51)

[0108] [Chemical formula 3]

[0109]

[0110] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2).

[0111] As R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0112] [Chemical formula 4]

[0113]

[0114] In formula (61), R 58 and R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2).

[0115] Examples of the diamine that imparts the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

[0116] R in formula (2) 115 The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

[0117] In formula (5) or (6), * each independently represents a bonding site with another structure.

[0118] [Chemical formula 5]

[0119]

[0120] In formula (5), R 112It is a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO2-, further preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0121] Specifically, R 115 Examples include a tetracarboxylic acid residue remaining after the anhydride group is removed from tetracarboxylic dianhydride. 115 The polyimide precursor may contain only one tetracarboxylic dianhydride residue or two or more tetracarboxylic dianhydride residues.

[0122] It is preferable that tetracarboxylic dianhydride is represented by the following formula (O).

[0123] [Chemical formula 6]

[0124]

[0125] In formula (O), R 115 Represents a tetravalent organic group. 115 The meaning of is the same as R in formula (2) 115 The meanings are the same, and the preferred ranges are also the same.

[0126] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. , 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0127] Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be mentioned as preferred examples.

[0128] In formula (2), R 111 and R 115 At least one of R may have an OH group. 111 , for example, residues of bisaminophenol derivatives can be mentioned.

[0129] R in formula (2) 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, it is preferred to contain a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkyleneoxy group. 113 and R 114 At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group. 113 and R 114At least one of them contains more than two polymerizable groups. As a polymerizable group, it is a group that can undergo a crosslinking reaction by the action of heat, free radicals, etc., preferably a free radical polymerizable group. As a specific example of a polymerizable group, a group with an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group can be cited. As the free radical polymerizable group possessed by the polyimide precursor, a group with an ethylenically unsaturated bond is preferably present.

[0130] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, a group represented by the following formula (III), and the like. Preferably, the group represented by the following formula (III) is included.

[0131] [Chemical formula 7]

[0132]

[0133] In formula (III), R 200 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0134] In formula (III), * represents a bonding site with other structures.

[0135] In formula (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group or a polyalkyleneoxy group.

[0136] Preferred R 201 Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkyleneoxy groups. Alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkyleneoxy groups are more preferred. Alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are further preferred.

[0137] In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.

[0138] When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, an alternating arrangement, or the like.

[0139] The number of carbon atoms of the alkylene group (including the carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0140] Furthermore, the above-mentioned alkylene group may have a substituent, and preferred substituents include an alkyl group, an aryl group, a halogen atom, and the like.

[0141] Furthermore, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.

[0142] As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, preferably a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is polyethyleneoxy or polypropyleneoxy, and further preferably polyethyleneoxy. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternation. The preferred form of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

[0143] In formula (2), when R 113 When it is a hydrogen atom or R 114 When it is a hydrogen atom, the polyimide precursor can form a salt pair with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0144] In formula (2), R 113 and R 114 At least one of them may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but is preferably an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc., and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.

[0145] Specific examples of the acid-decomposable group include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, trimethylsilyl ether, etc. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0146] The polyimide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0147] Furthermore, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, as the diamine, there can be mentioned an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0148] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By containing a repeating unit represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further increased.

[0149] Formula (2-A)

[0150] [Chemical formula 8]

[0151]

[0152] In formula (2-A), A 1 and A 2 represents oxygen atom, R 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, and preferably both of them are groups containing a polymerizable group.

[0153] In the present specification, a structure bonded to the side of a ring structure means that any hydrogen atom among hydrogen atoms directly bonded to a ring-constituting atom of the ring structure can be substituted.

[0154] In the present specification, direct bonding means bonding without via a linking group.

[0155] A 1 , A 2 , R 111 , R 113 and R 114 The meanings of are independent of A in formula (2) 1 , A 2 , R 111 , R 113 and R 114 has the same meaning and the preferred range is also the same. 112 The meaning of is the same as R in formula (5)112 The meanings are the same, and the preferred ranges are also the same.

[0156] The polyimide precursor may contain one or more repeating units represented by formula (2). Furthermore, the polyimide precursor may contain structural isomers of the repeating units represented by formula (2). In addition to the repeating units represented by the above formula (2), the polyimide precursor may also contain other types of repeating units.

[0157] As one embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by formula (2) can be cited as 50 mol% or more of the total repeating units. The above-mentioned total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyimide except the terminal can be repeating units represented by formula (2).

[0158] The number average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000.

[0159] The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0160] In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[0161] Furthermore, when the resin composition contains a plurality of polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyimide precursor are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion degree calculated using the plurality of polyimide precursors as one resin are within the above ranges, respectively.

[0162] 〔Polyimide〕

[0163] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly composed of an organic solvent.

[0164] In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23° C., preferably 0.5 g or more, and more preferably 1.0 g or more from the viewpoint of pattern formation. The upper limit of the above-mentioned dissolution amount is not particularly limited, but is preferably 100 g or less.

[0165] From the viewpoint of film strength and insulation properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

[0166] -Fluorine atom-

[0167] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has fluorine atoms.

[0168] The fluorine atom is preferably contained in R in the repeating unit represented by the formula (4) described later. 132 or R in the repeating unit represented by the formula (4) described later 131 Among them, R contained in the repeating unit represented by the formula (4) described later is more preferably 132 or R in the repeating unit represented by the formula (4) described later 131 as a fluorinated alkyl group.

[0169] The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0170] -Silicon Atoms-

[0171] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a silicon atom.

[0172] The silicon atom is preferably contained in R in the repeating unit represented by the formula (4) described later. 131 Among them, R contained in the repeating unit represented by the formula (4) described later is more preferably 131 Here, it is used as the organic modified (poly)siloxane structure described later.

[0173] The silicon atom or the organo-modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.

[0174] The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0175] -Ethylenically unsaturated bond-

[0176] From the viewpoint of film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0177] The polyimide may have an ethylenically unsaturated bond at a main chain terminal or on a side chain, but preferably has an ethylenically unsaturated bond on a side chain.

[0178] The ethylenically unsaturated bond preferably has radical polymerizability.

[0179] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described later. 132 or R 131 More preferably, it is included in R 132 or R 131 As a group having an ethylenically unsaturated bond.

[0180] Among these, the ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described later. 131 More preferably, it is included in R 131 As a group having an ethylenically unsaturated bond.

[0181] Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group which may be substituted, a (meth)acryloyl group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0182] [Chemical formula 9]

[0183]

[0184] In formula (IV), R 20 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0185] In formula (IV), R 21 It represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3, and the number of repetitions of the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3) or a group formed by combining two or more of them.

[0186] The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, cyclic, or combinations thereof.

[0187] The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0188] Among these, R 21It is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).

[0189] [Chemical formula 10]

[0190]

[0191] In formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these groups, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bond with R in formula (IV). 21 The bonding site of the bonded oxygen atom.

[0192] In formulae (R1) to (R3), the preferred embodiment of L being an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms is the same as that of R in formula (IV). 21 The preferred embodiments are the same as those of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.

[0193] In formula (R1), X is preferably an oxygen atom.

[0194] In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.

[0195] The structure represented by the formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanateethyl methacrylate).

[0196] The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).

[0197] The structure represented by the formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

[0198] In formula (IV), * represents a bonding site to other structures, and * is preferably a bonding site to the main chain of the polyimide.

[0199] The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g.

[0200] -Polymerizable groups other than groups having ethylenically unsaturated bonds-

[0201] The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.

[0202] Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.

[0203] The polymerizable group other than the group having an ethylenically unsaturated bond is preferably contained in R 131 middle.

[0204] The amount of the polymerizable groups other than the group having an ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g, based on the total mass of the polyimide.

[0205] -Polarity conversion group-

[0206] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide and R in the above formula (2) 113 and R 114 The acid-decomposable groups described above are the same and the preferred embodiments are also the same.

[0207] The polarity conversion group is, for example, contained in R in the repeating unit represented by the formula (4) described later. 131 , R 132 , the end of polyimide, etc.

[0208] -Acid value-

[0209] When the polyimide is subjected to alkali development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more from the viewpoint of improving developability.

[0210] 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.

[0211] When the polyimide is subjected to development using a developer containing an organic solvent as a main component (eg, "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and further preferably 5 to 20 mgKOH / g.

[0212] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0213] As the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferred, and an acid group having a pKa of 3 to 8 is more preferred, from the viewpoint of achieving both storage stability and developability.

[0214] pKa is a value expressed by the negative common logarithm pKa of the equilibrium constant Ka in consideration of the dissociation reaction of releasing hydrogen ions from an acid. In this specification, unless otherwise specified, pKa is set to a calculated value based on ACD / ChemSketch (registered trademark). pKa can also refer to the value published in the "Fifth Revised Edition of the Chemical Handbook Basic Edition" compiled by the Chemical Society of Japan.

[0215] When the acid group is a polyacid such as phosphoric acid, the pKa is the first dissociation constant.

[0216] As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0217] -Phenolic hydroxyl group-

[0218] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0219] The polyimide may have a phenolic hydroxyl group at a main chain terminal or may have a phenolic hydroxyl group on a side chain.

[0220] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R 131 middle.

[0221] The amount of the phenolic hydroxyl group relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0222] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).

[0223] [Chemical formula 11]

[0224]

[0225] In formula (4), R 131 Represents a divalent organic group, R 132 represents a tetravalent organic group.

[0226] When there is a polymerizable group, the polymerizable group may be located at R 131 and R 132 At least one of them may be located at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0227] Formula (4-1)

[0228] [Chemical formula 12]

[0229]

[0230] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4).

[0231] Formula (4-2)

[0232] [Chemical formula 13]

[0233]

[0234] R 134 and R 135 At least one of them is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as those in formula (4).

[0235] Examples of the polymerizable group include a group containing the above-mentioned ethylenically unsaturated bond or a crosslinkable group other than the group having the above-mentioned ethylenically unsaturated bond.

[0236] R 131 The divalent organic group includes the following: 111 The same organic group has the same preferred range.

[0237] As R 131 , and the diamine residue remaining after removing the amino group of the diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, R in the formula (2) of the polyimide precursor can be cited. 111 Example.

[0238] From the viewpoint of more effectively suppressing the warping during calcination, R 131 Preferably, the diamine residue has at least two alkylene glycol units in the main chain. More preferably, the diamine residue contains two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule. Still more preferably, the diamine residue contains no aromatic ring.

[0239] Examples of the diamine containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (these are trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, and 1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, but are not limited to these.

[0240] R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include 115 The same organic group has the same preferred range.

[0241] For example, as R 115 The four connectors of the exemplified tetravalent organic group are bonded to the four -C(=O)- moieties in the above formula (4) to form a condensed ring.

[0242] R 132 Examples thereof include tetracarboxylic acid residues remaining after the anhydride groups are removed from tetracarboxylic dianhydride. Specific examples thereof include R in the formula (2) of the polyimide precursor. 115 From the perspective of the strength of the organic film, R 132 An aromatic diamine residue having 1 to 4 aromatic rings is preferred.

[0243] R is also preferred 131 and R 132 More specifically, at least one of R 131 , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) can be mentioned as preferred examples, and R 132 As more preferred examples, the above-mentioned (DAA-1) to (DAA-5) can be cited.

[0244] The polyimide also preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0245] In order to improve the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

[0246] In order to improve the storage stability of the resin composition, the main chain terminal of the polyimide is preferably blocked with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, or a monoactive ester compound. Among these, monoamines are more preferably used, and preferred compounds of the monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 2-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

[0247] -Imidization rate (ring closure rate)-

[0248] From the viewpoint of film strength, insulation properties, etc. of the obtained organic film, the imidization ratio (also referred to as “ring closure ratio”) of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0249] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0250] The imidization ratio can be measured, for example, by the following method.

[0251] Measure the infrared absorption spectrum of polyimide and find the absorption peak at 1377 cm-1 derived from the imide structure. -1 Next, after the polyimide was heat treated at 350°C for 1 hour, the infrared absorption spectrum was measured again to obtain the peak intensity P1 at 1377 cm -1 The imidization ratio of the polyimide can be determined from the following formula using the obtained peak intensities P1 and P2.

[0252] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0253] Polyimide can contain all repeating units R 131 and R 132 The repeating unit represented by the above formula (4) may contain two or more R 131 and R 132 The polyimide may contain repeating units represented by the above formula (4) in addition to the repeating units represented by the above formula (4). As other types of repeating units, for example, repeating units represented by the above formula (2) can be cited.

[0254] Polyimide can be synthesized by, for example, the following methods: a method of reacting tetracarboxylic dianhydride with diamine (a portion of which is substituted with a capping agent that is a monoamine) at low temperature; a method of reacting tetracarboxylic dianhydride (a portion of which is substituted with a capping agent that is an acid anhydride, a monoacyl chloride compound, or a monoactive ester compound) with diamine at low temperature; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting the diester with a diamine (a portion of which is substituted with a capping agent that is a monoamine) in the presence of a condensation agent; a method of obtaining a polyimide precursor by a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, then chlorinating the remaining dicarboxylic acid, and reacting the diester with a diamine (a portion of which is substituted with a capping agent that is a monoamine), and completely imidizing the diester using a known imidization reaction method; or a method of stopping the imidization reaction midway and introducing a portion of an imide structure; and a method of introducing a portion of an imide structure by mixing a completely imidized polymer and the polyimide precursor. Furthermore, other known methods for synthesizing polyimide can also be applied.

[0255] The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.

[0256] The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000.

[0257] The molecular weight dispersion of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0258] When the resin composition contains multiple polyimides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyimide are within the above ranges. It is also preferred that the weight average molecular weight, number average molecular weight and dispersion degree calculated for the multiple polyimides as one resin are within the above ranges.

[0259] 〔Polyamide-imide precursor〕

[0260] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).

[0261] [Chemical formula 14]

[0262]

[0263] In the formula (PAI-2), R 117 Represents a trivalent organic group, R 111 Represents a divalent organic group, A 2 represents an oxygen atom or -NH-, R 113 represents a hydrogen atom or a monovalent organic group.

[0264] In the formula (PAI-2), R 117 Examples include a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked via a single bond or a linking group. Preferably, it is a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0265] As the above-mentioned connecting group, preferred are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these, more preferred are -O-, -S-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these.

[0266] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0267] As the above-mentioned haloalkylene group, a haloalkylene group having 1 to 20 carbon atoms is preferred, a haloalkylene group having 1 to 10 carbon atoms is more preferred, and a haloalkylene group having 1 to 4 carbon atoms is more preferred. Furthermore, as the halogen atom in the above-mentioned haloalkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred. The above-mentioned haloalkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by halogen atoms, but preferably all hydrogen atoms are substituted by halogen atoms. As examples of preferred haloalkylene groups, (ditrifluoromethyl)methylene and the like can be mentioned.

[0268] The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0269] And, R 117 It is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the halogenation, chlorination is preferred.

[0270] In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound.

[0271] Two of the three carboxyl groups of the tricarboxylic acid compound may be converted to anhydride.

[0272] Examples of the tricarboxylic acid compound which may be halogenated and is used in the production of the polyamideimide precursor include branched aliphatic, cycloaliphatic or aromatic tricarboxylic acid compounds.

[0273] These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0274] Specifically, as the tricarboxylic acid compound, a tricarboxylic acid compound containing a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these groups are combined via a single bond or a linking group is preferred, and a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group is more preferred.

[0275] 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, and 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 a phenylene group.

[0276] These compounds may be compounds in which two carboxyl groups are anhydrified (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride chloride).

[0277] In the formula (PAI-2), R 111 , A 2 , R 113 The meanings of are respectively the same as those of R in the above formula (2) 111 , A 2 , R 113 The meanings are the same and the preferred aspects are also the same.

[0278] The polyamideimide precursor may also contain other repeating units.

[0279] Examples of other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).

[0280] [Chemical formula 15]

[0281]

[0282] In the formula (PAI-1), R 116 Represents a divalent organic group, R 111 It represents a divalent organic group.

[0283] In the formula (PAI-1), R 116 Examples include a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked via a single bond or a linking group. Preferably, it is a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0284] As the above-mentioned connecting group, preferred are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, halogenated alkylene, arylene or a connecting group formed by bonding two or more of these, and more preferred are -0-, -S-, alkylene, halogenated alkylene, arylene or a connecting group formed by bonding two or more of these.

[0285] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0286] As the above-mentioned haloalkylene group, a haloalkylene group having 1 to 20 carbon atoms is preferred, a haloalkylene group having 1 to 10 carbon atoms is more preferred, and a haloalkylene group having 1 to 4 carbon atoms is more preferred. Furthermore, as the halogen atom in the above-mentioned haloalkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred. The above-mentioned haloalkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by halogen atoms, but preferably all hydrogen atoms are substituted by halogen atoms. As examples of preferred haloalkylene groups, (ditrifluoromethyl)methylene and the like can be mentioned.

[0287] The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0288] And, R 116 Preferably, it is derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.

[0289] In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound.

[0290] The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

[0291] Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound which may be halogenated and is used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds.

[0292] These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0293] Specifically, as the dicarboxylic acid compound or dicarboxylic acid dihalide compound, a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group is preferred, and a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferred.

[0294] Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecanoic acid, Fluorosebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, henodecanedioic acid, dohenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyldiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0295] Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxyl groups in the above-mentioned specific examples of the dicarboxylic acid compound are halogenated.

[0296] In the formula (PAI-1), R 111 The meaning of is the same as R in the above formula (2) 111 The meanings are the same and the preferred aspects are also the same.

[0297] Furthermore, the polyamide-imide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0298] Furthermore, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, as the diamine component, there can be mentioned an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0299] As one embodiment of the polyamideimide precursor in the present invention, there can be mentioned a method containing a repeating unit represented by formula (PAI-2), a repeating unit represented by formula (PAI-1), and a repeating unit represented by formula (2). The total content of the above repeating units is preferably 50 mol% or more of the total repeating units, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited and is 100 mol% or less. All repeating units in the polyamideimide precursor except the terminal can be any one of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2).

[0300] Furthermore, as another embodiment of the polyamideimide precursor of the present invention, a method containing a repeating unit represented by formula (PAI-2) and a repeating unit represented by formula (PAI-1) can be cited. The total content of the above repeating units is preferably 50 mol% or more of the total repeating units, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited and is 100 mol% or less. All repeating units in the polyamideimide precursor except the terminal can be any one of the repeating units represented by formula (PAI-2) or the repeating units represented by formula (PAI-1).

[0301] The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0302] The molecular weight dispersion of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyamideimide precursor is not particularly specified, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less. When the resin composition contains a plurality of polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one polyamideimide precursor are within the above range. In addition, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated using the plurality of polyamideimide precursors as one resin are within the above range, respectively.

[0303] 〔Polyamide-imide〕

[0304] The polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer mainly composed of an organic solvent.

[0305] In this specification, the alkali-soluble polyamide-imide means that in 100 g of a 2.38 mass % tetramethylammonium aqueous solution, 0.1 g or more of the polyamide-imide is dissolved at 23° C., and from the viewpoint of pattern formation, 0.5 g or more of the polyamide-imide is preferably dissolved, and 1.0 g or more of the polyamide-imide is more preferably dissolved. The upper limit of the above-mentioned dissolution amount is not particularly limited, but is preferably 100 g or less.

[0306] Furthermore, from the viewpoint of film strength and insulation properties of the obtained organic film, the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.

[0307] -Fluorine atom-

[0308] From the viewpoint of the film strength of the obtained organic film, the polyamideimide preferably has fluorine atoms.

[0309] The fluorine atom is preferably contained in R in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 Among them, R contained in the repeating unit represented by the formula (PAI-3) described later as a fluorinated alkyl group is more preferably 117 or R 111 middle.

[0310] The amount of fluorine atoms relative to the total mass of the polyamideimide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0311] -Ethylenically unsaturated bond-

[0312] From the viewpoint of the film strength of the obtained organic film, the polyamideimide may have an ethylenically unsaturated bond.

[0313] The polyamideimide may have an ethylenically unsaturated bond at a main chain terminal or on a side chain, but preferably has an ethylenically unsaturated bond on a side chain.

[0314] The ethylenically unsaturated bond preferably has radical polymerizability.

[0315] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 Among them, R in the repeating unit represented by the formula (PAI-3) described later is more preferably 117 or R 111 middle.

[0316] Preferred embodiments of the group having an ethylenically unsaturated bond are the same as preferred embodiments of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

[0317] The amount of ethylenically unsaturated bonds relative to the total mass of the polyamide-imide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0318] -Polymerizable groups other than ethylenically unsaturated bonds-

[0319] The polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.

[0320] Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyamideimide include the same polymerizable groups other than the ethylenically unsaturated bond in the above-mentioned polyimide.

[0321] The polymerizable group other than the ethylenically unsaturated bond is preferably contained in, for example, R 111 middle.

[0322] The amount of the polymerizable groups other than the ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[0323] -Polarity conversion group-

[0324] The polyamideimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamideimide and R in the above formula (2) 113 and R 114 The acid-decomposable groups described above are the same and the preferred embodiments are also the same.

[0325] -Acid value-

[0326] When the polyamideimide is subjected to alkali development, the acid value of the polyamideimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more from the viewpoint of improving developability.

[0327] Furthermore, the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0328] When the polyamideimide is subjected to development using a developer containing an organic solvent as a main component (eg, "solvent development"), the acid value of the polyamideimide is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g.

[0329] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0330] Furthermore, examples of the acid group contained in the polyamide-imide include the same groups as the acid groups in the above-mentioned polyimide, and preferred aspects are also the same.

[0331] -Phenolic hydroxyl group-

[0332] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyamideimide preferably has a phenolic hydroxyl group.

[0333] The polyamideimide may have a phenolic hydroxyl group at a main chain terminal or may have a phenolic hydroxyl group on a side chain.

[0334] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 middle.

[0335] The amount of the phenolic hydroxyl group relative to the total mass of the polyamide-imide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0336] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but preferably contains a repeating unit represented by the following formula (PAI-3).

[0337] [Chemical formula 16]

[0338]

[0339] In the formula (PAI-3), R 111 and R 117 The meanings are the same as those of R in formula (PAI-2) 111 and R 117 The meanings are the same and the preferred aspects are also the same.

[0340] When there is a polymerizable group, the polymerizable group may be located at R 111 and R 117 At least one of them may be located at the end of the polyamideimide.

[0341] In order to improve the storage stability of the resin composition, the main chain ends of the polyamide-imide are preferably capped with a capping agent such as a monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound. The preferred embodiment of the capping agent is the same as the preferred embodiment of the capping agent in the polyimide.

[0342] -Imidization rate (ring closure rate)-

[0343] From the viewpoint of film strength and insulation properties of the obtained organic film, the imidization ratio (also referred to as "ring closure ratio") of the polyamideimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0344] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0345] The imidization ratio is measured by the same method as the ring closure ratio of the polyimide.

[0346] The polyamide-imide may contain R 111 and R 117 The repeating unit represented by the above formula (PAI-3) may contain two or more R 111 and R 117 The polyamide-imide may contain repeating units represented by the above formula (PAI-3) in combination with different repeating units. In addition to the repeating units represented by the above formula (PAI-3), the polyamide-imide may also contain other types of repeating units. Examples of other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0347] Polyamideimide can be synthesized, for example, by a method in which a polyamideimide precursor is obtained by a known method and completely imidized using a known imidization reaction method, or by a method in which the imidization reaction is stopped during the process and a part of the imide structure is introduced, or by a method in which a part of the imide structure is introduced by mixing a completely imidized polymer with the polyamideimide precursor.

[0348] The weight average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more.

[0349] Furthermore, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0350] The molecular weight dispersion of the amide polyimide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyamide imide is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0351] Furthermore, when the resin composition contains a plurality of polyamide-imides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyamide-imide are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion degree calculated using the plurality of polyamide-imides as one resin are within the above ranges, respectively.

[0352] 〔Polyamide〕

[0353] The polyamide preferably contains a repeating unit represented by the above formula (PAI-1).

[0354] Preferred embodiments of the repeating unit represented by the formula (PAI-1) contained in the polyamide are the same as preferred embodiments of the repeating unit represented by the formula (PAI-1) contained in the polyamideimide precursor.

[0355] Furthermore, the polyamide also preferably contains a repeating unit represented by the following formula (PA-1).

[0356] [Chemical formula 17]

[0357]

[0358] In formula (PA-1), R 118 is a trivalent organic group, R 119 is a divalent organic group, R 120 represents a hydrogen atom or a monovalent organic group.

[0359] In the formula (PA-1), R 118 , which may be the same as R in the above formula (PAI-2) 117 The same groups. In addition, the following structures can be particularly preferably mentioned. In the following structures, * represents the bonding sites to the two carboxyl groups and the nitrogen atom in the formula (PA-1).

[0360] [Chemical formula 18]

[0361]

[0362] In the formula (PA-1), R119 , which may be the same as R in the above formula (PAI-2) 111 The same group. In addition, the following structure can be particularly preferably cited. In the following structure, * represents the bonding site with the two nitrogen atoms in formula (PA-1). In addition, the hydrogen atom in the ring structure in the following structure can be substituted. As the substituent, an alkyl group (preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group), a hydroxyl group, etc. can be cited.

[0363] [Chemical formula 19]

[0364]

[0365] In the above structure, X 1 ~X 8 Each independently represents a single bond, -O-, -C(=O)-, -S(=O)2-, -CH2-, -C(CH3)2-, -C(CF3)2-, -C(CH3)(Ph)- or 1,1-cyclohexanediyl. Furthermore, Ph represents a phenyl group.

[0366] X 2 , X 3 , X 4 , X 5 , X 6 and X 8 Preferred is -O-.

[0367] X 7 Preferred is a single bond, -O-, -S(=O)2-, -C(CH3)2- or -C(CF3)2-.

[0368] And, R 119 The following structure is also preferred. In the following structure, R P1 Each independently represents a single bond or an alkylene group, and * represents a bonding site to two nitrogen atoms in formula (PA-1). P1 Each independently represents a single bond or an alkylene group having 2 to 6 carbon atoms. In addition, the hydrogen atoms in the ring structure in the following structure may be substituted. As the substituent, an alkyl group (preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group) and the like can be mentioned.

[0369] [Chemical formula 20]

[0370]

[0371] And, R 119 The following structure is also preferred. In the following structure, R P2 Each independently represents an alkylene group, R P3 Each independently represents an alkylene group, n1 represents an integer of 1 to 10, and RP4 represents an alkylene group, R P5 Each independently represents an alkylene group, R R6 Each independently represents an alkyl group or a phenyl group, n2 represents an integer of 1 to 40, and * represents a bonding site to two nitrogen atoms in the formula (PA-1).

[0372] R P2 Each independently is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 2 to 12 carbon atoms.

[0373] R P3 Each independently is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an ethylene group or a propylene group, and still more preferably an ethylene group.

[0374] n1 is preferably an integer of 1-5, more preferably an integer of 1-3.

[0375] R P4 Each independently is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an ethylene group or a propylene group, and still more preferably an ethylene group.

[0376] R P5 Each independently is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, further preferably an ethylene group, a propylene group or a trimethylene group, and particularly preferably a trimethylene group.

[0377] R P6 Each independently thereof is preferably 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 still more preferably a methyl group or a phenyl group.

[0378] More preferably, n2 is an integer of 1-20.

[0379] [Chemical formula 21]

[0380]

[0381] In formula (PA-1), R 120 It is preferably a monovalent organic group, more preferably a group containing a radical polymerizable group, and still more preferably a group represented by the following formula (PR-1).

[0382] As R 120 The free radical polymerizable group contained therein is preferably a group having an ethylenically unsaturated bond, more preferably a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), a (meth)acrylamide group or a (meth)acryloyloxy group, further preferably a vinylphenyl group, a (meth)acrylamide group or a (meth)acryloyloxy group.

[0383] [Chemical formula 22]

[0384]

[0385] In formula (PR-1), R P represents a group having a radical polymerizable group, and * represents a bonding site to the nitrogen atom in formula (PA-1).

[0386] In order to improve the storage stability of the resin composition, the main chain ends of the polyamide are preferably capped with a capping agent such as a monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound. The preferred embodiment of the capping agent is the same as the preferred embodiment of the capping agent in the polyimide.

[0387] Polyamides may contain R 118 , R 119 and R 120 The repeating unit represented by the above formula (PA-1) may contain two or more R 118 , R 119 and R 120 The polyamide may contain repeating units represented by the above formula (PA-1) in different combinations. In addition to the repeating units represented by the above formula (PA-1), the polyamide may also contain other types of repeating units. Examples of other types of repeating units include repeating units represented by the above formula (PAI-1).

[0388] The polyamide is synthesized, for example, by the following method, but the synthesis method is not limited to this.

[0389] A divalent carboxylic acid substituted with an amino group is reacted with a compound reactive with an amino group to obtain a compound in which the amino group in the divalent carboxylic acid is blocked with an organic group (preferably a group having a radical polymerizable group) (hereinafter also referred to as a "blocked product").

[0390] Examples of the compound that reacts with the amino group include acid chlorides, isocyanates, epoxy compounds, etc. That is, by using these compounds having a radical polymerizable group as the compound that reacts with the amino group, a terminal-capped product having a radical polymerizable group can be obtained.

[0391] Then, polyamide can be obtained by polycondensing the above-mentioned sealant with diamine. As diamine, R in the above-mentioned formula (PA-1) can be used. 119 A compound having amino groups bonded to both ends.

[0392] The weight average molecular weight (Mw) of the polyamide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more.

[0393] Furthermore, the number average molecular weight (Mn) of the polyamide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0394] The molecular weight dispersion of polyamide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of polyamide is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0395] Furthermore, when the resin composition contains multiple polyamides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersity of at least one polyamide are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersity calculated using the multiple polyamides as one resin are within the above ranges.

[0396] [Method for producing polyimide precursor, etc.]

[0397] The polyimide precursor can be obtained, for example, by the following methods: a method of reacting tetracarboxylic dianhydride with diamine at low temperature, a method of reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamic acid and esterifying it with a condensing agent or an alkylating agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting it in the presence of a diamine and a condensing agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine, etc. Among the above production methods, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine is more preferred.

[0398] Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N′-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0399] Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate and the like.

[0400] Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.

[0401] In the method for producing a polyimide precursor, etc., it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds.

[0402] The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.

[0403] In the method for producing a polyimide precursor, etc., it is preferred to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.

[0404] The basic compound can be appropriately determined depending on the starting material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-azabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0405] -Capping agent-

[0406] In the manufacture method of polyimide precursor etc., in order to further improve storage stability, preferably the carboxylic acid anhydride, anhydride derivative or amino group remaining in the resin end of polyimide precursor etc. is blocked. When the carboxylic acid anhydride and anhydride derivative remaining in the resin end are blocked, as end-capping agent, monoalcohol, phenol, mercaptan, thiophenol, monoamine etc. can be cited, and from the perspective of reactivity and film stability, monoalcohol, phenols, monoamines are more preferably used. As the preferred compound of monoalcohol, methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, primary alcohols such as furfuryl alcohol, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary alcohols such as ... Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene. , 2-carboxyl-7-aminonaphthalene, 2-carboxyl-6-aminonaphthalene, 2-carboxyl-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 can be used, and a variety of different terminal groups can also be introduced by reacting a variety of end-capping agents.

[0407] Furthermore, when the amino group at the end of the resin is blocked, it can be blocked with a compound having a functional group that can react with the amino group. The preferred sealant for the amino group is preferably carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonyl chloride, sulfonic acid anhydride, sulfonic acid carboxylic anhydride, etc., and more preferably carboxylic acid anhydride and carboxylic acid chloride. As preferred compounds of carboxylic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. can be cited. Furthermore, as preferred compounds of carboxylic acid chloride, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc. can be cited.

[0408] -Solid Precipitation-

[0409] In the manufacture method of polyimide precursor etc., the process of solid precipitation can be included. Specifically, after filtering the water absorption byproduct of the dehydration condensation agent coexisting in the reaction solution as required, the obtained polymer component is put into poor solvents such as water, aliphatic lower alcohol or its mixed solution and the polymer component is precipitated, so that it can be precipitated with solid and dried to obtain polyimide precursor etc. In order to improve the degree of purification, operations such as redissolution, reprecipitation, precipitation, drying, etc. can be repeatedly performed to polyimide precursor etc. In addition, the process of using ion exchange resin to remove ionic impurities can also be included.

[0410] 〔content〕

[0411] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and further preferably 50% by mass or more relative to the total solid content of the resin composition. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 95% by mass or less relative to the total solid content of the resin composition.

[0412] The resin composition of the present invention may contain only one specific resin or two or more specific resins. When containing two or more specific resins, the total amount is preferably within the above range.

[0413] The resin composition of the present invention also preferably contains at least two types of resins.

[0414] Specifically, the resin composition of the present invention may contain two or more specific resins in total and other resins described below, or may contain two or more specific resins, but preferably contains two or more specific resins.

[0415] When the resin composition of the present invention contains two or more specific resins, for example, it preferably contains a structure derived from a dianhydride (R in the above formula (2)) as a polyimide precursor. 115 ) Two or more different polyimide precursors.

[0416] <Other resins>

[0417] The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins").

[0418] Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.

[0419] For example, by further adding a (meth)acrylic resin, a resin composition having excellent coating properties can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.

[0420] For example, by adding a (meth)acrylic resin to the resin composition instead of or in addition to the polymerizable compound described below, the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. The (meth)acrylic resin has a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the molar amount of the polymerizable group in 1 g of the resin is 1×10 -3 mol / g or more).

[0421] When the resin composition of the present invention contains other resins, the content of other resins is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, further preferably 1 mass % or more, further preferably 2 mass % or more, further preferably 5 mass % or more, and further preferably 10 mass % or more, relative to the total solid content of the resin composition.

[0422] The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0423] As a preferred mode of the resin composition of the present invention, it is also possible to set it as a mode in which the content of other resins is low. In the above-mentioned mode, relative to the total solid content of the resin composition, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less. The lower limit of the above-mentioned content is not particularly limited, and 0% by mass or more is sufficient.

[0424] The resin composition of the present invention may contain only one other resin or two or more other resins. When containing two or more specific resins, the total amount is preferably within the above range.

[0425] <Solvent>

[0426] The resin composition of the present invention contains a solvent.

[0427] Here, in the first aspect of the present invention, each content of N-methylpyrrolidone and γ-butyrolactone is 0.1% by mass or less relative to the total mass of the resin composition.

[0428] In the second aspect of the present invention, each content of N-methylpyrrolidone and γ-butyrolactone is preferably 0.1% by mass or less relative to the total mass of the resin composition.

[0429] 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, more preferably 0.01 mass % or less. The lower limit of the content is not particularly limited, and may be 0 mass % or more.

[0430] 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, more preferably 0.01 mass % or less. The lower limit of the content is not particularly limited, and may be 0 mass % or more.

[0431] In the first aspect of the present invention, the resin composition preferably contains γ-valerolactone as the solvent.

[0432] In the second aspect of the present invention, the resin composition contains γ-valerolactone as the solvent.

[0433] The content of γ-valerolactone relative to the total mass of the solvent contained in the resin combination of the present invention is preferably more than 50 mass %, more preferably more than 60 mass %, further preferably more than 70 mass %, particularly preferably more than 75 mass %, most preferably more than 80 mass %. The upper limit of the above content is not particularly limited, and 100 mass % or less is sufficient. And, considering the solubility of the component contained in the resin combination of specific resins, it can also be set to less than 90 mass %, etc.

[0434] An embodiment further comprising dimethyl sulfoxide as a solvent is also one of the preferred embodiments of the present invention.

[0435] By containing dimethyl sulfoxide, the solubility of the component contained in the resin composition, such as a specific resin, can be increased in some cases.

[0436] The content of dimethyl sulfoxide relative to the total mass of the solvent contained in the resin composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. As the upper limit, for example, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less.

[0437] When the resin composition of the present invention contains γ-valerolactone and dimethyl sulfoxide, the content of γ-valerolactone relative to the total amount of γ-valerolactone and dimethyl sulfoxide is preferably 60 to 95% by mass, more preferably 70 to 90% by mass.

[0438] When the resin composition of the present invention contains γ-valerolactone and dimethyl sulfoxide, the total amount of γ-valerolactone and dimethyl sulfoxide relative to the total mass of the solvent contained in the resin composition is preferably 80 mass % or more, more preferably 90 mass % or more. The upper limit of the above content is not particularly limited, and can be 100 mass % or less.

[0439] Furthermore, the resin composition of the present invention may further contain other solvents other than the above-mentioned γ-valerolactone and dimethyl sulfoxide.

[0440] Examples of other solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0441] Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred esters.

[0442] As the ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like are preferred ethers.

[0443] Examples of the ketones preferably include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0444] Examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene. Preferred cyclic hydrocarbons include these.

[0445] As amides, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like are preferred amides.

[0446] As the ureas, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are mentioned as preferred ureas.

[0447] Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol and diacetone alcohol.

[0448] From the viewpoint of coating property, the content of solvent is preferably set to the amount of 5 to 80 mass % of the total solid content concentration of the resin composition of the present invention, more preferably set to the amount of 5 to 75 mass % of the total solid content concentration, further preferably set to the amount of 10 to 70 mass % of the total solid content concentration, and further preferably set to the amount of 20 to 70 mass % of the total solid content concentration. The solvent content can be adjusted according to the thickness and coating method required for the coating film. When containing two or more solvents, it is preferred that the total is within the above range.

[0449] <Polymerizable Compound and Photopolymerization Initiator>

[0450] The resin composition of the present invention preferably contains a polymerizable compound and a photopolymerization initiator.

[0451] According to this aspect, for example, the resin composition of the present invention can be used as a negative photosensitive resin composition.

[0452] Preferred embodiments of each compound are described below in detail.

[0453] <Polymerizable Compound>

[0454] The resin composition of the present invention preferably contains a polymerizable compound.

[0455] Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

[0456] 〔Free radical crosslinking agent〕

[0457] The resin composition of the present invention preferably contains a radical crosslinking agent.

[0458] The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenically unsaturated bond is preferred. As the above-mentioned group containing an ethylenically unsaturated bond, vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, (meth)acrylamide, etc. can be cited.

[0459] Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and a (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0460] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

[0461] As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 ethylenically unsaturated bonds is further preferred.

[0462] From the viewpoint of film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0463] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0464] As a specific example of a free radical crosslinking agent, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, and sulfanyl groups and monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups and epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are preferred, and substitution reaction products of unsaturated carboxylic acid esters or amides with leaving substituents such as halogen groups and tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, the above unsaturated carboxylic acid can be replaced with a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, and allyl ether. As a specific example, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

[0465] The radical crosslinking agent is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples of the compound having a boiling point of 100° C. or higher under normal pressure include compounds described in paragraph 0203 of International Publication No. 2021 / 112189, etc. This content is incorporated into this specification.

[0466] Preferred radical crosslinking agents other than those described above include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189, etc. The contents are incorporated into the present specification.

[0467] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.)), A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), A-DPH (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. Oligomer types of these can also be used.

[0468] Commercially available products of the radical crosslinking agent include, for example, tetrafunctional acrylate SR-494 having four vinyloxy chains, bifunctional methacrylate SR-209, 231, 239 having four vinyloxy chains (all manufactured by Sartomer Company, Inc.), hexafunctional acrylate DPCA-60 having six pentyleneoxy chains, trifunctional acrylate TPA-330 having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (all manufactured by NIPPON PAPER INDUSTRIES 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 CHEMICAL Co., Ltd.), DPHA-4OH (all manufactured by Nippon Kayaku Co., Ltd.), and NK ESTER 4G. Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOFCORPORATION.), etc.

[0469] As the radical crosslinking agent, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. As the radical crosslinking agent, compounds having an amino structure or a thioether structure in the molecule described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 01-105238 can also be used.

[0470] The free radical crosslinking agent can be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a free radical crosslinking agent that reacts the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to make it have an acid group. Particularly preferred is the following compound: in the free radical crosslinking agent that reacts the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to make it have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. As a commercially available product, for example, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEICO., LTD. can be cited.

[0471] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and more preferably 1 to 100 mgKOH / g. As long as the acid value of the radical crosslinking agent is within the above range, the workability in production and the developability are excellent. In addition, the polymerizability is good. The above acid value is measured according to the description of JIS K 0070: 1992.

[0472] As the radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as “crosslinking agent U”) is also preferred.

[0473] In the present invention, the urea bond refers to the bond consisting of *-NR N -C(=O)-NR N -* indicates a key, R N Each independently represents a hydrogen atom or a monovalent organic group, and * each represents a bonding site to a carbon atom.

[0474] In the present invention, a urethane bond refers to a bond consisting of *-OC(=O)-NR N -* indicates a key, R Nrepresents a hydrogen atom or a monovalent organic group, and * represents a bonding site to a carbon atom.

[0475] When the resin composition contains the crosslinking agent U, chemical resistance, resolution, etc. may be improved.

[0476] The mechanism by which the above effect can be obtained is not clear, but it is considered that, for example, when curing is performed by heating or the like, a part of the crosslinking agent U is thermally decomposed to generate amines or the like, and the amines or the like promote the cyclization of the precursor of the cyclized resin such as the polyimide precursor.

[0477] The crosslinking agent U may have only one urea bond or one urethane bond, one or more urea bonds and one or more urethane bonds, two or more urea bonds without a urethane bond, or two or more urethane bonds without a urea bond.

[0478] The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0479] When the crosslinking agent U does not have a urethane bond, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0480] When the crosslinking agent U does not have a urea bond, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0481] The free radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamide, vinylphenyl or maleimide, and more preferably (meth)acryloyloxy.

[0482] When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different.

[0483] The number of radical polymerizable groups in the crosslinking agent U may be only one or two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0484] The radical polymerizable group value (mass of the compound per 1 mol of the radical polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol.

[0485] From the viewpoint of chemical resistance of the cured product, the lower limit of the free radical polymerizable group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, further preferably 220 g / mol or more, further preferably 230 g / mol or more, further preferably 240 g / mol or more, and particularly preferably 250 g / mol or more.

[0486] From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, particularly preferably 300 g / mol or less.

[0487] The polymerizable group value of the crosslinking agent U is preferably 210 to 400 g / mol, more preferably 220 to 400 g / mol.

[0488] The crosslinking agent U preferably has a structure represented by the following formula (U-1), for example.

[0489] [Chemical formula 23]

[0490]

[0491] In formula (U-1), R U1 is a hydrogen atom or a monovalent organic group, A is -0- or -NR N -, R N is a hydrogen atom or a monovalent organic group, Z U1 is an m-valent organic group, Z U2 is an n+1-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

[0492] R U1 A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[0493] R N A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[0494] Z U1 Preferred are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N -A group formed by bonding at least one group in the group consisting of

[0495] The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and still more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by bonds of these. N It represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or a methyl group.

[0496] Z U2 Preferred are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N -A group formed by bonding at least one group in the group consisting of

[0497] Examples of the hydrocarbon group include U1 The same as those mentioned above, the preferred embodiments are also the same.

[0498] X is not particularly limited and examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamide, vinylphenyl or maleimide, and more preferably (meth)acryloyloxy.

[0499] n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0500] m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0501] The crosslinking agent U also preferably has at least one of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group.

[0502] The hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but is preferably an alcoholic hydroxyl group, from the viewpoint of chemical resistance of the obtained cured film.

[0503] From the viewpoint of chemical resistance of the obtained cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, further preferably an alkyleneoxy group having 2 to 4 carbon atoms, further preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.

[0504] The alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0505] Amide refers to -C(=O)-NR N - indicates a bond. N As described above, when the crosslinking agent U has an amide group, the crosslinking agent U can contain, for example, a N -* or a group represented by *-C(=O)-NR N - A group represented by R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0506] The crosslinking agent U may have two or more structures selected from the group consisting of a hydroxyl group, an alkyleneoxy group (in the case of a polyalkyleneoxy group, a polyalkyleneoxy group), an amide group, and a cyano group in the molecule, but preferably has only one structure in the molecule.

[0507] The above-mentioned hydroxyl group, alkyleneoxy group and cyano group may be present at any position of the crosslinking agent U, but from the viewpoint of chemical resistance, in the crosslinking agent U, at least one selected from the group consisting of the above-mentioned hydroxyl group, alkyleneoxy group and cyano group is preferably connected to at least one free radical polymerizable group contained in the crosslinking agent U via a connecting group containing a urea bond or a urethane bond (hereinafter also referred to as "connecting group L2-1").

[0508] In particular, when the crosslinking agent U contains only one free radical polymerizing group, the free radical polymerizing group contained in the crosslinking agent U is preferably connected to at least one selected from the group consisting of a hydroxyl group, an alkylene oxide group, an amide group and a cyano group via a connecting group containing a urea bond or a carbamate bond (hereinafter also referred to as "connecting group L2-2").

[0509] When the crosslinking agent U contains an alkyleneoxy group (wherein, when constituting a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the above-mentioned connecting group L2-1 or the above-mentioned connecting group L2-2, the structure bonded to the connecting group L2-1 or the connecting group L2-2 on the opposite side to the alkyleneoxy group (wherein, when constituting a polyalkyleneoxy group, it is a polyalkyleneoxy group) is not particularly limited, but is preferably a group represented by a hydrocarbon group, a free radical polymerizable group or a combination thereof. As the above-mentioned hydrocarbon group, a hydrocarbon group with a carbon number of 20 or less is preferred, a hydrocarbon group with a carbon number of 18 or less is more preferred, and a hydrocarbon group with a carbon number of 16 or less is further preferred. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group represented by a bond of these can be cited. In addition, the preferred embodiment of the free radical polymerizable group is the same as the preferred embodiment of the free radical polymerizable group in the above-mentioned crosslinking agent U.

[0510] When the crosslinking agent U contains an amide group and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the amide group is not particularly limited, but is preferably a group represented by a hydrocarbon group, a free radical polymerizable group or a combination thereof. As the above-mentioned hydrocarbon group, a hydrocarbon group with a carbon number of 20 or less is preferred, a hydrocarbon group with a carbon number of 18 or less is more preferred, and a hydrocarbon group with a carbon number of 16 or less is further preferred. In addition, as the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group represented by their bonds can be cited. The preferred mode of the free radical polymerizable group is the same as the preferred mode of the free radical polymerizable group in the above-mentioned crosslinking agent U. In addition, in the above-mentioned mode, the carbon atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2, and the nitrogen atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2.

[0511] Among these, the crosslinking agent U preferably has a hydroxyl group from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids.

[0512] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group.

[0513] The aromatic group is preferably directly bonded to the urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferred that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.

[0514] The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may be a condensed ring structure formed by these groups, but is preferably an aromatic hydrocarbon group.

[0515] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and still more preferably a group obtained by removing two or more hydrogen atoms from a benzene ring structure.

[0516] As the above-mentioned aromatic heterocyclic group, a 5-membered or 6-membered aromatic heterocyclic group is preferred. As the aromatic heterocyclic ring in such an aromatic heterocyclic group, pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. can be cited. These rings can be further condensed with other rings, such as indole and benzimidazole.

[0517] As the hetero atom contained in the above aromatic heterocyclic group, a nitrogen atom, an oxygen atom or a sulfur atom is preferred.

[0518] The above-mentioned aromatic group is preferably included in the following linking group, for example: a linking group that links two or more free radical polymerizing groups and contains a urea bond or a carbamate bond; or a linking group that links at least one of the group consisting of the above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group and at least one free radical polymerizing group contained in the crosslinking agent U.

[0519] The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2-20, and even more preferably 2-10.

[0520] When the crosslinking agent U contains a total of more than 2 urea bonds or urethane bonds, when it contains more than 2 free radical polymerizable groups, or when it contains more than 2 urea bonds or urethane bonds and more than 2 free radical polymerizable groups, the minimum number of atoms (connection chain length) between the urea bond or urethane bond and the free radical polymerizable group can be within the above range.

[0521] In this specification, "the number of atoms (connection chain length) between the urea bond or urethane bond and the polymerizable group" means that in the atomic chain on the path connecting two atoms or atomic groups as the connection objects, these connection objects are connected by the shortest (smallest number of atoms) path. For example, in the structure represented by the following formula, the number of atoms (connection chain length) between the urea bond and the free radical polymerizable group (methacryloyloxy) is 2.

[0522] [Chemical formula 24]

[0523]

[0524] 〔Axis of symmetry〕

[0525] The crosslinking agent U is also preferably a compound having a structure without a symmetry axis.

[0526] The crosslinking agent U does not have an axis of symmetry means that it is a bilaterally asymmetric compound and does not have an axis that produces a molecule identical to the original molecule by rotating the entire compound. In addition, when the structural formula of the crosslinking agent U is marked on paper, the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be marked as having an axis of symmetry.

[0527] It is considered that since the cross-linking agent U has no symmetric axis, aggregation of the cross-linking agents U in the composition film is suppressed.

[0528] 〔Molecular weight〕

[0529] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and more preferably 200 to 900.

[0530] The method for producing the crosslinking agent U is not particularly limited, but for example, the crosslinking agent U can be obtained by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxyl group and an amino group.

[0531] Specific examples of the cross-linking agent U are shown below, but the cross-linking agent U is not limited thereto.

[0532] [Chemical formula 25]

[0533]

[0534] [Chemical formula 26]

[0535]

[0536] [Chemical formula 27]

[0537]

[0538] From the viewpoint of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate as the resin composition.

[0539] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate can be used. , 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylates having a carbamate bond, bifunctional methacrylates having a carbamate bond. These can be used in combination of two or more as needed.

[0540] For example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain with a formula weight of about 200.

[0541] From the viewpoint of suppressing the warping of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as a radical crosslinking agent. As a monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate and other (meth)acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether, etc. can be preferably used. As a monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of more than 100°C at normal pressure is also preferred.

[0542] Examples of the bifunctional or higher-functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0543] When a free radical crosslinking agent is contained, the content of the free radical crosslinking agent is preferably more than 0% by mass and less than 60% by mass relative to the total solid content of the resin composition. The lower limit is more preferably more than 5% by mass. The upper limit is more preferably less than 50% by mass, and further preferably less than 30% by mass.

[0544] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used in combination, the total amount thereof is preferably within the above range.

[0545] 〔Other cross-linking agents〕

[0546] The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.

[0547] The other crosslinking agent refers to a crosslinking agent other than the above-mentioned free radical crosslinking agent, and is preferably a compound having a plurality of groups in the molecule that promote the reaction (form a covalent bond with other compounds in the composition or their reaction products) by the photosensitization of the above-mentioned photoacid generator or photobase generator, and more preferably a compound having a plurality of groups in the molecule that promote the reaction (form a covalent bond with other compounds in the composition or their reaction products) by the action of an acid or a base.

[0548] The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

[0549] As other cross-linking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[0550] As other crosslinking agents, for example, compounds having the following structure can be cited: a structure in which an amino-containing compound such as melamine, acetylene carbamide, urea, alkylene urea, benzoguanamine, etc. is reacted with formaldehyde, or formaldehyde is reacted with an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a hydroxymethyl group, a hydroxyethyl group, or an alkoxymethyl group. The production method of these compounds is not particularly limited, as long as the compounds have the same structure as the compounds produced by the above methods. These compounds may be oligomers formed by self-condensation of the hydroxymethyl groups of these compounds.

[0551] As the above-mentioned amino-containing compound, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using acetylene urea, urea or alkylene urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.

[0552] Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea crosslinking agents and melamine crosslinking agents, and more preferably contains at least one compound selected from the group consisting of acetylene urea crosslinking agents and melamine crosslinking agents described below.

[0553] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of a urea structure described below, or a triazine.

[0554] The alkoxymethyl group or acyloxymethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, preferably has 2 or 3 carbon atoms, and more preferably has 2 carbon atoms.

[0555] The total number of the alkoxymethyl groups and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0556] The molecular weight of the compound is preferably 1,500 or less, more preferably 180 to 1,200.

[0557] [Chemical formula 28]

[0558]

[0559] R 100 represents an alkyl group or an acyl group.

[0560] R 101 and R 102 Each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0561] Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted with an aromatic group include compounds represented by the following general formula.

[0562] [Chemical formula 29]

[0563]

[0564] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each independently represents an alkyl group or an acyl group, R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that leaves by the action of an acid, a group consisting of -C(R 4 )2COOR 5 The group (R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 It represents a group that leaves by the action of an acid.

[0565] R 105 Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

[0566] Regarding the group that decomposes by the action of an acid to generate an alkali-soluble group, the group that leaves by the action of an acid, and the group consisting of -C(R 4 )2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 )wait.

[0567] In the formula, R 36 ~R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0568] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0569] The above-mentioned alkyl group may be either linear or branched.

[0570] The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.

[0571] The cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.

[0572] The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.

[0573] The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an alkyl group having 7 to 16 carbon atoms.

[0574] The above-mentioned aralkyl group means an aryl group substituted by an alkyl group, and preferred embodiments of these alkyl groups and aryl groups are the same as the preferred embodiments of the above-mentioned alkyl groups and aryl groups.

[0575] The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

[0576] These groups may further have a known substituent.

[0577] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0578] As the group that decomposes by the action of an acid to generate an alkali-soluble group or the group that leaves by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. A tertiary alkyl ester group and an acetal group are more preferred.

[0579] Furthermore, as the compound having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl, a compound having at least one group selected from the group consisting of urea bond and urethane bond is also preferred. A preferred embodiment of the above compound is the same as the preferred embodiment of the crosslinking agent U except that the polymerizable group is at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl instead of the free radical polymerizable group.

[0580] As a compound having at least one group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group and a hydroxyethyl group, specifically, the following structures can be cited. As a compound having an acyloxymethyl group, a compound in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group can be cited. As a compound having an alkoxymethyl group or an acyloxymethyl group in the molecule, the following compounds can be cited, but are not limited to these.

[0581] [Chemical formula 30]

[0582]

[0583] [Chemical formula 31]

[0584]

[0585] [Chemical formula 32]

[0586]

[0587] As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available product may be used, or a compound synthesized by a known method may be used.

[0588] From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0589] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0590] Specific examples of the urea-based crosslinking agent include monomethylolated acetylene urea, dimethylolated acetylene urea, trimethylolated acetylene urea, tetramethylolated acetylene urea, monomethoxymethylated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetramethoxymethylated acetylene urea, monoethoxymethylated acetylene urea, diethoxymethylated acetylene urea, triethoxymethylated acetylene urea, tetraethoxymethylated acetylene urea, monopropoxymethylated acetylene urea, dipropoxymethylated acetylene urea, tripropoxymethylated acetylene urea, tetrapropoxymethylated acetylene urea, monobutoxymethylated acetylene urea, dibutoxymethylated acetylene urea, tributoxymethylated acetylene urea, tetrabutoxymethylated acetylene urea, and the like.

[0591] Urea crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea,

[0592] Ethylene urea crosslinking agents such as monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea,

[0593] Acrylene urea crosslinking agents such as monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea,

[0594] 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0595] Specific examples of the benzoguanamine-based crosslinking agent include monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0596] Furthermore, as the compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[0597] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenylhydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl Benzophenone, methoxymethylbenzoic acid methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4"-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0598] As other crosslinking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM -PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, hereinafter the same) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO., LTD.), etc.

[0599] The resin composition of the present invention also preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[0600] -Epoxy compounds (compounds having epoxy groups)-

[0601] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a cross-linking reaction below 200°C and does not cause a dehydration reaction due to cross-linking, so it is not easy to cause film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition can be effectively suppressed.

[0602] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and preferably the number of repeating units is 2 to 15.

[0603] Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; silicones containing epoxy groups such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specific examples include EPICLON (registered trademark, the same hereinafter) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON HP-4770, EPICLON EXA-830LVP, EPICLON EXA-8183, EPICLON EXA-8169, EPICLON N-660, EPICLON N-665-EXP-S, and EPICLON N-740 (these are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark, the same hereinafter) BEO-20E, RIKARESIN BEO-60E, RIKARESIN HBE-100, RIKARESIN DME-100, and RIKARESIN L-200 (these are trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (these are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark, the same below) 2021P, CELLOXIDE 2081, CELLOXIDE 2000, EHPE3150, EPOLEAD (registered trademark, the same below) GT401, EPOLEAD PB4700, EPOLEAD PB3600 (these are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.Furthermore, the following compounds can also be preferably used.

[0604] [Chemical formula 33]

[0605]

[0606] In the formula, n is an integer of 1-5, and m is an integer of 1-20.

[0607] In the above structure, from the viewpoint of achieving both improvement in heat resistance and elongation, it is preferred that n is 1 to 2 and m is 3 to 7.

[0608] -Oxetane compound (compound having an oxetane group)-

[0609] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

[0610] -Benzoxazine compound (compound having a benzoxazolyl group)-

[0611] Benzoxazine compounds are preferred because they cause a crosslinking reaction by a ring-opening addition reaction and thus do not cause outgassing during curing, thereby further reducing thermal shrinkage and suppressing the occurrence of warpage.

[0612] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0613] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass relative to the total solid content of the resin composition. Other crosslinking agents may contain only one or more. When containing more than two other crosslinking agents, it is preferred that the total amount is within the above range.

[0614] 〔Polymerization initiator〕

[0615] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferred to contain a photopolymerization initiator.

[0616] The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that acts with a photoexcited sensitizer to generate active free radicals.

[0617] The photoradical polymerization initiator preferably contains at least one having a photopolymerization activity of at least about 50 L·mol in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). -1 cm -1 The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferably measured by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0618] As a photo-radical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbimidazoles, oxime compounds such as 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 aromatic complexes, etc. can be cited. For details of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and the content is incorporated into this specification. In addition, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, Japanese Patent Publication No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313 can be cited, and these contents are incorporated into this specification.

[0619] Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0620] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents are incorporated into this specification.

[0621] As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF) can be used.

[0622] As the α-aminoketone initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0623] As the aminoacetophenone-based initiator, the acylphosphine oxide-based initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be preferably used. The contents are incorporated into the present specification.

[0624] As the photo-radical polymerization initiator, an oxime compound can be more preferably used. By using an oxime compound, the exposure latitude can be further effectively improved. Oxime compounds have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator, so they are particularly preferred.

[0625] Specific examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science. and Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Publication No. 2000-066385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Application 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., the contents of which are incorporated into this specification.

[0626] Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferred to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group >C=NOC(=O)- in the molecule.

[0627] [Chemical formula 34]

[0628]

[0629] Commercially available products of oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in JP-A-2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, oxime compounds of the following structures can also be used.

[0630] [Chemical formula 35]

[0631]

[0632] As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, and an oxime compound having a fluorine atom can also be used.

[0633] Furthermore, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a substituent having a hydroxyl group bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359 can also be used. These contents are incorporated into this specification.

[0634] As the photopolymerization initiator, an aromatic ring group Ar having an electron-withdrawing group introduced into the aromatic ring can also be used. OX1 As the aromatic ring group Ar OX1The electron withdrawing group may include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano. Acyl and nitro are preferred. Acyl is more preferred because it is easy to form a film with excellent light resistance, and benzoyl is further preferred. The benzoyl may have a substituent. As a substituent, a halogen atom, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclicoxy, alkenyl, alkylsulfanyl, arylsulfanyl, acyl or amino is preferred. An alkyl, alkoxy, aryl, aryloxy, heterocyclicoxy, alkylsulfanyl, arylsulfanyl or amino is more preferred. An alkoxy, alkylsulfanyl or amino is further preferred.

[0635] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by the formula (OX1) and a compound represented by the formula (OX2), and is more preferably a compound represented by the formula (OX2).

[0636] [Chemical formula 36]

[0637]

[0638] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphonyl group, a carbamoyl group or a sulfamoyl group,

[0639] R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group,

[0640] R X3 ~R X14 Each independently represents a hydrogen atom or a substituent.

[0641] Among them, R X10 ~R X14 At least one of them is an electron withdrawing group.

[0642] In the above formula, preferably R X12 is an electron-withdrawing group and R X10 , R X11 , R X13 , R X14 A hydrogen atom.

[0643] Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.

[0644] Particularly preferred oxime compounds include oxime compounds having specific substituents described in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having thioaryl groups described in Japanese Patent Application Laid-Open No. 2009-191061, and the like, and the contents thereof are incorporated into the present specification.

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

[0646] Furthermore, the photoradical polymerization initiator is a trihalomethyl triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyl triazine compound, an α-amino ketone compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, and a benzophenone compound, and further preferably a metallocene compound or an oxime compound.

[0647] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, and the contents are incorporated into the present specification.

[0648] As the photo-radical polymerization initiator, a photo-radical polymerization initiator of difunctional or trifunctional or more can be used. By using this type of photo-radical polymerization initiator, more than two free radicals are generated from one molecule of the photo-radical polymerization initiator, so good sensitivity can be obtained. And, in the case of using a compound of asymmetric structure, crystallinity decreases and the solubility in solvents etc. becomes higher, becomes difficult to separate out over time, and can thus improve the stability over time of resin combination. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include dimers of oxime compounds described in paragraphs 0407 to 0412 of JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015 / 004565, JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and compounds (E) and ( G), Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Publication No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc., the contents of which are incorporated into this specification.

[0649] When the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and further preferably 1.0 to 10% by mass relative to the total solid content of the resin composition. The photopolymerization initiator may contain only one or more. When containing more than two photopolymerization initiators, the total amount is preferably within the above range.

[0650] In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0651] 〔Sensitizer〕

[0652] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with a thermal free radical polymerization initiator, a photo free radical polymerization initiator, etc., and generates electron transfer, energy transfer, heat generation, etc. As a result, the thermal free radical polymerization initiator and the photo free radical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids or bases.

[0653] As sensitizers that can be used, compounds such as benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used.

[0654] Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamindanone, and p-dimethylaminoindanone. Benzyl indanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene)benzothiazole, 2-(p-dimethylaminophenyl vinylene) isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl -7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylamino isopentyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc.

[0655] Furthermore, other sensitizing pigments may also be used.

[0656] For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification.

[0657] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass relative to the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0658] 〔Chain transfer agent〕

[0659] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a compound group having -SS-, -SO2-S-, -NO-, SH, PH, SiH and GeH in the molecule, dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthate compounds having thiocarbonylthio groups for RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, etc. can be used. These can generate free radicals by supplying hydrogen to low-activity free radicals, or can generate free radicals by deprotonating after oxidation. In particular, thiol compounds can be preferably used.

[0660] Furthermore, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used, and the contents are incorporated into the present specification.

[0661] When the resin composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be only one or more. When there are two or more chain transfer agents, it is preferred that the total is within the above range.

[0662] <Alkali Generator>

[0663] The resin composition of the present invention may contain a base generator. Here, the base generator refers to a compound that can generate a base by physical action or chemical action. Preferred base generators include thermal base generators and photobase generators.

[0664] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains an alkali generator. When the resin composition contains a thermal alkali generator, the cyclization reaction of the precursor can be promoted by heating, so that the mechanical properties and chemical resistance of the cured product are good, and the performance as an interlayer insulating film for a redistribution layer contained in a semiconductor package becomes good.

[0665] The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.

[0666] The base generating agent is not particularly limited, and a known base generating agent can be used. Examples of known base generating agents include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imide salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like.

[0667] Specific examples of the nonionic base generating agent include compounds represented by formula (B1), formula (B2) or formula (B3).

[0668] [Chemical formula 37]

[0669]

[0670] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 Each independently represents an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. 1 and Rb 2 will not become a hydrogen atom at the same time. 1 , Rb 2 and Rb 3 In addition, in this specification, a tertiary amine structure refers to a structure in which the three bonds of a trivalent nitrogen atom are covalently bonded to the carbon atom of a hydrocarbon group. Therefore, when the carbon atom bonded to the trivalent nitrogen atom is a carbon atom constituting a carbonyl group, that is, when an amide group is formed with the nitrogen atom, it is not a tertiary amine structure.

[0671] In formula (B1) and (B2), Rb is preferably 1 , Rb 2 and Rb 3 At least one of the rings contains a cyclic structure, and more preferably at least two of the rings contain a cyclic structure. As the cyclic structure, it can be any one of a monocyclic ring and a condensed ring, preferably a monocyclic ring or a condensed ring formed by condensing two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

[0672] More specifically, Rb 1 and Rb 2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). These groups may have a substituent. Rb 1 With Rb 2 They may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and Rb 2 Preferably, it is a linear, branched or cyclic alkyl group which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), and further preferably a cyclohexyl group which may have a substituent.

[0673] As Rb 3 Examples of the group include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and more preferably 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and more preferably 2 to 6 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and more preferably 7 to 12 carbon atoms), arylalkenyl groups (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and more preferably 8 to 16 carbon atoms), alkoxy groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12 carbon atoms), aryloxy groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and more preferably 6 to 12 carbon atoms), and arylalkoxy groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and more preferably 7 to 12 carbon atoms). Among these, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), arylalkenyl groups, and arylalkoxy groups are preferred. R 3 It may further have a substituent.

[0674] The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0675] [Chemical formula 38]

[0676]

[0677] In the formula, Rb 11 and Rb 12 and Rb31 and Rb 32 Respectively with Rb in formula (B1) 1 and Rb 2 same.

[0678] R 13 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and may have a substituent. 13 Aralkyl groups are preferred.

[0679] R 33 and Rb 34 Each of them independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom.

[0680] R 35 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and an aryl group is preferred.

[0681] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0682] [Chemical formula 39]

[0683]

[0684] R 11 and Rb 12 The meaning is the same as Rb in formula (B1-1) 11 and Rb 12 have the same meaning.

[0685] R 15 and Rb 16It is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

[0686] R 17 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), among which an aryl group is preferred.

[0687] [Chemical formula 40]

[0688]

[0689] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain linking adjacent oxygen atoms and carbon atoms and having 3 or more atoms on the path of the connecting chain. N1 and R N2 Each independently represents a monovalent organic group.

[0690] In this specification, "connection chain" refers to an atom chain on a path connecting two atoms or groups of atoms as connection objects, connecting these connection objects with the shortest (minimum number of atoms) path. For example, in the compound represented by the following formula, L is composed of phenylene ethylene and has ethylene as a saturated hydrocarbon group, the connection chain is composed of 4 carbon atoms, and the number of atoms on the path of the connection chain (that is, the number of atoms constituting the connection chain, hereinafter also referred to as "connection chain length" or "length of the connection chain") is 4.

[0691] [Chemical formula 41]

[0692]

[0693] The number of carbon atoms in L in formula (B3) (including carbon atoms other than carbon atoms in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above-mentioned intramolecular cyclization reaction, the upper limit of the connecting chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, the connecting chain length of L is preferably 4 or 5, and most preferably 4. As specific preferred compounds of the alkali generator, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002 can also be cited.

[0694] Furthermore, the base generating agent also preferably contains a compound represented by the following formula (N1).

[0695] [Chemical formula 42]

[0696]

[0697] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group, R Cl represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0698] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and further preferably 5 or less. The linking chain length refers to the number of atoms present in the atomic arrangement, and the atomic arrangement becomes the shortest distance between the two carbonyl groups in the formula.

[0699] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 10), and specifically, an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 10) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), preferably an aliphatic hydrocarbon group. When an aliphatic hydrocarbon group is used as R N1 and R N2, the basicity of the generated base is high, so it is preferred. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring or in the substituent. In particular, the aliphatic hydrocarbon group can be exemplified as having an oxygen atom in the hydrocarbon chain.

[0700] As a component of R N1 and R N2 The aliphatic hydrocarbon group includes a linear or branched chain alkyl group, a cyclic alkyl group, a group including a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The number of carbon atoms in the linear or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and further preferably 3 to 12. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and the like.

[0701] The number of carbon atoms in the cyclic alkyl group is preferably 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0702] The number of carbon atoms of the group comprising a combination of a chain alkyl group and a cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and further preferably 4 to 12. Examples of the group comprising a combination of a chain alkyl group and a cyclic alkyl group include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0703] The number of carbon atoms in the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like, cyclic, linear or branched.

[0704] However, from the viewpoint of increasing the boiling point of the base generated by decomposition described later, R N1 and R N2 An alkyl group having 5 to 12 carbon atoms is preferred. However, in a formulation where adhesion to a metal (eg, copper) layer is important, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0705] R N1 With R N2 The ring structure may have oxygen atoms, etc. in the chain. N1 and R N2The formed cyclic structure can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the formed cyclic structure, a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1) is preferred, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc. can be cited, and preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring can be cited.

[0706] R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0707] As the protecting group, a protecting group that is decomposed by the action of an acid or a base is preferred, and a protecting group that is decomposed by an acid is preferably used.

[0708] As a specific example of the protecting group, a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain can be cited. As chain or cyclic alkyl groups, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, etc. can be cited. As chain alkyl groups having an oxygen atom in the chain, alkoxyalkyl groups can be cited, preferably methoxymethyl (MOM) groups, ethoxyethyl (EE) groups, etc. can be cited. As cyclic alkyl groups having an oxygen atom in the chain, epoxy groups, glycidyl groups, oxetanyl groups, tetrahydrofuranyl groups, tetrahydropyranyl (THP) groups, etc. can be cited.

[0709] In formula (N1), the divalent linking group constituting L is not particularly limited, and is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may also have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, and further preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a group comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain, and further preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom.

[0710] The number of carbon atoms of the divalent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and further preferably 2 to 6. The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and further preferably 2 to 4. The number of carbon atoms of the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 10. The number of carbon atoms of the group comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., aralkylene group) is preferably 7 to 22, more preferably 7 to 18, and further preferably 7 to 10.

[0711] Specifically, the linking group L is preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group comprising a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.

[0712] The linear or branched alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.

[0713] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

[0714] The number of carbon atoms of the group consisting of a combination of a linear alkylene group and a cyclic alkylene group is preferably 4 to 24, more preferably 4 to 12, and even more preferably 4 to 6.

[0715] The alkylene group having an oxygen atom in its chain may be chain or cyclic, and may be linear or branched. The number of carbon atoms in the alkylene group having an oxygen atom in its chain is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0716] The number of carbon atoms in the linear or branched alkenylene group is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 3. The number of C═C bonds in the linear or branched alkenylene group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 3.

[0717] The number of carbon atoms in the cyclic alkenylene group is preferably 3 to 12, more preferably 3 to 6. The number of C═C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

[0718] The arylene group has preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms.

[0719] The arylenealkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms.

[0720] Among them, preferred are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, and arylene alkylene groups; more preferred are 1,2-ethylene, propylene (particularly 1,3-propylene), cyclohexanediyl (particularly 1,2-cyclohexanediyl), vinylene (particularly cis-vinylene), phenylene (1,2-phenylene), phenylene methylene (particularly 1,2-phenylene methylene), and ethyleneoxyethylene (particularly 1,2-ethyleneoxy-1,2-ethylene).

[0721] Examples of the base generating agent include the following compounds, but the base generating agent is not limited to these compounds.

[0722] [Chemical formula 43]

[0723]

[0724] The molecular weight of the nonionic base generating agent is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0725] Specific examples of preferred compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0726] Specific examples of the ammonium salt include the following compounds, but are not limited to these.

[0727] [Chemical formula 44]

[0728]

[0729] Specific examples of the imide salt include the following compounds, but are not limited to these.

[0730] [Chemical formula 45]

[0731]

[0732] When the resin composition contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.

[0733] The base generating agent can be used alone or in combination. When two or more base generating agents are used, the total amount is preferably within the above range.

[0734] <Metal Adhesion Improver>

[0735] From the viewpoint of improving the adhesion to the metal material used in electrodes or wiring, the resin composition of the present invention preferably contains a metal adhesion improver. Examples of the metal adhesion improver include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0736] 〔Silane coupling agent〕

[0737] As a silane coupling agent, for example, the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Publication No. 2018-173573 can be cited, and these contents are incorporated into this specification. In addition, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358, it is also preferred to use two or more different silane coupling agents. The following compounds are also preferably used as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group. In addition, the following R can cite the structure of a blocking agent derived from a blocked isocyanate group. As a blocking agent, it can be selected according to the desorption temperature, and alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, etc. can be cited. For example, from the viewpoint of setting the desorption temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available products of such a compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0738] [Chemical formula 46]

[0739]

[0740] Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3- Acryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyl trialkoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

[0741] Furthermore, as the silane coupling agent, an oligomer type compound having a plurality of alkoxysilyl groups can also be used.

[0742] Examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).

[0743] [Chemical formula 47]

[0744]

[0745] In formula (S-1), R G1 Represents a monovalent organic group, R S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group, and n represents an integer of 0 to 2.

[0746] R S1 It is preferred to have a structure containing a polymerizable group. As a polymerizable group, a group with an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, an amino group, etc. can be cited. As a group with an ethylenically unsaturated bond, a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group with an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), a (methyl) acrylamide group, a (methyl) acryloxy group, etc. can be cited, preferably vinylphenyl, (methyl) acrylamide group or (methyl) acryloxy group, more preferably vinylphenyl or (methyl) acryloxy group, further preferably (methyl) acryloxy group.

[0747] R S2 It is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.

[0748] n represents an integer of 0 to 2, and is preferably 1.

[0749] Here, the structures of the plurality of repeating units represented by the formula (S-1) contained in the oligomer type compound may be the same.

[0750] Here, among the multiple repeating units represented by formula (S-1) contained in the oligomer type compound, n is preferably 1 or 2 in at least one, more preferably 1 or 2 in at least two, and even more preferably 1 in at least two.

[0751] As such an oligomer type compound, a commercially available product can be used, and examples of the commercially available product include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0752] 〔Aluminum-based adhesive additive〕

[0753] Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and ethyl acetoacetate aluminum diisopropoxide.

[0754] As other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used, and these contents are incorporated into the present specification.

[0755] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be only one or more. When two or more are used, it is preferred that the total is within the above range.

[0756] <Migration Inhibitor>

[0757] The resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0758] The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring, a 6H-pyran ring, and a triazine ring), compounds having a thiourea or a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0759] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions may also be used.

[0760] As other migration inhibitors, for example, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015 / 199219, etc. can be used, and the contents are incorporated into this specification.

[0761] Specific examples of the migration inhibitor include the following compounds.

[0762] [Chemical formula 48]

[0763]

[0764] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass based on the total solid content of the resin composition.

[0765] The migration inhibitor may be one or two or more. When the migration inhibitor is two or more, the total amount thereof is preferably within the above range.

[0766] <Polymerization Inhibitor>

[0767] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0768] Specific examples of the polymerization inhibitor include compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. The contents are incorporated into this specification.

[0769] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0770] The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is used in combination of two or more, the total amount thereof is preferably within the above range.

[0771] <Other additives>

[0772] The resin composition of the present invention can contain various additives as needed within the scope of obtaining the effect of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliary agents (such as defoamers, flame retardants, etc.), compounds with pyridine rings, urea compounds such as dicyclohexyl urea and diisopropyl urea, etc. By appropriately containing these components, properties such as film properties can be adjusted. About these components, for example, the records of paragraphs 0183 and later of Japanese Patent Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812 specification), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Publication No. 2008-250074, etc., can be incorporated into this specification. When these additives are formulated, the total content thereof is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0773] 〔Surfactant〕

[0774] As the surfactant, various surfactants can be used, such as fluorine-based surfactants, silicone-based surfactants, hydrocarbon-based surfactants, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0775] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when preparing the coating liquid composition can be further improved, and the uniformity of the coating thickness or the liquid saving can be further improved. That is, when a coating liquid containing a surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and improving the coating property of the coated surface. Therefore, a uniform film with less uneven thickness can be formed more preferably.

[0776] Examples of the fluorine-based surfactant include compounds described in paragraph 0328 of International Publication No. 2021 / 112189, and the contents are incorporated into the present specification.

[0777] As the fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which contains: 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 and propyleneoxy groups), for example, the following compounds can be mentioned.

[0778] [Chemical formula 49]

[0779]

[0780] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0781] Regarding fluorine-based surfactants, fluorine-containing polymers having ethylenically unsaturated groups on the side chains can also be used as fluorine-based surfactants. As specific examples, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965 can be cited, and the contents are incorporated into this specification. In addition, as commercially available products, for example, MEGAFACE RS-101, RS-102, RS-718K, etc. manufactured by DIC Corporation can be cited.

[0782] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorine-based surfactants having a fluorine content within this range are effective in terms of thickness uniformity and liquid saving of the coating film, and also have good solubility in the composition.

[0783] Examples of the silicone-based surfactant, hydrocarbon-based surfactant, nonionic surfactant, cationic surfactant, and anionic surfactant include compounds described in paragraphs 0329 to 0334 of International Publication No. 2021 / 112189, and the contents are incorporated into the present specification.

[0784] The surfactant may be used alone or in combination of two or more.

[0785] The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[0786] 〔Higher fatty acid derivatives〕

[0787] In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention so that it is localized on the surface of the resin composition of the present invention during the drying process after coating.

[0788] Furthermore, as the higher fatty acid derivatives, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used, and the contents are incorporated into the present specification.

[0789] When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition. The higher fatty acid derivative may be only one or more. When there are more than two higher fatty acid derivatives, it is preferred that the total is within the above range.

[0790] 〔Thermal polymerization initiator〕

[0791] As a thermal polymerization initiator, for example, a thermal free radical polymerization initiator can be cited. A thermal free radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, a polymerization reaction of a resin and a polymerizable compound can also be performed, so that solvent resistance can be further improved. In addition, sometimes a photopolymerization initiator also has the function of initiating polymerization by heat, and sometimes it can be added as a thermal polymerization initiator.

[0792] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.

[0793] When the resin composition contains a thermal polymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.5 to 15% by mass relative to the total solid content of the resin composition. The thermal polymerization initiator may contain only one or more. When containing more than two thermal polymerization initiators, the total amount is preferably within the above range.

[0794] 〔Inorganic particles〕

[0795] Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0796] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[0797] The above average particle size of the inorganic particles is a primary particle size and a volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.), for example.

[0798] When the above measurement is difficult to perform, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.

[0799] 〔Ultraviolet light absorber〕

[0800] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers.

[0801] Specific examples of the ultraviolet absorber include the compounds described in paragraphs 0341 to 0342 of International Publication No. 2021 / 112189, and the contents are incorporated into the present specification.

[0802] The ultraviolet absorber may be used alone or in combination of two or more.

[0803] When the resin composition contains a UV absorber, the content of the UV absorber is preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 0.1% by mass, based on the total solid content of the resin composition.

[0804] 〔Organotitanium compounds〕

[0805] When the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when the resin composition is cured at a low temperature.

[0806] Examples of the organic titanium compound that can be used include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0807] Specific examples of the organic titanium compound are shown in the following I) to VII).

[0808] I) Titanium chelate compound: From the aspect that the storage stability of the resin composition is excellent and a good curing pattern can be obtained, a titanium chelate compound having more than two alkoxy groups is more preferred. Specific examples are diisopropyl bis(triethanolamine) titanium, di(n-butyl alcohol)bis(2,4-pentanedione) titanium, diisopropyl bis(2,4-pentanedione) titanium, diisopropyl bis(tetramethylheptanedione) titanium, diisopropyl bis(ethyl acetoacetate) titanium, etc.

[0809] II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenol, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetrastearylate, titanium tetra[bis{2,2-(allyloxymethyl)butoxide}], and the like.

[0810] III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[0811] IV) Monoalkoxy titanium compound: for example, tris(dioctyl phosphate)titanium isopropoxide, tris(dodecylbenzene sulfonate)titanium isopropoxide, and the like.

[0812] V) Titanium oxide compound: for example, bis(pentanedione)titanium oxide, bis(tetramethylheptanedione)titanium oxide, titanium phthalocyanine oxide, and the like.

[0813] VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

[0814] VII) Titanate coupling agent: for example, isopropyl tri(dodecyl)benzenesulfonyl titanate.

[0815] Among them, as the organic titanium compound, from the viewpoint of better chemical resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) titanocene compounds is preferred. In particular, bis(ethyl acetoacetate)titanium diisopropoxide, tetra(n-butoxide)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0816] Furthermore, it is also preferable to contain a compound represented by the following formula (T-1) as the organic titanium compound or in place of the organic titanium compound.

[0817] [Chemical formula 50]

[0818]

[0819] In formula (T-1), M is titanium, zirconium or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1+l2×2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, l1+l2+m+n×2=4, R 11 are each independently a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted alkoxy, or a substituted or unsubstituted phenoxy, R 12is a substituted or unsubstituted hydrocarbon group, R 2 Each independently is a group containing a structure represented by the following formula (T-2), R 3 Each independently represents a group containing a structure represented by the following formula (T-2), X A are each independently an oxygen atom or a sulfur atom.

[0820] [Chemical formula 51]

[0821]

[0822] In formula (T-2), X 1 ~X 3 Each independently represents -C(-*)= or -N=, * represents a bonding site with other structures, and # represents a bonding site with a metal atom.

[0823] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium.

[0824] In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention.

[0825] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0826] In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1.

[0827] Here, in formula (T-1), it is also preferred that 11 and 12 are 0 and m is 0, 2 or 4.

[0828] In formula (T-1), from the viewpoint of stability of the specific metal complex, R 11 Substituted or unsubstituted cyclopentadiene ligands are preferred.

[0829] And, R 11 The cyclopentadienyl group, alkoxy group and phenoxy group in the above-mentioned group may be substituted, but an unsubstituted group is also a preferred embodiment of the present invention.

[0830] In formula (T-1), R 12 It is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.

[0831] As R 12 The hydrocarbon group in may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and is preferably an aromatic hydrocarbon group.

[0832] The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.

[0833] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and further preferably a phenylene group.

[0834] As R 12 The substituent in is preferably a monovalent substituent, and examples thereof include a halogen atom. 12 In the case of an aromatic hydrocarbon group, it may have an alkyl group as a substituent.

[0835] Among these, in formula (T-1), R 12 Preferably, it is an unsubstituted phenylene group. 12 The phenylene group in the is preferably 1,2-phenylene group.

[0836] In formula (T-1), m is 2 or more, when it contains 2 or more R 2 When the two or more R 2 The structures of can be the same or different.

[0837] In formula (T-1), n ​​is 2 or more, when it contains 2 or more R 3 When the two or more R 3 The structures of can be the same or different.

[0838] In formula (T-2), X 1 ~X 3 Each independently represents -C(-*)= or -N=, preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

[0839] Specific examples of the compound represented by formula (T-1) include compounds having the following structures, but are not limited thereto.

[0840] [Chemical formula 52]

[0841]

[0842] When an organic titanium compound is contained, the content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0843] 〔Antioxidant〕

[0844] By containing an antioxidant as an additive, the elongation characteristics of the cured film or the adhesion to the metal material can be improved. As antioxidants, phenol compounds, phosphite compounds, thioether compounds, etc. can be mentioned. As specific examples of antioxidants, compounds described in paragraphs 0348 to 0357 of International Publication No. 2021 / 112189 can be mentioned, and the content is incorporated into this specification.

[0845] The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By setting the addition amount to 0.1 parts by mass or more, even in a high temperature and high humidity environment, it is easy to obtain the effect of improving the elongation characteristics or the adhesion to the metal material, and by setting it to 10 parts by mass or less, for example, the sensitivity of the resin composition is improved by interaction with the photosensitizer. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, it is preferred that their total amount is within the above range.

[0846] 〔Anti-agglomerating agent〕

[0847] As the anti-agglomerating agent, sodium polyacrylate and the like can be mentioned.

[0848] One anti-agglomerating agent may be used alone, or two or more anti-agglomerating agents may be used in combination.

[0849] When the resin composition contains an anti-aggregating agent, the content of the anti-aggregating agent is preferably 0.01% by mass to 10% by mass, and more preferably 0.02% by mass to 5% by mass, based on the total solid content of the resin composition.

[0850] 〔Phenolic compounds〕

[0851] As phenolic compounds, there can be mentioned Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (the above are trade names, manufactured by ASAHI YUKIZAICORPORATION), etc.

[0852] The phenolic compounds may be used alone or in combination of two or more.

[0853] When the resin composition contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass to 30% by mass, and more preferably 0.02% by mass to 20% by mass, based on the total solid content mass of the resin composition.

[0854] 〔Other polymer compounds〕

[0855] Examples of other polymer compounds include silicone resins, (meth)acrylic acid polymers obtained by copolymerization with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products into which crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups are introduced.

[0856] The other polymer compounds may be used alone or in combination of two or more.

[0857] When the resin composition contains other polymer compounds, the content of the other polymer compounds is preferably 0.01 mass % to 30 mass % and more preferably 0.02 mass % to 20 mass % based on the total solid content of the resin composition.

[0858] [Compounds having a pyridine ring]

[0859] The resin composition may further contain a compound having a pyridine ring.

[0860] Examples of the compound 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-lutidine, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 2-mercaptopyridine, 3-mercaptopyridine, and 4-mercaptopyridine.

[0861] The compound having a pyridine ring may be used alone or in combination of two or more.

[0862] When the resin composition contains a compound having a pyridine ring, the content of the other polymer compound is preferably 0.01% by mass to 30% by mass, more preferably 0.02% by mass to 20% by mass, based on the total solid content of the resin composition.

[0863] <Characteristics of Resin Composition>

[0864] The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 / s~12,000mm 2 / s, more preferably 2,000 mm 2 / s~10,000mm 2 / s, more preferably 2,500mm 2 / s~8,000mm 2 / s. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000mm 2 / s or more, it is easy to apply the film thickness required as a redistribution insulating film. If it is 12,000mm 2 / s or less, a coating film with excellent coating surface shape can be obtained.

[0865] <Regarding Restrictions on Substances Contained in Resin Compositions>

[0866] The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and further preferably less than 1.0% by mass. When the water content is less than 2.0%, the storage stability of the resin composition is improved.

[0867] Examples of methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0868] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., except for metals contained as complexes of organic compounds and metals. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0869] In addition, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting raw materials with a low metal content as raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible, etc.

[0870] Regarding the resin composition of the present invention, if the use as a semiconductor material is considered, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, the halogen atoms present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. The total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is preferably within the above range, respectively.

[0871] As a method for adjusting the content of halogen atoms, ion exchange treatment or the like is preferably mentioned.

[0872] As a storage container for the resin composition of the present invention, a conventionally known storage container can be used. As a storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the resin composition of the present invention, a multilayer bottle having an inner wall of the container composed of six kinds of six layers of resins or a bottle having a seven-layer structure composed of six kinds of resins is preferably used. As such a container, for example, a container described in Japanese Patent Publication No. 2015-123351 can be cited.

[0873] <Cured product of resin composition>

[0874] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0875] The cured product of the present invention is a cured product obtained by curing the resin composition.

[0876] The curing of the resin composition is preferably carried out by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and a film, a rod, a sphere, a granular shape, etc. can be selected according to the purpose. In the present invention, the cured product is preferably in a film shape. Through the pattern processing of the resin composition, the shape of the cured product can also be selected according to the purpose of forming a protective film on the wall, forming a conductive through hole, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film formed by the cured product) is preferably 0.5μm or more and 150μm or less.

[0877] The shrinkage rate when curing the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after curing of the resin composition, and can be calculated by the following formula.

[0878] Shrinkage rate [%] = 100-(volume after curing ÷ volume before curing) × 100

[0879] <Characteristics of Cured Product of Resin Composition>

[0880] The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is 70% or more, the cured product may have excellent mechanical properties.

[0881] The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[0882] The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

[0883] <Preparation of resin composition>

[0884] The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

[0885] Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing while rotating a pot.

[0886] The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0887] For the purpose of removing foreign matter such as dust or particles in the resin composition of the present invention, it is preferred to filter using a filter. Regarding the filter pore size, for example, it is preferably less than 5 μm, more preferably less than 1 μm, further preferably less than 0.5 μm, and further preferably less than 0.1 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter can use a filter pre-cleaned with an organic solvent. In the filter filtering process, multiple filters can be connected in series or in parallel for use. When multiple filters are used, filters with different pore sizes or materials can be used in combination. As a connection method, for example, a method of connecting a HDPE filter with a pore size of 1 μm as the first stage and a HDPE filter with a pore size of 0.2 μm as the second stage in series can be cited. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be a circulation filter. In addition, filtering can also be performed after pressurization. When filtering is performed after pressurization, the pressure applied is preferably 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, further preferably 0.05 MPa to 0.7 MPa, and still further preferably 0.05 MPa to 0.5 MPa.

[0888] In addition to filtering using a filter, an impurity removal treatment using an adsorbent may also be performed. Filter filtering and impurity removal treatment using an adsorbent may also be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be cited.

[0889] After filtering with a filter, the resin composition filled in the bottle may be placed under reduced pressure for degassing.

[0890] (Method for producing cured product)

[0891] The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0892] The method for producing a cured product more preferably includes the film forming step, an exposure step of selectively exposing the film formed in the film forming step, and a developing step of developing the film exposed in the exposure step with a developer to form a pattern.

[0893] The method for producing a cured product particularly preferably includes the film forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.

[0894] Furthermore, it is also preferable that the method for producing a cured product includes the above-mentioned film forming step and the step of heating the above-mentioned film.

[0895] Hereinafter, the details of each step will be described.

[0896] <Film Formation Step>

[0897] The resin composition of the present invention can be used in a film forming step of applying the composition to a substrate to form a film.

[0898] The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0899] 〔Base material〕

[0900] The type of substrate can be appropriately determined according to the purpose and is not particularly limited. As the substrate, there can be cited semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates (for example, it can be any one of a substrate formed by a metal and a substrate having a metal layer formed by, for example, plating, vapor deposition, etc.), paper, SOG (Spin On Glass: Spin-on Glass), TFT (Thin Film Transistor) array substrate, mold substrate, plasma display panel (PDP) electrode plate, etc. In particular, the substrate is preferably a semiconductor manufacturing substrate, more preferably a silicon substrate, a Cu substrate and a mold substrate.

[0901] On the surface of these substrates, a layer such as an adhesive layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided.

[0902] The shape of the substrate is not particularly limited, and may be circular or rectangular.

[0903] Regarding the size of the substrate, for example, if the substrate is circular, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm, and for example, if the substrate is rectangular, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm.

[0904] As the substrate, for example, a plate-shaped substrate (substrate) can be used, and preferably a panel-shaped substrate (substrate) is used.

[0905] When a film is formed by applying the resin composition on the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as a substrate.

[0906] As a method of applying the resin composition to a substrate, coating is preferred.

[0907] As the method applied, specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet can be cited. From the viewpoint of uniformity of film thickness, preferably spin coating, slit coating, spray coating or inkjet, from the viewpoint of uniformity of film thickness and productivity, more preferably spin coating and slit coating. According to the method applied, the solid content concentration or coating conditions of the resin composition are adjusted, thereby a film of desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, preferably spin coating or spray coating, inkjet, etc., if it is a rectangular substrate, preferably slit coating, spray coating, inkjet, etc. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.

[0908] Furthermore, a method of transferring a coating film formed on a temporary support body in advance by the above-mentioned imparting method to a substrate can also be applied.

[0909] As for the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used.

[0910] Furthermore, a process of removing excess film at the edge of the substrate may be performed. Examples of such a process include edge bead rinse (EBR) and backwash.

[0911] A pre-wetting step may be adopted in which various solvents are applied on the substrate to improve the wettability of the substrate before applying the resin composition on the substrate, and then the resin composition is applied.

[0912] <Drying process>

[0913] After the film forming step (layer forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent.

[0914] That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.

[0915] The drying step is preferably performed after the film forming step and before the exposure step.

[0916] The drying temperature of the film in the drying step is preferably 50° C. to 150° C., more preferably 70° C. to 130° C., and further preferably 90° C. to 110° C. Furthermore, the drying may be performed by reducing pressure. The drying time may be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0917] <Exposure Process>

[0918] The film may be subjected to an exposure step of selectively exposing the film.

[0919] The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film forming step.

[0920] Selective exposure refers to exposing a portion of the film to light, and by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.

[0921] The exposure amount is not particularly limited as long as it can cure the resin composition of the present invention. For example, it is preferably 50 to 10,000 mJ / cm 2 , more preferably 200 to 8,000 mJ / cm 2 .

[0922] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0923] Regarding the exposure wavelength, in relation to the light source, there can be mentioned (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), wide wavelengths (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) second harmonics of YAG lasers of 532 nm and third harmonics of 355 nm, etc. In particular, exposure using a high-pressure mercury lamp is preferred for the resin composition of the present invention, and exposure using i-rays is more preferred from the viewpoint of exposure sensitivity.

[0924] The exposure method is not particularly limited as long as at least a part of the film formed from the resin composition of the present invention is exposed, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0925] <Post-exposure heating process>

[0926] The film may be subjected to a step of heating after exposure (post-exposure heating step).

[0927] That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.

[0928] The post-exposure heating step can be performed after the exposure step and before the development step.

[0929] The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.

[0930] The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0931] The temperature increase rate in the post-exposure heating step is preferably 1 to 12° C. / min, more preferably 2 to 10° C. / min, and even more preferably 3 to 10° C. / min from the temperature at the start of heating to the maximum heating temperature.

[0932] Furthermore, the heating rate can be appropriately changed during the heating process.

[0933] The heating method in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.

[0934] Furthermore, during heating, it is also preferred to conduct the heating in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0935] <Development Process>

[0936] The film after exposure may be subjected to a developing step of developing with a developer to form a pattern.

[0937] That is, the method for producing a cured product of the present invention may include a developing step of developing the film exposed in the exposing step using a developing solution to form a pattern.

[0938] By performing development, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern.

[0939] Here, development in which the non-exposed portion of the film is removed by the development step is referred to as negative development, and development in which the exposed portion of the film is removed by the development step is referred to as positive development.

[0940] 〔Developer〕

[0941] As a developer used in the development step, an aqueous alkali solution or a developer containing an organic solvent can be mentioned.

[0942] When the developer is an alkaline aqueous solution, examples of the alkaline compound that the alkaline aqueous solution can contain include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass, based on the total amount of the developer.

[0943] When the developer contains an organic solvent, the compound described in paragraph 0387 of International Publication No. 2021 / 112189 can be used as the organic solvent. This content is incorporated into this specification. In addition, as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc. can also be preferably mentioned, and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can also be preferably mentioned.

[0944] Furthermore, when the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0945] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content may also be 100% by mass.

[0946] When the developer contains an organic solvent, the developer may further contain at least one of an alkaline compound and an alkali generator. When at least one of the alkaline compound and the alkali generator in the developer penetrates into the pattern, the properties such as elongation at break of the pattern may be improved.

[0947] As the basic compound, an organic base is preferred from the viewpoint of reliability when remaining in a film after curing (adhesion to a substrate when the cured product is further heated).

[0948] As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides and the like are preferred. In order to promote the imidization 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 further preferred, and tertiary amines are particularly preferred.

[0949] As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, a compound that is not likely to remain in the cured film (the cured product obtained) is preferred, and from the viewpoint of promoting cyclization, a compound whose residual amount is not likely to be reduced by gasification before heating is preferred.

[0950] Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and further preferably 100°C to 230°C at normal pressure (101, 325 Pa).

[0951] The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.

[0952] For example, when the boiling point of the 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.

[0953] The developer may contain only one kind of basic compound or may contain two or more kinds of basic compounds.

[0954] Specific examples of the basic compound 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, butylenediamine, 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-diphenylamineethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propylenediamine, N-[3-(dimethylamino)propyl]acetamide, N-[3-(dimethylamino)propyl]acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-methyl-N-(2-methylaminopropyl)acetamide, and the like.

[0955] Preferred embodiments of the base generator are the same as those of the base generator contained in the above-mentioned composition. In particular, the base generator is preferably a thermal base generator.

[0956] When the developer contains at least one of an alkaline compound and an alkali generator, the content of the alkaline compound or the alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the developer. The lower limit of the above content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[0957] When the alkaline compound or the base generator is solid in an environment where a developer is used, the content of the alkaline compound or the base generator is preferably 70 to 100% by mass based on the total solid content of the developer.

[0958] The developer may contain only one or more of the alkaline compound and the alkali generator. When the alkaline compound and the alkali generator are two or more, the total amount thereof is preferably within the above range.

[0959] The developer may further contain other components.

[0960] As other components, for example, a known surfactant or a known defoaming agent can be mentioned.

[0961] [Developer supply method]

[0962] As long as the desired pattern can be formed, the method of supplying the developer is not particularly limited, and there are the following methods: a method of immersing the substrate formed with a film in the developer, a method of supplying the developer to the film formed on the substrate using a nozzle by a capping immersion development, or a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, and the like.

[0963] From the viewpoints of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, it is preferred to supply the developer using a straight nozzle or continuously supply the developer using a spray nozzle. From the viewpoint of the permeability of the developer to the image area, it is more preferred to supply the developer using a spray nozzle.

[0964] In addition, the following process can be adopted: after continuously supplying the developer with a straight nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a straight nozzle again, and the substrate is rotated to remove the developer from the substrate. This process can also be repeated multiple times.

[0965] Examples of a method for supplying the developer in the development step include a step of continuously supplying the developer to the substrate, a step of keeping the developer substantially stationary on the substrate, a step of vibrating the developer on the substrate using ultrasonic waves or the like, and a combination of these steps.

[0966] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0967] In the development step, the pattern may be cleaned (rinsed) with a rinse liquid after the processing with the developer. Alternatively, a method may be adopted in which the rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0968] 〔Rinsing fluid〕

[0969] When the developer is an alkaline aqueous solution, water can be used as the rinse liquid, and when the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0970] As the organic solvent in the case where the rinse solution contains an organic solvent, the same organic solvents as exemplified in the case where the developer contains an organic solvent can be mentioned.

[0971] The organic solvent contained in the rinse solution is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent having a lower solubility in the pattern than the organic solvent contained in the developer.

[0972] When the rinse liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, PGME, and further preferably cyclohexanone and PGMEA.

[0973] When the rinse liquid contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more relative to the total mass of the rinse liquid. Furthermore, the organic solvent may be 100% by mass relative to the total mass of the rinse liquid.

[0974] The rinse solution may contain at least one of a basic compound and an alkali generator.

[0975] Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains at least one of an organic solvent, an alkaline compound, and an alkali generator is also one of the preferred embodiments of the present invention.

[0976] Examples of the alkaline compound and the alkaline generator contained in the rinse solution include the alkaline compounds and the compounds exemplified as the alkaline generator that may be contained in the developer containing an organic solvent, and preferred embodiments are also the same.

[0977] The basic compound and the base generating agent contained in the rinse liquid may be selected in consideration of their solubility in the solvent in the rinse liquid.

[0978] When the rinse liquid contains at least one of an alkaline compound and an alkali generator, the content of the alkaline compound or the alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the rinse liquid. The lower limit of the above content is not particularly limited, for example, preferably 0.1% by mass or more.

[0979] When the basic compound or base generator is solid in the environment where the rinse liquid is used, the content of the basic compound or base generator is preferably 70 to 100% by mass based on the total solid content of the rinse liquid.

[0980] When the rinse liquid contains at least one of an alkaline compound and an alkali generator, the rinse liquid may contain only one alkaline compound and at least one of an alkali generator, or may contain two or more alkaline compounds and at least one of an alkali generator. When at least one of the alkaline compound and the alkali generator is two or more, the total amount thereof is preferably within the above range.

[0981] The rinse solution may also contain other ingredients.

[0982] As other components, for example, a known surfactant or a known defoaming agent can be mentioned.

[0983] [Method of supplying flushing fluid]

[0984] As long as the desired pattern can be formed, there is no particular limitation on the method for supplying the rinsing liquid, and the following methods are available: a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate through liquid accumulation, a method of supplying the rinsing liquid to the substrate through spraying, and a method of continuously supplying the rinsing liquid to the substrate through a straight nozzle or the like.

[0985] From the viewpoint of the permeability of the rinse liquid, the removal of the non-image part, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., preferably a method of continuously supplying using a spray nozzle, and from the viewpoint of the permeability of the rinse liquid to the image part, more preferably a method of supplying using a spray nozzle. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.

[0986] That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle.

[0987] The method for supplying the rinsing liquid in the rinsing step may include continuously supplying the rinsing liquid to the substrate, maintaining the rinsing liquid in a substantially static state on the substrate, vibrating the rinsing liquid on the substrate using ultrasound or the like, and a combination of these.

[0988] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0989] In the development process, after processing with a developer or cleaning the pattern with a rinse solution, a process of bringing the treatment solution into contact with the pattern may be included. In addition, a method of supplying the treatment solution before the developer or rinse solution in contact with the pattern is completely dried may also be adopted.

[0990] Examples of the treatment liquid include a treatment liquid containing at least one of water and an organic solvent and at least one of a basic compound and an alkali generator.

[0991] Preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator are the same as preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator used in the rinse solution.

[0992] The method for supplying the processing liquid to the pattern can be the same method as the method for supplying the rinse liquid, and the preferred aspects are also the same.

[0993] The content of the basic compound or base generating agent in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment liquid. The lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example.

[0994] Furthermore, when the basic compound or the base generating agent is solid in the environment where the treatment liquid is used, the content of the basic compound or the base generating agent is preferably 70 to 100% by mass based on the total solid content of the treatment liquid.

[0995] When the treatment liquid contains at least one of an alkaline compound and an alkali generator, the treatment liquid may contain only one alkaline compound and at least one of an alkali generator, or may contain two or more alkaline compounds and at least one of an alkali generator. When at least one of the alkaline compound and the alkali generator is two or more, the total amount thereof is preferably within the above range.

[0996] <Heating process>

[0997] The pattern obtained by the development step (the pattern after the rinsing step when the rinsing step is performed) can be subjected to a heating step of heating the pattern obtained by the development.

[0998] That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step.

[0999] Furthermore, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a development step or a film obtained by a film forming step.

[1000] In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as a polyimide.

[1001] Furthermore, crosslinking of unreacted crosslinking groups in the specific resin or the crosslinking agent other than the specific resin is also performed.

[1002] The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, further preferably 160 to 250°C, particularly preferably 160 to 230°C.

[1003] The heating step is preferably a step of accelerating the cyclization reaction of the polyimide precursor in the pattern by heating and utilizing the action of a base or the like generated by the base generator.

[1004] Regarding the heating in the heating process, it is preferred to perform the 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 further preferably 3 to 10°C / min. By setting the heating rate to be 1°C / min or more, productivity can be ensured and excessive volatilization of the acid or solvent can be prevented. By setting the heating rate to be 12°C / min or less, the residual stress of the cured product can be relaxed.

[1005] In the case of an oven capable of rapid heating, the heating is preferably performed at a heating rate of 1 to 8°C / sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C / sec, and still more preferably 3 to 6°C / sec.

[1006] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, it is the temperature of the dried film (layer), for example, preferably starting from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[1007] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and further preferably 15 to 240 minutes.

[1008] In particular, when a multilayer laminate is formed, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, further preferably 100° C. or higher, and particularly preferably 120° C. or higher from the viewpoint of interlayer adhesion.

[1009] The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and further preferably 240°C or lower.

[1010] Heating can be performed in stages. As an example, the following process can be performed: heating from 25°C to 120°C at 3°C / min and maintaining at 120°C for 60 minutes, heating from 120°C to 180°C at 2°C / min and maintaining at 180°C for 120 minutes. In addition, as described in the specification of U.S. Patent No. 9159547, it is also preferred to treat while irradiating with ultraviolet rays. The properties of the film can be improved by this pretreatment process. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be set as a process of more than two stages, for example, the first stage pretreatment process can be performed in the range of 100 to 150°C, and then the second stage pretreatment process can be performed in the range of 150 to 200°C.

[1011] Furthermore, the heating may be followed by cooling, and the cooling rate at this time is preferably 1 to 5° C. / min.

[1012] The heating step is preferably performed in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon under reduced pressure, etc., from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[1013] The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[1014] <Exposure Step after Development>

[1015] The pattern obtained by the development step (the pattern after the rinse step when the rinse step is performed) may be subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.

[1016] That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step.

[1017] In the post-development exposure step, for example, a cyclization reaction of a polyimide precursor or the like by photosensitization of a photobase generator, a leaving reaction of an acid-decomposable group by photosensitization of a photoacid generator, and the like can be promoted.

[1018] In the post-development exposure step, at least a portion of the pattern obtained in the development step may be exposed, but it is preferred that the entire pattern be exposed.

[1019] The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm2 in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. 2 , more preferably 100 to 15,000 mJ / cm 2 .

[1020] The post-development exposure step can be performed, for example, using the light source in the above-mentioned exposure step, and preferably using broadband light.

[1021] <Metal Layer Formation Step>

[1022] The pattern obtained in the development step (preferably the pattern provided to at least one of the heating step and the post-development exposure step) may be provided to the metal layer forming step of forming a metal layer on the pattern.

[1023] That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained in the development step (preferably a pattern provided for at least one of the heating step and the post-development exposure step).

[1024] The metal layer is not particularly limited, and any existing metal species can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is further preferred.

[1025] The formation method of metal layer is not particularly limited, and existing method can be applied.For example, the method described in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used.For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), peeling (lift off), electrolytic plating, electroless plating, etching, printing and combining these methods etc. can be considered.More specifically, the patterning method of combining sputtering, photolithography and etching, the patterning method of combining photolithography and electrolytic plating can be enumerated.As the preferred mode of plating, the electrolytic plating using copper sulfate or copper cyanide plating solution can be enumerated.

[1026] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, based on the thickest portion.

[1027] <Purpose>

[1028] As the fields to which the manufacturing method of the cured product of the present invention or the cured product can be applied, there can be cited insulating films of electronic devices, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, there can be cited sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, interlayer insulating films), or the case where patterns are formed on insulating films for installation purposes such as the above by etching, etc. For these uses, for example, reference can be made to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimides" April 2008, Kakimoto Masaaki / Supervision, CMC Technical Library "Basics and Development of Polyimide Materials" November 2011, Japan Polyimide and Aromatic Polymer Research Society / Editor "Latest Polyimide Basics and Applications" NTS, August 2010, etc.

[1029] The method for producing the cured product of the present invention or the cured product of the present invention can also be used in the production of offset printing plates or screen printing plates, the use of etched parts, the production of protective varnishes and dielectric layers in electronic products, especially microelectronic products, etc.

[1030] (Laminate and method for producing laminate)

[1031] The laminate of the present invention refers to a structure having a plurality of layers formed of the cured product of the present invention.

[1032] The laminated body is a laminated body including two or more layers formed of a cured product, and may be a laminated body including three or more layers.

[1033] Among the two or more layers formed by the above-mentioned cured product contained in the above-mentioned laminate, at least one layer is a layer formed by the cured product of the present invention. From the viewpoint of suppressing the shrinkage of the cured product or the deformation of the cured product accompanying the above-mentioned shrinkage, it is also preferred that all the layers formed by the cured product contained in the above-mentioned laminate are layers formed by the cured product of the present invention.

[1034] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes a step of repeating the method for producing a cured product of the present invention a plurality of times.

[1035] The laminate of the present invention preferably includes two or more layers formed of a cured product, and preferably includes a metal layer between any of the layers formed of the cured product. The metal layer is preferably formed by the metal layer forming step.

[1036] That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer formed of a cured product before performing the method for producing a cured product a plurality of times. A preferred embodiment of the metal layer forming step is as described above.

[1037] As the above-mentioned laminate, for example, a laminate having a layer structure including at least three layers stacked in this order: a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product is preferably used.

[1038] The layer formed by the first cured product and the layer formed by the second cured product are preferably layers formed by the cured product of the present invention. The resin composition of the present invention for forming a layer formed by the first cured product and the resin composition of the present invention for forming a layer formed by the second cured product can be compositions with the same composition or compositions with different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

[1039] <Lamination process>

[1040] The method for producing a laminated body of the present invention preferably includes a lamination step.

[1041] The lamination process is a series of processes including performing at least one of (a) a film forming process (layer forming process), (b) an exposure process, (c) a developing process, (d) a heating process, and a post-development exposure process again in sequence on the surface of a pattern (resin layer) or a metal layer. Among them, it can be a method of repeating at least one of (a) a film forming process, (d) a heating process, and a post-development exposure process. In addition, (e) a metal layer forming process can be included after at least one of (d) a heating process and a post-development exposure process. Of course, the lamination process can further include the above-mentioned drying process, etc. as appropriate.

[1042] When the lamination process is further performed after the lamination process, a surface activation process may be further performed after the exposure process and after the heating process or after the metal layer forming process. As the surface activation process, plasma treatment is exemplified. The details of the surface activation process will be described later.

[1043] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.

[1044] For example, the resin layer may have a structure of resin layer / metal layer / resin layer / metal layer / resin layer / metal layer. The resin layer may have a structure of preferably 2 to 20 layers, more preferably 2 to 9 layers.

[1045] The composition, shape, film thickness, etc. of each of the above-mentioned layers may be the same or different.

[1046] In the present invention, it is particularly preferred that the cured product (resin layer) of the resin composition of the present invention is further formed after the metal layer is set to cover the above-mentioned metal layer. Specifically, the method of repeating the order of (a) film forming process, (b) exposure process, (c) developing process, (d) heating process and at least one of the post-exposure process, (e) metal layer forming process, or (a) film forming process, (d) heating process and at least one of the post-exposure process, (e) metal layer forming process can be cited. By alternately stacking the stacking process and the metal layer forming process of the resin composition layer (resin layer) of the present invention, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately stacked.

[1047] (Surface activation treatment process)

[1048] The method for producing a laminate of the present invention preferably includes a surface activation step of subjecting at least a portion of the metal layer and the resin composition layer to surface activation treatment.

[1049] The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step may be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) or after the resin composition layer is subjected to the surface activation treatment step.

[1050] The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and preferably on a portion or all of the region in the metal layer where the resin composition layer is formed on the surface. In this way, by performing a surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) disposed on the surface thereof can be improved.

[1051] The surface activation treatment is also preferably performed on a part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, the adhesion with the metal layer and the resin layer provided on the surface after the surface activation treatment can be improved. In particular, when the resin composition layer is cured, such as when negative development is performed, it is not easy to be damaged by the surface treatment, and the adhesion is easily improved.

[1052] The surface activation treatment can be performed by the method described in paragraph 0415 of International Publication No. 2021 / 112189, for example. This content is incorporated into this specification.

[1053] (Semiconductor device and method of manufacturing the same)

[1054] The present invention also discloses a semiconductor device comprising the cured product or the laminate of the present invention.

[1055] Furthermore, the present invention discloses a method for producing a semiconductor device including the method for producing a cured product or a method for producing a laminate according to the present invention.

[1056] As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated herein.

[1057] Example

[1058] Hereinafter, the present invention will be further specifically described by giving examples. The materials, usage amounts, ratios, processing contents, processing sequences, etc. shown in the following examples can be appropriately changed without departing from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are weight references.

[1059] <Synthesis of Resin>

[1060] [Synthesis Example 1: Synthesis of polymer P-1]

[1061] 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 diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, after the obtained diester was chlorinated with SOCl2, a solution obtained by dissolving 4,4'-diaminodiphenyl ether in N-methylpyrrolidone was added dropwise to the reaction mixture in the same manner as in Synthesis Example 2 described later, and then the obtained reaction mixture was purified and dried. The weight average molecular weight of the polyimide precursor (polymer P-1) was 18,000. Polymer P-1 is a resin having the following structure.

[1062] [Chemical formula 53]

[1063]

[1064] [Synthesis Example 2: Synthesis of polymer P-2]

[1065] 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) and 6.23 g (25 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride were added to 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 heat generated by the reaction ended, the mixture was naturally cooled to room temperature and further left to stand for 16 hours.

[1066] Next, 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 under ice cooling over 40 minutes with stirring. Subsequently, a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring.

[1067] After stirring at room temperature for 2 hours, 3 ml of ethanol was added and stirred for 1 hour. Then, 100 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

[1068] The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate consisting of a crude polymer. The generated 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 vacuum dried to obtain a powdered polymer P-2.

[1069] The weight average molecular weight (Mw) of the polymer was measured and found to be 23,000.

[1070] The polymer P-2 is a resin having the following structure.

[1071] [Chemical formula 54]

[1072]

[1073] ※Compounds with a molar ratio of 50:50 between the skeletons derived from two types of acid anhydrides

[1074] [Synthesis Example 3: Synthesis of polymer P-3]

[1075] 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 diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture was cooled and 16.12 g (135.5 mmol) of SOCl2 was added over 2 hours. Next, a solution obtained by dissolving 12.74 g (60.0 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine in 100 mL of N-methylpyrrolidone was adjusted to a temperature range of -5 to 0°C and added dropwise to the reaction mixture over a period of 2 hours. After the reaction mixture was reacted at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature for 1 hour. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried under reduced pressure for two days. The weight average molecular weight of the polyimide precursor (polymer P-3) was 29,000.

[1076] The polymer P-3 is a resin having the following structure.

[1077] [Chemical formula 55]

[1078]

[1079] <Examples and Comparative Examples>

[1080] In each example, the components described in the following table were mixed to obtain each composition. In addition, in the comparative example, the components described in the following table were mixed to obtain a comparative composition.

[1081] Specifically, the content (compound amount) of each component in the composition is set to the amount (parts by mass) described in each column of the table.

[1082] The obtained composition and the comparative composition were filtered under pressure using a polytetrafluoroethylene filter having a pore width of 0.45 μm.

[1083] In the table, "-" indicates that the composition does not contain the corresponding component.

[1084] [Table 1]

[1085]

[1086] [Table 2]

[1087]

[1088] [Table 3]

[1089]

[1090] [Table 4]

[1091]

[1092] The details of each component described in the table are as follows.

[1093] 〔Polyimide precursor〕

[1094] · P-1 to P-3: polymers P-1 to P-3 obtained by the above-mentioned synthesis examples

[1095] 〔Polymerizable compounds〕

[1096] B-1: SR-209 (manufactured by Sartomer Company, Inc.)

[1097] ·B-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[1098] ·B-3 to B-8: Compounds of the following structures

[1099] [Chemical formula 56]

[1100]

[1101] 〔Photopolymerization initiator〕

[1102] C-1: Irgacure OXE01

[1103] C-2: Irgacure 784

[1104] ·C-3 to C-5: Compounds of the following structures

[1105] C-6: Irgacure OXE02

[1106] C-7: NCI-930

[1107] [Chemical formula 57]

[1108]

[1109] 〔Inhibitor〕

[1110] ·D-1: Compound with the following structure

[1111] ·D-2: TEMPO, 2,2,6,6-tetramethylpiperidinyl 1-oxyl

[1112] ·D-3: POLYSTOP 7300P (manufactured by Hakuto Co., Ltd.)

[1113] ·D-4~D-5: Compounds with the following structures

[1114] [Chemical formula 58]

[1115]

[1116] 〔Silane coupling agent〕

[1117] ·E-1 to E-4: compounds of the following structures, where Et represents ethyl

[1118] ·E-5: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1119] ·E-6: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1120] [Chemical formula 59]

[1121]

[1122] 〔Migration inhibitor〕

[1123] ·F-1 to F-4: Compounds of the following structures

[1124] [Che...

Claims

1. 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 Solvents, The content of each of N-methylpyrrolidone and γ-butyrolactone is 0.1% by mass or less relative to the total mass of the resin composition. 2 . The resin composition according to claim 1 , comprising γ-valerolactone as the solvent.

3. 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 γ-Valerolactone.

4. The resin composition according to claim 2 or 3, wherein The content of the γ-valerolactone is 60% by mass or more based on the total mass of the solvent. 5 . The resin composition according to claim 1 , further comprising dimethyl sulfoxide as the solvent. 6 . The resin composition according to claim 1 , further comprising a polymerizable compound and a photopolymerization initiator. 7 . The resin composition according to claim 1 , which is used for forming an interlayer insulating film for a redistribution layer. 8 . A cured product obtained by curing the resin composition according to claim 1 . 9 . A laminate comprising two or more layers formed of the cured product according to claim 8 , wherein a metal layer is provided between any of the layers formed of the cured product. 10 . A method for producing a cured product, comprising a film forming step of applying the resin composition according to claim 1 to a substrate to form a film.

11. The method for producing a cured product according to claim 10, comprising: An exposure step of selectively exposing the film to light; and In the development step, the film is developed using a developer to form a pattern. 12 . The method for producing a cured product according to claim 10 , comprising a heating step of heating the film at 50° C. to 450° C. 13 . A method for producing a laminate, comprising the method for producing a cured product according to claim 10 .

14. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 10.

15. A semiconductor device comprising the cured product according to claim 8.

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