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

Abstract

The present application provides a resin composition, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a semiconductor device including the cured product or the laminate, and a novel compound, the resin composition including at least one resin selected from a cyclized resin and a precursor thereof and a polymerizable compound having a polymerizable group and an amide bond which are bonded to each other via a linking group, the amide bond being bonded to the linking group at a carbonyl group side, and in a case where a homopolymer is synthesized using the polymerizable compound, the homopolymer exhibits a property of generating a base liberated from a main chain by heating at 250°C.

Description

Technical Field

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

[0002] Cyclic resins such as polyimide possess excellent heat resistance and insulation properties, making them suitable for a wide range of applications. While there are no particular limitations on these applications, for example, in the case of semiconductor devices used for actual mounting, they can be used as insulating films, sealing materials, or protective films. Furthermore, they can also be used as base films or cover films for flexible substrates.

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

[0004] This resin composition is applied to a substrate, for example, by coating, to form a photosensitive film. Then, exposure, development, heating, etc., are performed as needed to form a cured product on the substrate.

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

[0006] The resin composition can be applied using known coating methods, thus exhibiting excellent manufacturing adaptability. For example, the applicable resin composition offers a high degree of freedom in designing its shape, size, and application location. In addition to the high performance of cyclized resins such as polyimide, the excellent manufacturing adaptability makes the industrial application development of the aforementioned resin composition increasingly anticipated.

[0007] For example, Patent Document 1 describes a photosensitive resin composition containing a polymeric precursor that promotes the reaction of the final product by means of an alkaline substance or by heating in the presence of an alkaline substance, and an alkali-generating agent having a specific structure that generates alkali by irradiation and heating with electromagnetic waves.

[0008] Previous technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2013-194205 Summary of the Invention

[0011] The technical problem to be solved by the invention

[0012] In a resin composition comprising at least one of a cyclized resin and a precursor of a cyclized resin, it is required that the film shrinkage of the obtained cured product is reduced.

[0013] Film shrinkage refers to the reduction (shrinkage) in volume of the cured product (e.g., cured film) obtained after curing compared to the composition before curing (e.g., the composition film before heating). From the viewpoints of easily obtaining cured products of the target size and the adhesion between the cured product and the substrate, it is desirable to have a small reduction in the volume of the cured product, i.e., to reduce film shrinkage.

[0014] The purpose of this invention is to provide a resin composition with reduced film shrinkage of the obtained cured product, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, a method for manufacturing the above cured product, and a semiconductor device containing the above cured product or the above laminate.

[0015] Furthermore, the object of this invention is to provide a new compound.

[0016] means for solving technical problems

[0017] Examples of representative embodiments of the present invention are shown below.

[0018] <1> A resin composition comprising:

[0019] At least one resin selected from cyclized resins and their precursors; and

[0020] Polymerizable compounds having polymerizable groups and amide bonds bonded together via linking groups.

[0021] The amide bond described above is bonded to the linker group on the carbonyl side.

[0022] When a homopolymer was synthesized using the above-mentioned polymeric compound, the homopolymer exhibited the property of producing a base free from the main chain upon heating to 250°C.

[0023] <2> according to <1> The resin composition wherein the polymeric groups in the polymeric compound are free radical polymeric groups.

[0024] <3> according to <1> or <2> The resin composition wherein the polymeric compound is a compound represented by the following formula (1-1).

[0025] [Chemical Formula 1]

[0026]

[0027] In equation (1-1), R 1 Each is an independent hydrogen atom or a monovalent organic group, with two R atoms. 1 They can bond together to form a ring structure, R 2 Each of the following is an organic group that is independently a hydrogen atom, a halogen atom, or a monovalent organic group, and has at least two R atoms. 2They can bond together to form a ring structure, L 1 This indicates a trivalent organic group.

[0028] <4> according to <1> to <3> The resin composition of any one of the above, wherein the polymerizable compound is a compound represented by the following formula (1-2).

[0029] [Chemical Formula 2]

[0030]

[0031] In equation (1-2), R 1 Each of the two Rs can independently represent a hydrogen atom or a monovalent organic group. 1 They can bond together to form a ring structure, L 2 Represents a single bond or a divalent linker; Cy represents a ring structure; L 3 R represents a linker base that is either a single bond or divalent. 2 Each of the following groups independently represents a hydrogen atom, a halogen atom, or a monovalent organic group, with at least two R atoms. 2 They can bond together to form a ring structure.

[0032] <5> according to <1> to <4> The resin composition of any one of the above, wherein the resin has polymerizable groups.

[0033] <6> according to <1> to <5> The resin composition of any one thereof further comprises a photopolymerization initiator.

[0034] <7> according to <1> to <6> The resin composition of any one of the above-described resins further comprises a polymeric compound different from the polymeric compound described above.

[0035] <8> according to <1> to <7> The resin composition described herein is used to form an interlayer insulating film for a rewiring layer.

[0036] <9> A solidified substance, which is... <1> to <8> It is formed by curing any one of the resin compositions described herein.

[0037] <10> A laminate comprising two or more layers of material <9> The cured material forms a layer, and the layers formed by the cured material include metal layers between each other at will.

[0038] <11> A method for manufacturing a cured material, comprising: <1> to <8> Any of the resin compositions described herein is suitable for a film forming process in which a film is formed on a substrate.

[0039] <12> according to <11> The method for manufacturing the cured material includes an exposure step of selectively exposing the film and a development step of developing the film using a developing solution to form a pattern.

[0040] <13> according to <11> or <12> The method for manufacturing the cured material includes a heating step of heating the film at 50 to 450°C.

[0041] <14> A semiconductor device comprising <9> The solidified material or <10> The aforementioned laminated body.

[0042] <15> A compound represented by the following formula (1-1),

[0043] [Chemical Formula 3]

[0044]

[0045] In equation (1-1), R 1 Each is an independent hydrogen atom or a monovalent organic group, with two R atoms. 1 They can bond together to form a ring structure, R 2 Each of the following is an organic group that is independently a hydrogen atom, a halogen atom, or a monovalent organic group, and has at least two R atoms. 2 They can bond together to form a ring structure, L 1 This indicates a trivalent organic group.

[0046] <16> A compound, represented by the following formula (1-2),

[0047] [Chemical Formula 4]

[0048]

[0049] In equation (1-2), R 1 Each of the two Rs can independently represent a hydrogen atom or a monovalent organic group. 1 They can bond together to form a ring structure, L 2 Represents a single bond or a divalent linker; Cy represents a ring structure; L 3 R represents a linker base that is either a single bond or divalent. 2 Each of the following groups independently represents a hydrogen atom, a halogen atom, or a monovalent organic group, with at least two R atoms. 2 They can bond together to form a ring structure.

[0050] Invention Effects

[0051] According to the present invention, a resin composition with reduced film shrinkage of the obtained cured product is provided, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate.

[0052] Furthermore, according to the present invention, a novel compound is provided. Detailed Implementation

[0053] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown.

[0054] In this specification, the numerical range indicated by the symbol “~” represents the range included by the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0055] In this specification, the term "process" not only refers to an independent process, but also includes processes that cannot be clearly distinguished from other processes, as long as the intended function of the process can be achieved.

[0056] Regarding the designation of groups (atomic groups) in this specification, the designations for unsubstituted and unsubstituted groups (atomic groups) include both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0057] In this specification, unless otherwise stated, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and activated light or radiation such as electron beams.

[0058] In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either one; “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid” or either one; and “(meth)acryloyl” means “acryloyl” and “methacryloyl” or either one.

[0059] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0060] In this specification, total solids content refers to the total mass of all components of the composition, excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0061] In this specification, unless otherwise stated, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined using gel permeation chromatography (GPC) and are defined as polystyrene equivalents. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise stated, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. Where THF is unsuitable as the eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise stated, the detection in GPC measurements is performed using a UV (ultraviolet) detector with a wavelength of 254 nm.

[0062] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer in the multilayer of interest. That is, a third layer or element may be further sandwiched between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Furthermore, unless otherwise stated, the direction in which the layers are gradually stacked relative to the substrate is referred to as "upper," or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." In addition, this setting of up and down directions is for the convenience of explaining this specification; in practice, the "upper" direction in this specification may also be different from vertically upward.

[0063] In this specification, unless otherwise stated, each component included in the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise stated, the content of each component in the composition represents the total content of all compounds corresponding to that component.

[0064] In this specification, unless otherwise stated, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0065] In this specification, the preferred combination of methods is a more preferred method.

[0066] (Resin Composition)

[0067] The resin composition of the present invention comprises at least one resin selected from cyclized resins and their precursors (hereinafter also referred to as "specific resin") and a polymeric compound having polymeric groups and amide bonds bonded to each other via linking groups (hereinafter also referred to as "specific polymeric compound"). The amide bonds are bonded to the linking groups on the carbonyl side. When a homopolymer is synthesized using the polymeric compound, the homopolymer exhibits the property of generating a base free from the main chain upon heating to 250°C. Furthermore, the homopolymer preferably exhibits the property of generating a base free from the main chain upon heating to 220°C, more preferably upon heating to 200°C, even more preferably upon heating to 190°C, and particularly preferably upon heating to 180°C.

[0068] The resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and more preferably to form a film for exposure and development using a developer containing an organic solvent.

[0069] The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for rewiring layers.

[0070] Furthermore, the resin composition of the present invention can be used to form a photosensitive film for positive development or for negative development.

[0071] In this invention, negative development refers to the development that removes the non-exposed areas through development during exposure and development, while positive development refers to the development that removes the exposed areas through development.

[0072] The exposure method, the developer, and the development method described above can be, for example, the exposure method described in the exposure step of the description of the method for manufacturing cured material described later, and the developer and development method described in the development step.

[0073] In the resin composition of the present invention, the film shrinkage of the cured product is reduced.

[0074] The mechanism by which the above effects are achieved is not yet clear, but it is speculated to be as follows.

[0075] A particular polymerizable compound has polymerizable groups and amide bonds bonded to each other via a linker, and the amide bonds are bonded to the linker on the carbonyl side.

[0076] A specific polymerizable compound is one that produces a base by breaking the amide bond through heating.

[0077] That is, the resin composition of the present invention contains a specific polymerizable compound having a polymerizable group on a side different from the generated alkali (carbonyl side). Specifically, when the composition composed of the resin composition of the present invention is heated before curing, the decomposition product of the specific polymerizable compound after the alkali is generated by heating becomes polymerized.

[0078] Therefore, it is believed that the glass transition temperature (Tg) of the membrane increases due to the reduction of low molecular weight components in the membrane during heating, and the increase in crosslinking density of the membrane through polymerization due to the polymerizable groups of certain polymerizable compounds, thus reducing membrane shrinkage during heating.

[0079] Furthermore, it is believed that the reduction of low-molecular-weight components remaining in the obtained cured material improves chemical resistance.

[0080] Furthermore, it is speculated that when a specific polymeric compound is polymerized during exposure before heating, the dissolution of the specific polymeric compound caused by development can be suppressed. Therefore, the amount of alkali generated during heating increases, and the elongation at break of the cured product increases. Additionally, it is believed that the alkali generated from the specific polymeric compound itself does not polymerize and therefore readily diffuses within the film. Therefore, it is thought that, for example, when a precursor of a specific resin is used as the specific resin, the cyclization-promoting effect of the alkali-based precursor of the specific resin is significant.

[0081] Furthermore, it is believed that the structure of certain polymeric compounds before the formation of alkali is close to neutral, and the resin composition containing such compounds also exhibits excellent storage stability.

[0082] Patent document 1 does not describe a specific polymerizable compound.

[0083] The components contained in the resin composition of the present invention will be described in detail below.

[0084] <Specific Resin>

[0085] The resin composition of the present invention comprises at least one resin (specific resin) selected from cyclized resins and their precursors.

[0086] Cyclic resins are preferably resins that contain an imide ring structure or an oxazole ring structure in their main chain structure.

[0087] In this invention, the main chain refers to the longest bonded chain in the resin molecule.

[0088] Examples of cyclized resins include polyimide, polybenzoxazole, and polyamide-imide.

[0089] The precursor of a cyclized resin refers to a resin that becomes a cyclized resin due to a change in its chemical structure caused by external stimuli. Preferably, it is a resin that becomes a cyclized resin due to a change in its chemical structure caused by heat. More preferably, it is a resin that becomes a cyclized resin by forming a ring structure through a ring-closing reaction caused by heat.

[0090] Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors.

[0091] That is, the resin composition of the present invention preferably contains at least one resin (specific resin) selected from polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide imide and polyamide imide precursor as a specific resin.

[0092] The resin compositions of the present invention preferably contain polyimide or polyimide precursor as a specific resin.

[0093] Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups.

[0094] When a particular resin has free radical polymerizable groups, the resin composition of the present invention preferably contains the free radical polymerization initiator described later, more preferably it contains both the free radical polymerization initiator described later and the free radical crosslinking agent described later. Furthermore, sensitizers described later may be included as needed. Such resin compositions of the present invention can be used to form, for example, negative photosensitive films.

[0095] Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups.

[0096] In cases where a particular resin has acid-degrading groups, the resin composition of the present invention preferably contains the photoacid-generating agent described later. Such resin compositions of the present invention can be used to form, for example, chemically amplified positive or negative photosensitive films.

[0097] Furthermore, when a particular resin has polymerizable groups, the particular resin preferably has polymerizable groups capable of polymerizing with the particular polymerizable compound. It is speculated that, in this way, polymerization occurs even between the particular resin and the particular polymerizable compound, and the particular polymerizable compound is distributed at intervals in the polymer formed by polymerization. As a result, it is speculated that the location of alkali generation in the membrane is less likely to shift, for example, easily promoting the ring closure of the precursor of the cyclized resin or easily promoting the polymerization of polymerizable compounds polymerized by alkali.

[0098] For example, the presence of free radical polymerizable groups in a particular resin and the presence of free radical polymerizable groups in a particular polymerizable compound are also preferred embodiments of the present invention.

[0099] [Polyimide precursor]

[0100] The type of polyimide precursor used in this invention is not particularly specified, but it is preferred to include repeating units represented by the following formula (2).

[0101] [Chemical Formula 5]

[0102]

[0103] In equation (2), A 1 and A 2 Each can be used independently to represent an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0104] A in equation (2) 1 and A 2 Each can be represented independently as an oxygen atom or -NH-, preferably an oxygen atom.

[0105] R in equation (2) 111 This refers to a divalent organic group. Examples of divalent organic groups include groups comprising straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, these are straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. More preferably, these are groups comprising aromatic groups with 6 to 20 carbon atoms. The aforementioned straight-chain or branched aliphatic groups can be substituted with groups whose hydrocarbon groups contain heteroatoms, and the aforementioned cyclic aliphatic groups and aromatic groups can be substituted with groups whose cyclic hydrocarbon groups contain heteroatoms. As a preferred embodiment of the invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, with groups represented by -Ar-L-Ar- being particularly preferred. Wherein, Ar is an aromatic group independently, and L is a group comprising a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. These preferred ranges are as described above.

[0106] R 111 The preferred derivative is a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more may be used.

[0107] Specifically, the preferred diamine is a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof; more preferably, a diamine is a group containing an aromatic group having 6 to 20 carbon atoms. The aforementioned straight-chain or branched aliphatic groups can be substituted with groups whose hydrocarbon groups in the chain contain heteroatoms, and the aforementioned cyclic aliphatic groups and aromatic groups can be substituted with groups whose hydrocarbon groups in the cyclic members contain heteroatoms. Examples of groups containing aromatic groups include the following.

[0108] [Chemical Formula 6]

[0109]

[0110] In the formula, A represents a single bond or a divalent linker, preferably a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof, more preferably a group selected from alkylene groups with 1 to 3 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0111] In the formula, * indicates the bonding site with other structures.

[0112] As a diamine, specifically, examples include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diamino... 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone or 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether or 3,3'-diaminodiphenyl ether, 4,4'-diaminodibenzophenone or 3,3'-diaminodibenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy- 4-Aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-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)furan, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2, 7-Diaminophen, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2- bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl At least one diamine selected from the following: 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0113] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0114] Furthermore, a diamine having two or more alkylene glycol units as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 on the main chain may also be preferred.

[0115] From the perspective of the flexibility of the obtained organic membrane, R 111Preferably represented by -Ar-L-Ar-. Wherein, Ar is an independent aromatic group, and L is a group comprising an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. Ar is preferably phenylene, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably alkylene.

[0116] Furthermore, considering i-ray transmittance, R 111 Preferably, it is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

[0117] Equation (51)

[0118] [Chemical Formula 7]

[0119]

[0120] In equation (51), R 50 ~R 57 R is an organic group that is independently composed of a hydrogen atom, a fluorine atom, or a monovalent organic group. 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * represents the bonding site with the nitrogen atom in formula (2) independently.

[0121] As R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0122] [Chemical Formula 8]

[0123]

[0124] In equation (61), R 58 and R 59 Each of the above can be independently represented by a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2).

[0125] Examples of diamines providing the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used in combination.

[0126] R in equation (2) 115 The term represents a tetravalent organic group. As a tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred.

[0127] In equation (5) or equation (6), * independently represents the bonding site with other structures.

[0128] [Chemical Formula 9]

[0129]

[0130] In equation (5), R 112 It is a single bond or a divalent linker, preferably a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO- and groups in combination thereof, more preferably a group selected from alkylene groups with 1 to 3 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -CO-, -S- and -SO2-, and even more preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0131] Regarding R 115 Specifically, examples include the tetracarboxylic acid residues remaining after the anhydride group is removed from tetracarboxylic dianhydrides. As for R... 115 The corresponding structure of the polyimide precursor can contain only one type of tetracarboxylic acid dianhydride residue, or it can contain two or more types.

[0132] Tetracarboxylic acid dianhydride is preferably represented by the following formula (O).

[0133] [Chemical Formula 10]

[0134]

[0135] In equation (O), R 115 R represents a tetravalent organic group. 115 The preferred range is the same as R in equation (2). 115 The meanings are the same, and the preferred ranges are also the same.

[0136] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propanedihydride. Anhydrides, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride and these alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0137] Furthermore, tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can be cited as preferred examples.

[0138] In equation (2), R 111 and R 115 At least one of them can also have an OH group. More specifically, as R 111 Examples of residues from diaminophenol derivatives can be cited.

[0139] R in equation (2) 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferred to include a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxide group. Furthermore, R is preferred. 113 and R 114 At least one of them contains a polymeric group, more preferably both contain polymeric groups. R is also preferred. 113 and R 114At least one of them contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a cross-linking reaction through the action of heat, free radicals, etc., and is preferably a free radical polymerizable group. Specific examples of polymerizable groups include groups having vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxybutyl, benzoxazolyl, block isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having vinyl unsaturated bonds is preferred.

[0140] Examples of groups having vinyl unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acryloylamino, (meth)acryloyloxy, and groups represented by formula (III) below, with groups represented by formula (III) below being preferred.

[0141] [Chemical Formula 11]

[0142]

[0143] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0144] In equation (III), * indicates the bonding site with other structures.

[0145] In formula (I[I), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0146] Preferred R 201 Examples include alkylene compounds such as ethylene, propyleneene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH2CH(OH)CH2-, and polyalkoxide compounds, more preferably alkylene compounds such as ethylene and propyleneene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkoxide compounds, and even more preferably alkylene compounds such as ethylene and propyleneene or polyalkoxide compounds.

[0147] In this invention, polyalkoxide refers to an alkoxide group directly bonded to two or more groups. The alkylene groups in the multiple alkoxide groups contained in a polyalkoxide group may be the same or different.

[0148] When a polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0149] The number of carbon atoms in the alkylene group (the number of carbon atoms including the substituent if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0150] Furthermore, the aforementioned alkylene group may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0151] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repetitions of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0152] From the viewpoint of solvent solubility and solvent resistance, polyoxyethylene, polypropylene, polytrimethylene, polytetramethethylene, or groups obtained by bonding multiple ethyleneoxy groups with multiple propyleneoxy groups are preferred as polyoxyethylene or polypropyleneoxy groups, and polyoxyethylene is even more preferred. In the groups obtained by bonding multiple ethyleneoxy groups with multiple propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, form blocks, or be arranged in alternating patterns. The preferred manner for the number of repetitions of ethyleneoxy groups in these groups is as described above.

[0153] In equation (2), in R 113 In the case of hydrogen atoms or in R 114 In the case of hydrogen atoms, polyimide precursors can form countersalts with tertiary amine compounds having vinyl unsaturated bonds. An example of such a tertiary amine compound with vinyl unsaturated bonds is N,N-dimethylaminopropyl methacrylate.

[0154] In equation (2), R 113 and R 114 At least one of them can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, there is no particular limitation as long as it is a base-soluble group such as a phenolic hydroxyl group or a carboxyl group that decomposes under the action of acid, but it is preferred to be an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. From the point of view of exposure sensitivity, an acetal group or a ketal group is more preferred.

[0155] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0156] Furthermore, the polyimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0157] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0158] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in this invention is preferably a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the width of the exposure latitude can be further increased.

[0159] Equation (2-A)

[0160] [Chemical Formula 12]

[0161]

[0162] In equation (2-A), A 1 and A 2 R represents an oxygen atom. 111 and R 112 Each of the following independently represents a divalent organic group, R 113 and R 114 R represents either a hydrogen atom or a monovalent organic group independently. 113 and R 114 At least one of them is a group containing a polymerizable group, preferably both of them are groups containing polymerizable groups.

[0163] A 1 A 2 R 111 R 113 and R 114 Independently with A in equation (2) 1 A 2 R 111 , R 1 13 and R 114 The meanings are the same, and the preferred ranges are also the same.

[0164] R 112 R in equation (5) 112 The meanings are the same, and the preferred ranges are also the same.

[0165] The polyimide precursor may contain one repeating unit represented by formula (2), or two or more repeating units. It may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it is self-evident that the polyimide precursor may contain other types of repeating units besides the repeating unit of formula (2).

[0166] As one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and especially preferably more than 90 mol%. There is no particular limitation on the upper limit of the total content, and all repeating units in the polyimide precursor except for the end units can also be repeating units represented by formula (2).

[0167] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. Furthermore, the number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0168] The molecular weight dispersion of the aforementioned polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0169] In this specification, the molecular weight dispersion is a value calculated using weight-average molecular weight / number-average molecular weight.

[0170] Furthermore, when the resin composition includes multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyimide precursors as a single resin are each within the aforementioned ranges.

[0171] [Polyimide]

[0172] The polyimide used in this invention can be an alkali-soluble polyimide or a polyimide soluble in a developer solution with organic solvents as the main component.

[0173] In this specification, alkali-soluble polyimide refers to polyimide that dissolves at least 0.1 g in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, it is preferable to dissolve at least 0.5 g of polyimide, and more preferably at least 1.0 g of polyimide. There is no particular upper limit to the above-mentioned dissolution amount, but it is preferably 100 g or less.

[0174] Furthermore, from the viewpoint of the strength and insulation of the obtained organic membrane, polyimide is preferably a polyimide having multiple imide structures on the main chain.

[0175] In this specification, "main chain" refers to the longest bonded chain in the polymer compound that constitutes the resin, and "side chain" refers to the other bonded chains.

[0176] -Fluorine atom-

[0177] From the viewpoint of the strength of the obtained organic membrane, polyimide is also preferably provided with fluorine atoms.

[0178] Fluorine atoms are preferably included, for example, in the repeating unit represented by formula (4) described later. 132 Or R in the repeating unit represented by equation (4) as described later 131 More preferably, R is included as a fluorinated alkyl group in the repeating unit represented by formula (4) described later. 132 Or R in the repeating unit represented by equation (4) as described later 131 middle.

[0179] The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0180] -Silicon atom-

[0181] From the viewpoint of the strength of the obtained organic membrane, polyimide is also preferably composed of silicon atoms.

[0182] Silicon atoms are preferably included, for example, in the repeating unit represented by formula (4) described later. 131 More preferably, R is included in the repeating unit represented by formula (4) as an organically modified (poly)siloxane structure described later. 131 middle.

[0183] Furthermore, the aforementioned silicon atoms or the aforementioned organically modified (poly)siloxane structure may also be included on the side chain of the polyimide, but preferably on the main chain of the polyimide.

[0184] The amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, more preferably 20% by mass or less.

[0185] -Ethylene unsaturated bond-

[0186] From the viewpoint of the strength of the obtained organic membrane, polyimide preferably has vinyl unsaturated bonds.

[0187] Polyimide can have vinyl unsaturated bonds at the end of the main chain or on the side chain, but it is preferred to have vinyl unsaturated bonds on the side chain.

[0188] The aforementioned ethylene unsaturated bonds preferably possess free radical polymerization properties.

[0189] The ethylene unsaturated bond is preferably contained in the repeating unit represented by formula (4) described later. 132 Or R in the repeating unit represented by equation (4) as described later 131 More preferably, R is included as a group having an ethylene unsaturated bond in the repeating unit represented by formula (4) described later. 132 Or R in the repeating unit represented by equation (4) as described later 131 middle.

[0190] Among these, the ethylene unsaturated bond is preferably contained in the repeating unit represented by formula (4) described later. 131 More preferably, R is included as a group having an ethylene unsaturated bond in the repeating unit represented by formula (4) described later. 131 middle.

[0191] Examples of groups having vinyl unsaturated bonds include vinyl, allyl, vinylphenyl, and other vinyl groups that are directly bonded to an aromatic ring and can be substituted, as well as (meth)acryloyl, (meth)acryloyloxy, and groups represented by the following formula (IV).

[0192] [Chemical Formula 13]

[0193]

[0194] In equation (IV), R 20 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0195] In equation (IV), R 21 The group represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkoxide group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, especially preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, especially preferably 1 to 3) or a group composed of two or more of these.

[0196] Furthermore, the alkylene group having 2 to 12 carbon atoms can be any one of linear, branched, cyclic, or combinations thereof.

[0197] As the aforementioned alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

[0198] Among these, R 21 Preferably, it is a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).

[0199] [Chemical Formula 14]

[0200]

[0201] In formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkoxide group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these; X represents an oxygen atom or a sulfur atom; * represents a bonding site with other structures; and ● represents a connection with R in formula (IV). 21 The bonding sites of the bonded oxygen atoms.

[0202] In formulas (R1) to (R3), the preferred form of L is an alkylene group having 2 to 12 carbon atoms or a (poly)alkene group having 2 to 30 carbon atoms, which is the same as that of R described above. 21 The preferred configurations are the same for alkylene groups with 2 to 12 carbon atoms or (poly)alkoxide groups with 2 to 30 carbon atoms.

[0203] In formula (R1), X is preferably an oxygen atom.

[0204] In equations (R1) to (R3), * has the same meaning as * in equation (IV), and the preferred method is also the same.

[0205] The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having phenolic hydroxyl groups or other hydroxyl groups with a compound having isocyanate groups and vinyl unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate).

[0206] The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an vinyl unsaturated bond (e.g., 2-hydroxyethyl methacrylate).

[0207] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having phenolic hydroxyl groups with a compound having glycidyl methacrylate and vinyl unsaturated bonds (e.g., glycidyl methacrylate).

[0208] In formula (IV), * indicates a bonding site with other structures, preferably a bonding site with the main chain of polyimide.

[0209] The amount of vinyl unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g.

[0210] - Polymerizable groups other than those with vinyl unsaturated bonds-

[0211] Polyimides can have polymerizable groups other than those with vinyl unsaturated bonds.

[0212] Examples of polymerizable groups other than those with vinyl unsaturated bonds include cyclic ether groups such as epoxy groups and cyclobutane groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups.

[0213] Polymerizable groups other than those with ethylene unsaturated bonds, preferably R contained in the repeating unit represented by formula (4) described below. 131 middle.

[0214] The amount of polymerizable groups other than those having vinyl unsaturated bonds is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g, relative to the total mass of the polyimide.

[0215] -Polar conversion group-

[0216] Polyimides can possess polar conversion groups such as acid-degrading groups. The acid-degrading groups in polyimides are analogous to the R groups in formula (2) above. 113 and R 114 The acid-decomposing groups described herein are the same, and the preferred methods are also the same.

[0217] The polarity conversion base, for example, is R contained in the repeating unit represented by equation (4) described later. 131 R 132 In the end of polyimide, etc.

[0218] -Acid Value-

[0219] When polyimide is used for alkaline development, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more.

[0220] Furthermore, the acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less.

[0221] Furthermore, when the polyimide is used for development with a developer solution mainly composed of organic solvents (e.g., "solvent development" as described below), the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g.

[0222] The acid value is determined by a known method, for example by the method described in JIS K 0070:1992.

[0223] Furthermore, from the viewpoint of balancing storage stability and developability, the acid groups contained in the polyimide preferably have a pKa of 0 to 10, and more preferably a pKa of 3 to 8.

[0224] pKa is the equilibrium constant Ka, expressed as its negative common logarithm, pKa, which takes into account the dissociation reaction that releases hydrogen ions from an acid. In this specification, unless otherwise stated, pKa is set as a calculated value based on ACD / ChemSketch (registered trademark). Alternatively, the value published in the "Revised 5th Edition of the Basic Chemical Handbook" edited by the Chemical Society of Japan may be consulted.

[0225] Furthermore, in the case of a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant.

[0226] As such an acid group, the polyimide preferably contains at least one selected from carboxyl groups and phenolic hydroxyl groups, and more preferably contains phenolic hydroxyl groups.

[0227] -Phenolic hydroxyl-

[0228] From the viewpoint of making the development speed based on alkaline developer appropriate, polyimide preferably has phenolic hydroxyl groups.

[0229] Polyimide can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0230] Phenolic hydroxyl groups are preferably included, for example, in the repeating unit represented by formula (4) described later. 132 Or R in the repeating unit represented by equation (4) as described later 131 middle.

[0231] The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0232] The polyimide used in this invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferred to contain repeating units represented by the following formula (4).

[0233] [Chemical Formula 15]

[0234]

[0235] In equation (4), R 131 R represents a divalent organic group. 132 This indicates a tetravalent organic group.

[0236] In the case of having polymerizable groups, the polymerizable groups can be located at R. 131 and R 132 At least one of them, as shown in formula (4-1) or formula (4-2) below, may also be located at the end of the polyimide.

[0237] Equation (4-1)

[0238] [Chemical Formula 16]

[0239]

[0240] In equation (4-1), R 133 The group is a polymerizable group, and the other groups have the same meaning as in formula (4).

[0241] Equation (4-2)

[0242] [Chemical Formula 17]

[0243]

[0244] R 134 and R 135 At least one of them is a polymeric group, and if it is not a polymeric group, it is an organic group. The other groups have the same meaning as in formula (4).

[0245] Examples of polymerizable groups include groups containing ethylene unsaturated bonds or crosslinking groups other than those containing ethylene unsaturated bonds.

[0246] R 131 This represents a divalent organic group. Examples of divalent organic groups include R in formula (2). 111 They are the same, and the preferred range is also the same.

[0247] Furthermore, as R 131 Examples of diamines include the diamine residue remaining after the amino group of the diamine is removed. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. As a specific example, R in formula (2) of a polyimide precursor can be cited. 111 Examples.

[0248] From the perspective of more effectively suppressing warping during calcination, R 131Preferably, it is a diamine residue having at least two alkylene glycol units on the main chain. More preferably, it is a diamine residue comprising a total of two or more ethylene glycol chains, propylene glycol chains, or both in a molecule. Further preferably, it is a diamine residue that does not contain an aromatic ring.

[0249] Examples of diamines containing a total of two or more ethylene glycol chains or propylene glycol chains 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, D-4000 (these are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., but are not limited to these.

[0250] R 132 This represents a tetravalent organic group. Examples of tetravalent organic groups include R in formula (2). 115 They are the same, and the preferred range is also the same.

[0251] For example, as R 115 The four bonds of the exemplified tetravalent organic group are bonded to the four -C (=0)- portions in the above formula (4) to form a condensation ring.

[0252] Furthermore, R 132 Examples include the tetracarboxylic acid residue remaining after the anhydride group is removed from a tetracarboxylic dianhydride. As a specific example, R in formula (2) of a polyimide precursor can be cited. 115 Examples. From the viewpoint of the strength of organic membranes, R 132 Preferably, it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0253] R is also preferred 131 and R 132 At least one of them has an OH group. More specifically, as R 131 Examples of preferred embodiments include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, as well as (DA-1) to (DA-18) mentioned above. 132 Examples of better examples include (DAA-1) to (DAA-5).

[0254] Furthermore, the polyimide 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.

[0255] Furthermore, to improve adhesion to the substrate, polyimide can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0256] Furthermore, to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyimide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochlorinated compounds, or monoactive ester compounds. Among these, monoamines are more preferred. Examples of 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-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-7-aminonaphthalene. Examples of amino acids include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, and 4-aminobenzenethiophenol. More than two of these can be used, and multiple different end groups can be introduced by reacting various end-capping agents.

[0257] -Imidization rate (ring-closure rate)-

[0258] From the perspective of the obtained organic film's strength and insulation properties, the imidization rate (also known as "ring-closing rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0259] There is no particular upper limit to the imidization rate mentioned above, as long as it is below 100%.

[0260] The imidization rate described above can be determined, for example, by the following method.

[0261] The infrared absorption spectrum of polyimide was measured, and the absorption peak at 1377 cm⁻¹, which originates from the imide structure, was determined. -1The peak intensity P1 was measured around 1377 cm⁻¹. Next, the polyimide was heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to determine the peak intensity P1. -1 The peak intensity P2 is approximately equal to the peak intensity P1. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated according to the following formula.

[0262] Imidification rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0263] Polyimide can contain all of one type of R 131 Or R 132 The repeating unit represented by the above equation (4) may also contain more than two different types of R. 131 Or R 132 The repeating unit represented by the above formula (4). In addition to the repeating unit represented by the above formula (4), polyimide may also contain other types of repeating units. For example, the repeating unit represented by the above formula (2) can be cited as another type of repeating unit.

[0264] Polyimides can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine (a capping agent partially replaced by a monoamine) at low temperature; by reacting a tetracarboxylic dianhydride (a capping agent partially replaced by an anhydride, a monochlorinated compound, or a monoactive ester compound) with a diamine at low temperature; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine (a capping agent partially replaced by a monoamine) in the presence of a condensing agent; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then chlorinating the remaining dicarboxylic acid and reacting it with a diamine (a capping agent partially replaced by a monoamine), and then fully imidizing it using a known imidization reaction method; or by stopping the imidization reaction midway and introducing a partial imide structure; and by introducing a partial imide structure by mixing a fully imidized polymer with the polyimide precursor. Furthermore, it can also be applied to other known methods for synthesizing polyimides.

[0265] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the folding 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.

[0266] Furthermore, the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0267] The molecular weight dispersion of the aforementioned polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyimide; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0268] Furthermore, when the resin composition contains multiple polyimides as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyimides as a single resin are each within the aforementioned ranges.

[0269] [Polybenzoxazole precursor]

[0270] There are no particular provisions regarding the structure of the polybenzoxazole precursor used in this invention, but it is preferred to include repeating units represented by the following formula (3).

[0271] [Chemical Formula 18]

[0272]

[0273] In equation (3), R 121 R represents a divalent organic group. 122 R represents a tetravalent organic group. 123 and R 124 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0274] In equation (3), R 123 and R 124 respectively with R in equation (2) 113 The meanings are the same, and the preferred ranges are also the same. That is, at least one of them is preferably a polymeric group.

[0275] In equation (3), R 121 This indicates a divalent organic group. Preferably, the divalent organic group comprises at least one of an aliphatic group and an aromatic group. As an aliphatic group, a straight-chain aliphatic group is preferred. R 121 The preferred choice is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

[0276] As dicarboxylic acid residues, dicarboxylic acid residues containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred.

[0277] As a dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferred; more preferably, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups is preferred. The straight-chain or branched (preferably straight-chain) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25, further preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The straight-chain aliphatic group is preferably an alkylene group.

[0278] Examples of dicarboxylic acids containing a straight-chain aliphatic group 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, and 2,2,6,6-tetrafluoroadipic acid. Methyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, docosanedioic acid, diglycolic acid acid) and dicarboxylic acids represented by the following formula, etc.

[0279] [Chemical Formula 19]

[0280]

[0281] (In the formula, Z is a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0282] As a dicarboxylic acid containing an aromatic group, it is preferred to be a dicarboxylic acid having the following aromatic groups, and more preferably a dicarboxylic acid consisting only of a group having the following aromatic groups and two -COOH groups.

[0283] [Chemical Formula 20]

[0284]

[0285] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * represents the bonding site with other structures independently.

[0286] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and phthalic acid.

[0287] In equation (3), R 122 This represents a tetravalent organic group. As a tetravalent organic group, it interacts with R in the above formula (2). 115 The meanings are the same, and the preferred ranges are also the same.

[0288] R 122 Preferably, the group is derived from a diaminophenol derivative. Examples of groups derived from diaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis-(4- Diaminophenols include (amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These diaminophenols can be used alone or in combination.

[0289] Among the diaminophenol derivatives, the following diaminophenol derivatives having aromatic groups are preferred.

[0290] [Chemical Formula 21]

[0291]

[0292] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, and -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. Furthermore, R... 122 The structure represented by the above formula is also preferred. In R122 In the case of the structure represented by the above formula, among the total of 4 * and #, it is preferable that any 2 are R in formula (3). 122 The bonding sites of the nitrogen atoms are those of the nitrogen atoms bonded together, and the other two are R in equation (3). 122 The bonding sites of the bonded oxygen atoms are further selected by choosing two as R in equation (3). 122 The bonding sites of the bonded oxygen atoms and the two #'s are related to R in equation (3). 122 The bonding sites of the nitrogen atoms, or the two asterisks, are related to R in equation (3). 122 The bonding sites of the nitrogen atoms and the two #'s are related to R in equation (3). 122 The bonding sites of the bonded oxygen atoms are further preferably two as R in equation (3). 122 The bonding sites of the bonded oxygen atoms and the two #'s are related to R in equation (3). 122 The bonding sites of the nitrogen atoms.

[0293] The diaminophenol derivative is also preferably a compound represented by formula (As).

[0294] [Chemical Formula 22]

[0295]

[0296] In formula (As), R1 is an organic group selected from hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, single bond, or the group consisting of the following formulas (A-sc). R2 is any one of hydrogen atom, alkyl, alkoxy, acyloxy, or cyclic alkyl, which may be the same or different. R3 is any one of hydrogen atom, straight-chain or branched alkyl, alkoxy, acyloxy, or cyclic alkyl, which may be the same or different.

[0297] [Chemical Formula 23]

[0298]

[0299] (In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

[0300] In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxyl group, i.e., at R3, would bring the carbonyl carbon of the amide bond closer to the hydroxyl group, which is particularly preferred in terms of further improving the effect of achieving a high cyclization rate when cured at low temperature.

[0301] Furthermore, in the above formula (As), when R2 is an alkyl group and R3 is an alkyl group, it can maintain high transparency to i-rays and achieve a high cyclization rate when cured at low temperature, which is therefore preferred.

[0302] Furthermore, in the above formula (As), R1 is preferably an alkylene or substituted alkylene. Specific examples of alkylene or substituted alkylene of R1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred in terms of achieving a good balance between maintaining high transparency to i-rays and high cyclization rate during low-temperature curing, while also obtaining a polybenzoxazole precursor with sufficient solubility in solvents.

[0303] As for the method of manufacturing the diaminophenol derivative represented by the above formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, and these contents are incorporated into this specification.

[0304] As specific examples of the structures of the diaminophenol derivatives represented by the above formula (As), those described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506 are provided and are incorporated herein by reference. Of course, it is self-evident that this is not the only possible embodiment.

[0305] In addition to the repeating unit in formula (3) above, the polybenzoxazole precursor may also contain other types of repeating units.

[0306] In terms of suppressing warping associated with ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0307] [Chemical Formula 24]

[0308]

[0309] In equation (SL), Z has structures a and b, and R 1s R is a hydrocarbon group consisting of 1 to 10 hydrogen atoms or carbon atoms. 2s R is a hydrocarbon group with 1 to 10 carbon atoms. 3s R 4s R 5s R 6s At least one of the radicals is an aromatic group, and the rest are organic groups consisting of hydrogen atoms or 1 to 30 carbon atoms, which may be the same or different. The polymerization of structures a and b can be block polymerization or random polymerization. Regarding the molar percentage of the Z part, structure a is 5–95 mol%, structure b is 95–5 mol%, and a+b is 100 mol%.

[0310] In equation (SL), Z, as a preferred option, can be represented by R in structure b.5s and R 6s The molecular weight is phenyl. Furthermore, the molecular weight of the structure shown in formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, achieving both the effect of suppressing warpage and improving solvent solubility.

[0311] In cases where the diamine residue represented by formula (SL) is used as another type of repeating unit, it is also preferable to further include a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit. An example of such a tetracarboxylic acid residue is R in formula (2). 115 Examples.

[0312] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Furthermore, the number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0313] The molecular weight dispersion of the aforementioned polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. There is no particular upper limit to the molecular weight dispersion of the polybenzoxazole precursor; for example, it is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.

[0314] Furthermore, when the resin composition includes multiple polybenzoxazole precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polybenzoxazole precursors as a single resin are each within the aforementioned ranges.

[0315] [Polybenzoxazole]

[0316] As for polybenzoxazole, there is no particular limitation as long as it is a polymeric compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) that has a polymerizable group. As the polymerizable group, a free radical polymerizable group is preferred. Furthermore, it may also be a compound represented by the following formula (X) that has a polar conversion group such as an acid-decomposing group.

[0317] [Chemical Formula 25]

[0318]

[0319] In equation (X), R 133 R represents a divalent organic group. 134 This indicates a tetravalent organic group.

[0320] In the case of having polar conversion groups such as polymerizable groups or acid-decomposable groups, the polymerizable groups or acid-decomposable groups can be located at R. 133 and R 134 At least one of them, as shown in formula (X-1) or formula (X-2) below, may also be located at the end of polybenzoxazole.

[0321] Equation (X-1)

[0322] [Chemical Formula 26]

[0323]

[0324] In equation (X-1), R 135 and R 136 At least one of them is a polymeric group or an acid-decomposable polar conversion group, and if it is not a polymeric group or an acid-decomposable polar conversion group, it is an organic group. The other groups have the same meaning as in formula (X).

[0325] Equation (X-2)

[0326] [Chemical Formula 27]

[0327]

[0328] In equation (X-2), R 137 One is a polar conversion group such as a polymerizable group or an acid-decomposable group, and the others are substituents. The meanings of the other groups are the same as those in formula (X).

[0329] The polar conversion groups, such as polymerizable groups or acid-degradable groups, have the same meaning as the polymerizable groups described in the above-mentioned polyimide precursors.

[0330] R 133 This indicates a divalent organic group. Examples of divalent organic groups include aliphatic and aromatic groups. As a specific example, R in formula (3) of the polybenzoxazole precursor can be cited. 121 Examples. Furthermore, its preferred example is related to R. 121 same.

[0331] R 134 This indicates a tetravalent organic group. Examples of tetravalent organic groups include R in formula (3) of the polybenzoxazole precursor. 122 Examples. Furthermore, its preferred example is related to R. 122same.

[0332] For example, as R 122 The four bonds of the exemplified tetravalent organic group bond with the nitrogen and oxygen atoms in formula (X) above to form a condensation ring. For example, in R 134 When the organic group is one of the following, the following structure is formed. In the following structure, * indicates the bonding site with the nitrogen or oxygen atom in formula (X).

[0333] [Chemical Formula 28]

[0334]

[0335] The oxazolization rate of polybenzoxazole is preferably 85% or more, more preferably 90% or more. There is no particular upper limit, and it can be 100%. With an oxazolization rate of 85% or more, membrane shrinkage caused by ring closure during oxazolization via heating is reduced, thereby more effectively suppressing warping.

[0336] The oxazolization rate described above can be determined, for example, by the following method.

[0337] The infrared absorption spectrum of polybenzoxazole was measured, and the absorption peak at 1650 cm⁻¹, representing the amide structure derived from the precursor, was determined. -1 The peak intensity Q1 is around 1490 cm⁻¹. Then, at 1490 cm⁻¹... -1 The absorption intensities of the aromatic rings discovered on both sides were normalized. After heat-treating the polybenzoxazole at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the 1650 cm⁻¹ value was determined. -1 The peak intensity Q2 is around 1490 cm⁻¹. -1 The absorption intensities of the aromatic rings discovered on the left and right sides were normalized. Using the obtained standard values ​​of peak intensities Q1 and Q2, the oxazolization rate of polybenzoxazole can be calculated according to the following formula.

[0338] Oxazoleization rate (%) = (Standard value of peak intensity Q1 / Standard value of peak intensity Q2) × 100

[0339] Polybenzoxazole can contain all of the following: one type of R 131 Or R 132 The repeating unit in the above equation (X) may also contain more than two different kinds of R. 131 Or R 132 The repeating unit of the above formula (X). In addition to the repeating unit of the above formula (X), polybenzoxazole may also contain other types of repeating units.

[0340] Regarding polybenzoxazole, for example by reacting a diaminophenol derivative with a compound containing R... 133The polybenzoxazole precursor is obtained by reacting a dicarboxylic acid or a compound selected from the dicarboxylic acid dichloride and dicarboxylic acid derivatives of the above dicarboxylic acids, and then oxazoleized by a known oxazoleization reaction.

[0341] In addition, in the case of dicarboxylic acids, in order to improve the reaction yield, an active ester-type dicarboxylic acid derivative obtained by pre-reacting 1-hydroxy-1,2,3-benzotriazole can be used.

[0342] The weight-average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. Setting the weight-average molecular weight to 5,000 or higher improves the folding resistance of the cured film. For obtaining an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, when containing two or more polybenzoxazoles, the weight-average molecular weight of at least one polybenzoxazole is preferably within the above range.

[0343] Furthermore, the number-average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0344] The molecular weight dispersion of the aforementioned polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. There is no particular upper limit to the molecular weight dispersion of the polybenzoxazole; for example, it is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.

[0345] Furthermore, when the resin composition contains multiple polybenzoxazoles as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility of at least one polybenzoxazole are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility calculated using the multiple polybenzoxazoles as a single resin are each within the aforementioned ranges.

[0346] [Polyamide-imide precursor]

[0347] The polyamide-imide precursor preferably comprises repeating units represented by the following formula (PAI-2).

[0348] [Chemical Formula 29]

[0349]

[0350] In formula (PAI-2), R 117R represents a trivalent organic group. 111 A represents a divalent organic group. 2 Represents oxygen atom or -NH-, R 113 It represents a hydrogen atom or an organic group with a valence of 1.

[0351] In formula (PAI-2), R 117 Examples of groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups obtained by linking two or more of these groups together via single bonds or linking groups. Preferably, groups are obtained by combining two or more of these groups, either straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more of these groups via single bonds or linking groups. More preferably, groups are obtained by combining two or more of these groups, either aromatic groups with 6 to 20 carbon atoms, or aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more of these groups via single bonds or linking groups.

[0352] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, aryl, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, alkyl halide, aryl, or linking groups formed by bonding two or more of these are more preferred.

[0353] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0354] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0355] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0356] Furthermore, R 117 Preferably, it is derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. As the halogenation mentioned above, chlorination is preferred.

[0357] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0358] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-treated.

[0359] Examples of tricarboxylic acid compounds that can be halogenated and used in the manufacture of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0360] These tricarboxylic acid compounds can be used in one or more forms.

[0361] Specifically, as a tricarboxylic acid compound, it is preferable to be a tricarboxylic acid compound comprising a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or a linker. More preferably, it is a tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linker.

[0362] Furthermore, specific examples of tricarboxylic acid compounds include compounds in which 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid are linked by single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or phenylene oxide.

[0363] These compounds can be compounds with two carboxyl groups anhydride-substituted (e.g., trimellitic anhydride) or compounds with at least one carboxyl group halogenated (e.g., trimellitic anhydride acyl chloride).

[0364] In formula (PAI-2), R 111 A 2 R 113 respectively with R in the above formula (2) 111 A 2 R 113 The meanings are the same, and the preferred methods are also the same.

[0365] The polyamide-imide precursor may further contain other repeating units.

[0366] Other repeating units can be exemplified by the repeating unit represented by equation (2) above, the repeating unit represented by equation (PAI-1) below, etc.

[0367] [Chemical Formula 30]

[0368]

[0369] In formula (PAI-1), R 116 R represents a divalent organic group. 111 This indicates a divalent organic group.

[0370] In formula (PAI-1), R 116 Examples of groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups obtained by linking two or more of these groups together via single bonds or linking groups. Preferably, groups are obtained by combining two or more of these groups, either straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more of these groups via single bonds or linking groups. More preferably, groups are obtained by combining two or more of these groups, either aromatic groups with 6 to 20 carbon atoms, or aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more of these groups via single bonds or linking groups.

[0371] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, aryl, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, alkyl halide, aryl, or linking groups formed by bonding two or more of these are more preferred.

[0372] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0373] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0374] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0375] Furthermore, R 116 Preferably derived from dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0376] In this invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide.

[0377] In dicarboxylic acid dihalides, the carboxyl group only needs to be halogenated, for example, preferably chlorinated. That is, dicarboxylic acid dihalides are preferably dicarboxylic acid dichloride compounds.

[0378] Examples of halogenable dicarboxylic acid compounds or dicarboxylic acid dihalides used in the manufacture of polyamide-imide precursors include linear or branched aliphatic, cyclic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0379] These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used in one or more forms.

[0380] Specifically, as a dicarboxylic acid compound or dicarboxylic acid dihalide, it is preferable to be a dicarboxylic acid compound or dicarboxylic acid dihalide that comprises 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 obtained by combining two or more of these groups via a single bond or a linker. More preferably, it is a dicarboxylic acid compound or dicarboxylic acid dihalide that comprises an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linker.

[0381] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, octanoic acid, dodecafluorooctanoic acid, azelaic acid, sebacic acid, and hexafluoro... Sebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, dohenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyl diphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0382] As a specific example of a dicarboxylic acid dihalide, a compound with a structure formed by halogenating two carboxyl groups in the above-mentioned dicarboxylic acid compound examples can be cited.

[0383] In formula (PAI-1), R 111 R in equation (2) above 111 The meanings are the same, and the preferred methods are also the same.

[0384] Furthermore, the polyamide-imide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0385] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc., as the diamine component can be cited.

[0386] As one embodiment of the polyamide-imide precursor of the present invention, the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular limitation on the upper limit of the total content; all repeating units in the polyamide-imide precursor, except for the terminal units, can be any one of the repeating units represented by formula (PAI-2), formula (PAI-1), and formula (2).

[0387] Furthermore, as another embodiment of the polyamide-imide precursor of the present invention, an example is provided where the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of all repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular limitation on the upper limit of the total content; all repeating units in the polyamide-imide precursor, except for the terminal units, can be any one of the repeating units represented by formula (PAI-2) or formula (PAI-1).

[0388] The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Furthermore, the number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0389] The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyamide-imide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Furthermore, when the resin composition includes multiple polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersion of at least one polyamide-imide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersion calculated when the multiple polyamide-imide precursors are considered as a single resin are each within the above-mentioned ranges.

[0390] [Polyamide-imide]

[0391] The polyamide imide used in this invention can be an alkali-soluble polyamide imide or a polyamide imide soluble in a developer solution with organic solvent as the main component.

[0392] In this specification, alkali-soluble polyamide-imide refers to polyamide-imide that dissolves at least 0.1 g in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, it is preferable to dissolve at least 0.5 g of polyamide-imide, and more preferably at least 1.0 g of polyamide-imide. There is no particular upper limit to the above-mentioned dissolution amount, but it is preferably 100 g or less.

[0393] Furthermore, from the viewpoint of the strength and insulation of the obtained organic membrane, polyamide-imide is preferably a polyamide-imide having multiple amide bonds and multiple imide structures on the main chain.

[0394] -Fluorine atom-

[0395] From the viewpoint of the membrane strength of the obtained organic membrane, polyamide-imide preferably has fluorine atoms.

[0396] Fluorine atoms are preferably included, for example, in the repeating unit represented by the formula (PAI-3) described later, in the R group. 117 Or R 111 More preferably, R is included as a fluorinated alkyl group in the repeating unit represented by the following formula (PAI-3). 117 Or R 111 middle.

[0397] The amount of fluorine atoms relative to the total mass of the polyamide imide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0398] -Ethylene unsaturated bond-

[0399] From the perspective of the membrane strength of the obtained organic membrane, polyamide-imide can have vinyl unsaturated bonds.

[0400] Polyamide-imide can have ethylene unsaturated bonds at the end of the main chain or on the side chain, but it is preferred to have ethylene unsaturated bonds on the side chain.

[0401] The aforementioned ethylene unsaturated bonds preferably possess free radical polymerization properties.

[0402] The vinyl unsaturated bond is preferably included in the repeating unit represented by the formula (PAI-3) described later. 117 Or R 111 More preferably, R is included as a group having an ethylene unsaturated bond in the repeating unit represented by the following formula (PAI-3). 117 Or R 111 middle.

[0403] The preferred manner of having groups with vinyl unsaturated bonds is the same as that of having groups with vinyl unsaturated bonds in the polyimide described above.

[0404] The amount of vinyl unsaturated bonds relative to the total mass of polyamide imide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0405] -polymeric groups other than ethylene unsaturated bonds-

[0406] Polyamide imides can have polymerizable groups other than vinyl unsaturated bonds.

[0407] As polymerizable groups in polyamide-imide other than ethylene unsaturated bonds, examples can be given that are the same polymerizable groups in the polyamide-imide mentioned above.

[0408] Polymerizable groups other than ethylene unsaturated bonds, preferably R contained in the repeating unit represented by the following formula (PAI-3). 111 middle.

[0409] The amount of polymeric groups other than ethylene unsaturated bonds is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g, relative to the total mass of polyamide-imide.

[0410] -Polar conversion group-

[0411] Polyamide-imides can possess polar conversion groups such as acid-degrading groups. The acid-degrading groups in polyamide-imides are analogous to the R group in formula (2) above. 113 and R 114The acid-decomposing groups described herein are the same, and the preferred methods are also the same.

[0412] -Acid Value-

[0413] When polyamide-imide is used for alkaline development, from the viewpoint of improving developability, the acid value of polyamide-imide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more.

[0414] Furthermore, the acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less.

[0415] Furthermore, when the polyamide-imide is used for development with a developer solution mainly composed of organic solvents (e.g., "solvent development" described below), the acid value of the polyamide-imide is preferably 2 to 35 mg KOH / g, more preferably 3 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g.

[0416] The acid value is determined by a known method, for example by the method described in JIS K 0070:1992.

[0417] Furthermore, the acid groups contained in the polyamide imide can be the same as those in the polyimide described above, and the preferred method is also the same.

[0418] -Phenolic hydroxyl-

[0419] From the viewpoint of making the development speed of alkaline developing solution appropriate, polyamide imide preferably has phenolic hydroxyl groups.

[0420] Polyamide imides can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0421] Phenolic hydroxyl groups are preferably included, for example, in the repeating unit represented by the following formula (PAI-3) as R. 117 Or R 111 middle.

[0422] The amount of phenolic hydroxyl groups relative to the total mass of polyamide imide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0423] The polyamide-imide used in this invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it is preferred to contain repeating units represented by the following formula (PAI-3).

[0424] [Chemical Formula 31]

[0425]

[0426] In formula (PAI-3), R 111 and R 117 respectively with R in equation (PAI-2) 111 and R 117 The meanings are the same, and the preferred methods are also the same.

[0427] In the case of having polymerizable groups, the polymerizable groups can be located at R. 111 and R 117 It can also be located at the end of at least one of the polyamide-imide components.

[0428] Furthermore, to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyamide-imide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochlorinated compounds, or monoactive ester compounds. The preferred methods for selecting end-capping agents are the same as those for those used in the polyimide composition described above.

[0429] -Imidization rate (ring-closure rate)-

[0430] From the perspective of the obtained organic membrane strength and insulation properties, the imidization rate (also known as "ring-closing rate") of polyamide imide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0431] There is no particular upper limit to the imidization rate mentioned above, as long as it is below 100%.

[0432] The imidization rate was determined using the same method as the ring-closure rate of the polyimide described above.

[0433] Polyamide imide can contain all of one type of R 111 Or R 117 The repeating unit represented by the above formula (PAI-3) may also contain more than two different types of R. 131 Or R 132 The repeating unit represented by the above formula (PAI-3). Furthermore, in addition to the repeating unit represented by the above formula (PAI-3), polyamide-imide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0434] Polyamide-imides can be synthesized, for example, by obtaining a polyamide-imide precursor by a known method and fully imidizing it using a known imidization reaction; or by stopping the imidization reaction midway and introducing a partial imide structure; and by introducing a partial imide structure by mixing a fully imidized polymer with the polyamide-imide precursor.

[0435] The weight-average molecular weight (Mw) of the polyamide-imide 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 folding 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.

[0436] Furthermore, the number average molecular weight (Mn) of the polyamide-imide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0437] The molecular weight dispersion of the polyamide-imide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyamide-imide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0438] Furthermore, when the resin composition contains multiple polyamide-imides as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamide-imide are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyamide-imides as a single resin are each within the aforementioned ranges.

[0439] [Methods for manufacturing polyimide precursors, etc.]

[0440] Polyimide precursors can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine at low temperature; by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid and then esterifying it with a condensing agent or alkylating agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, and then reacting it in the presence of diamine and a condensing agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acids with a halogenating agent, and then reacting it with diamine, etc. In the above manufacturing methods, it is more preferable to obtain a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acids with a halogenating agent, and then reacting it with diamine.

[0441] Examples of condensing agents mentioned above 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.

[0442] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0443] Examples of halogenating agents mentioned above include thioyl chloride, oxalyl chloride, and phosphorus oxychloride.

[0444] In methods for manufacturing polyimide precursors, organic solvents are preferably used during the reaction. One or more organic solvents may be used.

[0445] As an organic solvent, it can be appropriately selected according to the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0446] In methods for manufacturing polyimide precursors, etc., it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.

[0447] The basic compound can be appropriately set according to the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0448] -End- Capping Agent-

[0449] In methods for manufacturing polyimide precursors, etc., to further improve storage stability, it is preferable to seal the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin end of the polyimide precursor, etc. When sealing the carboxylic anhydride and anhydride derivative remaining at the resin end, end-capping agents include monohydric alcohols, phenols, thiols, benzenethiophenols, monoamines, etc. From the viewpoint of reactivity and film stability, monohydric alcohols, phenols, or monoamines are more preferred. Preferred monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tert-butanol, adamantanol, etc. Preferred phenols include phenols, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds for 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, and 1-carboxy-5-aminonaphthalene. Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and multiple different end groups can be introduced by reacting various end-capping agents.

[0450] Furthermore, when sealing the amino group at the end of the resin, a compound having a functional group capable of reacting with the amino group can be used for sealing. Preferred sealants for the amino group include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Examples of preferred carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of preferred carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearyl chloride, and benzoyl chloride.

[0451] -Solid precipitation-

[0452] In the manufacture of polyimide precursors, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, causing the polymer component to precipitate as a solid and then dried, thereby obtaining the polyimide precursor. To improve the purification degree, the operations of re-dissolving, re-precipitating, and drying the polyimide precursor may be repeated. Furthermore, a step of using an ion exchange resin to remove ionic impurities may be included.

[0453] 〔content〕

[0454] The content of a 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 even more preferably 50% by mass or more, relative to the total solids content of the resin composition. Furthermore, 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, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the resin composition.

[0455] The resin composition of the present invention may contain only one specific resin or may contain two or more resins. When two or more resins are contained, the total amount is preferably within the range described above.

[0456] Furthermore, the resin composition of the present invention preferably contains at least two resins.

[0457] Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or may contain two or more specific resins, but preferably contains two or more specific resins.

[0458] In the case where the resin composition of the present invention comprises two or more specific resins, it is preferable, for example, to include a structure derived from a polyimide precursor and derived from a dianhydride (R as described in formula (2) above). 115 Two or more different polyimide precursors.

[0459] <Other Resins>

[0460] The resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins").

[0461] Other resins include phenolic resins, polyamides, epoxy resins, resins containing polysiloxanes or siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, amine resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins.

[0462] For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.

[0463] For example, instead of the polymerizable compounds described later, or other polymerizable compounds described later, a polymerizable group with a high value of polymeric groups (e.g., the molar content of polymeric groups in 1 g of resin is 1 × 10⁻⁶) with a weight average molecular weight of 20,000 or less can be used. -3 Adding (meth)acrylic resin at a molar ratio of 1 g or higher to the resin composition can improve the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc.

[0464] When the resin composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0465] Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0466] Furthermore, as a preferred embodiment of the resin composition of the present invention, the content of other resins can also be set to a low level. In the above embodiment, the content of other resins relative to the total solids content of the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0467] The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When two or more other resins are contained, the total amount is preferably within the range described above.

[0468] <Specific polymerizable compounds>

[0469] The resin compositions of the present invention comprise polymeric compounds (specific polymeric compounds) having polymeric groups and amide bonds bonded to each other via linking groups.

[0470] [Amide bond]

[0471] In certain polymerizable compounds, amide bonds, in addition to those represented by (*-C(=O)NH-#), also include substituted amide bonds represented by (*-C(=O)NR-#). The * and # symbols above indicate bonding sites with other structures, respectively.

[0472] The substituent (R above) in the amide bond is not particularly limited, and known substituents can be used, such as alkyl, aromatic hydrocarbon groups, or groups represented by combinations thereof. The above hydrocarbon groups can be further substituted with halogen atoms, alkoxy, aryloxy, alkyl carbonyl, aryl carbonyl, hydroxyl, groups represented by the following formula (R-1), etc.

[0473] [Chemical Formula 32]

[0474]

[0475] In equation (R-1), R a R represents a monovalent organic group. b The symbol represents a divalent organic group, n represents an integer greater than or equal to 1, m represents 0 or 1, and * represents a bonding site with other structures.

[0476] In equation (R-1), R a Preferably a hydrocarbon group, more preferably an alkyl group, and even more preferably an alkyl group having 1 to 10 carbon atoms.

[0477] In equation (R-1), R b Preferably, it is a hydrocarbon group, more preferably an alkylene group, further preferably an alkylene group having 2 to 10 carbon atoms, especially preferably an alkylene group having 2 to 4 carbon atoms, and most preferably ethylene or propyleneene. When n is 2 or more, there are n R groups in formula (R-1). b They can be the same or different.

[0478] n represents an integer greater than or equal to 1, preferably an integer from 1 to 10.

[0479] m is preferably 1.

[0480] Furthermore, the aforementioned hydrocarbon group can bond to at least one of the structures bonded to the nitrogen atom in the aforementioned substituted amide bond and the # site to form a ring structure. Examples of the formed ring structures include piperidine rings and morpholine rings, where the nitrogen atom contained in the aforementioned amide bond is the ring element. These ring structures may further have substituents. Examples of substituents include groups identical to the substituents in the aforementioned hydrocarbon group.

[0481] Among these, from the viewpoint that the resulting alkali is highly basic and can easily improve elongation at break and chemical resistance, the amide bond in a particular polymerizable compound is preferably a substituted amide bond, and more preferably a substituted amide bond having a hydrocarbon group as a substituent.

[0482] A particular polymerizable compound may have only one amide bond or more than two amide bonds.

[0483] Furthermore, from the viewpoint of chemical resistance, certain polymeric compounds preferably do not have polyalkoxide groups in their structure.

[0484] [polymeric groups]

[0485] There are no particular limitations on the polymerizable groups in a specific polymerizable compound. Examples include free radical polymerizable groups and cationic polymerizable groups. However, from the viewpoint of reducing film shrinkage, free radical polymerizable groups are preferred.

[0486] Examples of polymerizable groups include groups with vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxybutyl, benzoxazolyl, block isocyanate, etc.

[0487] Among these, from the viewpoint of excellent reactivity and easy reduction of film shrinkage, groups with ethylene unsaturated bonds, epoxy groups, or cyclobutane groups are preferred.

[0488] Examples of groups having the aforementioned vinyl unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acryloylamino, (meth)acryloyloxy, maleimide, etc. From the viewpoint of excellent reactivity and easy reduction of film shrinkage, groups having an aromatic ring directly bonded to vinyl, (meth)acryloylamino, or (meth)acryloyloxy are preferred, and groups having an aromatic ring directly bonded to vinyl or (meth)acryloyloxy are more preferred.

[0489] Furthermore, the aforementioned epoxy groups can form acyclic epoxy groups (e.g., glycidyl, styrene oxide structures, etc.) or alicyclic epoxy groups (e.g., 3,4-epoxycyclohexyl structures, etc.).

[0490] A particular polymeric compound may have only one polymeric group or more than two. From the viewpoint of achieving an appropriate crosslinking density, having only one polymeric group is also one of the preferred embodiments of the present invention.

[0491] When a specific polymerizable compound has two or more polymerizable groups, the specific polymerizable compound may have two or more groups with ethylene unsaturated bonds, or it may have a total of two or more groups with ethylene unsaturated bonds and epoxy groups and other different types of polymerizable groups.

[0492] [Connecting base]

[0493] There are no particular limitations on the linking group, but a hydrocarbon group or one or more hydrocarbon groups selected from -O-, -S-, -C(=O)-, -S(=O)2- and -NR is preferred. N - The group represented by at least one structural bond in -. N The substituent 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.

[0494] As the aforementioned hydrocarbon group, saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, or the group represented by these bonds are preferred.

[0495] As the aforementioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferred, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferred. Furthermore, in this invention, unless otherwise stated, the descriptions of saturated aliphatic hydrocarbon groups, alkyl groups, alkylene groups, etc., all include any one of the structures represented by straight chain, branched chain, cyclic, or combinations thereof.

[0496] Examples of aromatic hydrocarbon groups include those with 6 to 20 carbon atoms. Preferably, they are groups obtained by removing multiple hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably, they are groups obtained by removing multiple hydrogen atoms from a benzene ring.

[0497] From the viewpoint of the elongation at break and chemical resistance of the obtained cured product, the linking group preferably contains an aliphatic hydrocarbon cyclic group or an aromatic hydrocarbon group as the aforementioned hydrocarbon group, more preferably contains an aromatic hydrocarbon group, and even more preferably contains a group obtained by removing multiple hydrogen atoms from the benzene ring.

[0498] There are no particular limitations on the aliphatic hydrocarbon cyclic groups mentioned above, but examples include groups obtained by removing multiple hydrogen atoms from a dicyclopentane ring, a borneol ring, an isoborneol ring, or an adamantane ring.

[0499] Examples of aromatic hydrocarbon groups include those with 6 to 20 carbon atoms. Preferably, they are groups obtained by removing multiple hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably, they are groups obtained by removing multiple hydrogen atoms from a benzene ring.

[0500] Furthermore, the aforementioned aromatic hydrocarbon group or aliphatic hydrocarbon cyclic group can condense with other rings. Examples of this method include groups obtained by removing multiple hydrogen atoms from a phthalimide ring.

[0501] Furthermore, the aforementioned hydrocarbon group may have substituents. There are no particular limitations on the substituents used, as long as they are within the range that achieves the effects of the present invention; known substituents can be used, such as preferably hydroxyl, carboxyl, etc.

[0502] Among these, hydroxyl-substituted hydrocarbon groups or carboxyl-substituted hydrocarbon groups are more preferred as linking groups.

[0503] The preferred configuration of the hydrocarbon group in the linker is as described above.

[0504] [Bonus location]

[0505] In a specific polymerizable compound, the aforementioned amide bond is bonded to the aforementioned linker on the carbonyl side.

[0506] The carbonyl side of the amide bond in a specific polymerizable compound refers to the * side in (*-C(=O)NH-#) or (*-C(=O)NR-#) mentioned above.

[0507] Furthermore, from the viewpoint of the elongation at break of the obtained cured product, the specific polymerizable compound preferably does not have a polymerizable group on the amino side of the amide bond (the # side in (*-C(=O)NH-#) or (*-C(=O)NR-#) above).

[0508] [Alkali produces energy]

[0509] When homopolymers are synthesized using specific polymerizable compounds, these homopolymers exhibit the property of producing a base free from the main chain upon heating to 250°C.

[0510] Specifically, when a particular polymerizable compound has a free radical polymerizable group, V-601 (dimethyl 2,2'-azobis(2-methylpropionate)) is used as a polymerization initiator to carry out a polymerization reaction in the solvent cyclohexanone, thereby synthesizing a homopolymer with a molecular weight of about 10,000.

[0511] When a specific polymerizable compound has cationic polymerizable groups, p-toluenesulfonic acid is used as a polymerization initiator to carry out a polymerization reaction in the solvent cyclohexanone, thereby synthesizing a homopolymer with a molecular weight of about 10,000.

[0512] Subsequently, when the obtained homopolymer was obtained by filtration and heated in a sealed container at 1 atmosphere, 250°C, and 3 hours, the homopolymer exhibited the property of producing a base free from the main chain by heating at 250°C when more than 1% of the amide bonds derived from the specific polymerizable compound were generated.

[0513] The aforementioned percentage is preferably 10% or more, more preferably 30% or more. There is no particular upper limit, and it can be 100%.

[0514] Furthermore, it is preferable that the specific polymerizable compound has a residual lactone structure in the resin, compared to the residual anhydride group after the alkali is generated by the above heating.

[0515] [Alkali]

[0516] From the viewpoint of the elongation at break of the obtained cured product, the base produced from a specific polymerizable compound is preferably an amine, and more preferably a secondary amine.

[0517] Furthermore, when an amine is generated from a specific polymerizable compound, the amine can be an aliphatic amine or an aromatic amine, but from the viewpoint of suppressing the shrinkage of the cured film, an amine having an aromatic ring structure is preferred. There is no particular limitation on the aforementioned aromatic ring structure, but an aromatic hydrocarbon ring structure is preferred, and a benzene ring structure is more preferred.

[0518] The molecular weight of the resulting alkali is preferably 70-500, more preferably 80-300, and even more preferably 90-220.

[0519] The resulting base is preferably a base with a pKa of 0 or higher for the conjugate acid, more preferably a base with a pKa of 3 or higher, and even more preferably a base with a pKa of 6 or higher. There is no particular limitation on the lower limit of the pKa of the conjugate acid, but it is preferably 30 or lower.

[0520] pKa is the equilibrium constant Ka, expressed as its negative common logarithm, pKa, which takes into account the dissociation reaction that releases hydrogen ions from the acid. In this specification, unless otherwise stated, pKa is assumed to be a calculated value based on ACD / ChemSketch (registered trademark).

[0521] In the presence of multiple pKa values ​​of the aforementioned conjugate acids, it is preferable that at least one is within the aforementioned range.

[0522] There are no particular limitations on the specific examples of the bases produced, but examples such as bases with the following structures can be given.

[0523] [Chemical Formula 33]

[0524]

[0525] Furthermore, the dimethylpiperidine ring in the above structure may contain both cis and trans arrangements, but either one is acceptable. From the viewpoint of the elongation at break of the obtained cured product, the cis arrangement is preferred.

[0526] Compared to the cis-isomer, the trans-isomer has a slightly increased number of atoms around the nitrogen atom. Therefore, the cis-isomer makes it easier for the matrix compound to approach the nitrogen atom at the active site, thereby improving the imidization promotion effect and resulting in excellent elongation at break. On the other hand, even the cis-isomer has a number that makes it difficult to react with the resin. Based on these reasons, compared to the trans-isomer, the cis-isomer maintains other properties while exhibiting excellent elongation at break.

[0527] [The compound represented by formula (1-1)]

[0528] The preferred polymerizable compound is the compound represented by the following formula (1-1).

[0529] [Chemical Formula 34]

[0530]

[0531] In equation (1-1), R 1 Each is an independent hydrogen atom or a monovalent organic group, with two R atoms. 1 They can bond together to form a ring structure, R 2 Each of the following is an organic group that is independently a hydrogen atom, a halogen atom, or a monovalent organic group, and has at least two R atoms. 2 They can bond together to form a ring structure, L 1 This indicates a trivalent organic group.

[0532] -R 1 -

[0533] From the perspective of improving the elongation at break, in equation (1-1), R 1 Preferably, each organic group is a monovalent organic group.

[0534] R 1 Preferably, it is a hydrocarbon group, more preferably an alkyl group, an aromatic hydrocarbon group or a combination thereof, and even more preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or a combination thereof, especially preferably an alkyl group having 1 to 10 carbon atoms.

[0535] The alkyl group can be any of straight-chain, branched, or cyclic, but from the viewpoint of improving elongation at break, branched alkyl groups (e.g., isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, etc.) or cyclic alkyl groups (e.g., cyclohexyl, etc.) are preferred.

[0536] R 1 It may have substituents, and examples of substituents include halogen atoms, alkoxy groups, aryloxy groups, alkyl carbonyl groups, aryl carbonyl groups, hydroxyl groups, and groups represented by the above formula (R-1).

[0537] As 2 R 1Examples of ring structures formed by bonding include piperidine rings and morpholine rings, where the nitrogen atom contained in the amide bond is the ring element. These ring structures may further have substituents. Examples of substituents are groups identical to the substituents in the hydrocarbon groups described above.

[0538] As R 1 Examples of preferred embodiments can be given by the following structures. The nitrogen atom contained in the nitrogen atom in the amide bond of formula (1-1) in the following specific examples. In the following specific examples, * indicates the bonding site with the carbonyl group.

[0539] [Chemical Formula 35]

[0540]

[0541] The dimethylpiperidine ring in the above structure can be either cis or trans. However, from the viewpoint of the elongation at break of the obtained cured product, the cis configuration is preferred. The reasons for the preference for the cis configuration are as described above.

[0542] -R 2 -

[0543] R 2 Each of the following is an organic group that is independently a hydrogen atom, a halogen atom, or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group, more preferably a hydrogen atom, methyl, ethyl, or hydroxymethyl, and especially preferably a hydrogen atom or a methyl group.

[0544] In R 2 When the atom is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom or a chlorine atom.

[0545] In particular, preferred and L 1 R bonded to adjacent carbon atoms 2 It is a hydrogen atom, methyl, ethyl or hydroxymethyl and the other two Rs are 2 For hydrogen atoms, more preferably with and L 1 R bonded to adjacent carbon atoms 2 It is a hydrogen atom or a methyl group and the other two Rs are either hydrogen atoms or methyl groups. 2 It is a hydrogen atom.

[0546] -L 1 -

[0547] L 1 There are no particular limitations, but it is preferred to have a hydrocarbon group or one or more hydrocarbon groups selected from -O-, -S-, -C(=O)-, -S(=O)2- and -NR. N - The group represented by at least one structural bond in -. N As stated above.

[0548] As the aforementioned hydrocarbon group, saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, or the group represented by these bonds are preferred.

[0549] As the aforementioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group with 1 to 20 carbon atoms is preferred, and a saturated aliphatic hydrocarbon group with 1 to 10 carbon atoms is more preferred.

[0550] Examples of aromatic hydrocarbon groups include those with 6 to 20 carbon atoms. Preferably, they are groups obtained by removing multiple hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably, they are groups obtained by removing multiple hydrogen atoms from a benzene ring.

[0551] Aliphatic hydrocarbon cyclic groups can be used as the aforementioned aliphatic hydrocarbon groups. There are no particular limitations on the aliphatic hydrocarbon cyclic groups, but examples include groups obtained by removing multiple hydrogen atoms from a dicyclopentane ring, a borneol ring, an isoborneol ring, or an adamantane ring.

[0552] Examples of aromatic hydrocarbon groups include those with 6 to 20 carbon atoms. Preferably, they are groups obtained by removing multiple hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably, they are groups obtained by removing multiple hydrogen atoms from a benzene ring.

[0553] Furthermore, the aforementioned aromatic hydrocarbon group or aliphatic hydrocarbon cyclic group can condense with other rings. Examples of this method include groups obtained by removing multiple hydrogen atoms from a phthalimide ring.

[0554] From the perspective of the elongation at break and chemical resistance of the obtained cured product, L 1 Preferably, it contains an aromatic hydrocarbon group as the aforementioned hydrocarbon group, and more preferably, it contains a group obtained by removing multiple hydrogen atoms from the benzene ring.

[0555] Furthermore, considering the efficiency of alkali production, in L 1 In the case of containing aromatic hydrocarbon groups, L is preferred. 1 The aromatic hydrocarbon group in the formula (1-1) is directly bonded to the OH group, bonded only through a single methylene group, or bonded only through a single carbonyl group, preferably directly bonded. 1 When the aromatic hydrocarbon group in formula (1-1) is directly bonded to the hydroxyl group in formula (1-1), the hydroxyl group and L are preferred. 1 The sites in L where the aromatic hydrocarbon group is directly or indirectly connected to the amide bond via a linker are located. 1 The adjacent position is located in the aromatic hydrocarbon group. The adjacent position means that the ring member bonded by one substituent and the ring member bonded by another substituent are adjacent ring members in the aromatic hydrocarbon group. In the case of the aromatic hydrocarbon group being a benzene ring, it is indicated as the ortho position.

[0556] As L 1Examples of preferred embodiments can be exemplified by the following structures. The carbonyl group in the amide bond of formula (1-1) bonded to the carbonyl group included in the structure of the following specific examples. In the following specific examples, * represents the bonding site with the carbonyl group in formula (1-1), and # represents the bonding site with the R group in formula (1-1). 2 The bonding sites of the carbon atoms that are bonded.

[0557] [Chemical Formula 36]

[0558]

[0559] [The compounds represented by formula (1-2)]

[0560] The specific polymerizable compound is preferably the compound represented by the following formula (1-2).

[0561] [Chemical Formula 37]

[0562]

[0563] In equation (1-2), R 1 Each of the two Rs can independently represent a hydrogen atom or a monovalent organic group. 1 They can bond together to form a ring structure, L 2 Represents a single bond or a divalent linker; Cy represents a ring structure; L 3 R represents a linker base that is either a single bond or divalent. 2 Each of the following groups independently represents a hydrogen atom, a halogen atom, or a monovalent organic group, with at least two R atoms. 2 They can bond together to form a ring structure.

[0564] -R 1 R 2 -

[0565] In equation (1-2), R 1 and R 2 respectively with R in equation (1-1) 1 and R 2 The meanings are the same, and the preferred methods are also the same.

[0566] -L 2 -

[0567] In equation (1-2), L 2 The linker group represents a single bond or a divalent group, preferably a single bond or a hydrocarbon group or one or more hydrocarbon groups selected from -O-, -S-, -C(=O)-, -S(=O)2- and -NR. N The group represented by a bond of at least one structure selected from -O- and -C(=O)-, more preferably a group represented by a bond of a single bond or a hydrocarbon group or one or more hydrocarbon groups to at least one structure selected from -O- and -C(=O)-. NAs stated above.

[0568] As the aforementioned hydrocarbon group, alkylene groups, divalent aromatic hydrocarbon groups, or groups represented by these bonds are preferred.

[0569] The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms.

[0570] Examples of divalent aromatic hydrocarbon groups include aromatic hydrocarbon groups with 6 to 20 carbon atoms, preferably phenylene or naphthylene, and more preferably phenylene.

[0571] -Cy-

[0572] In equation (1-2), Cy represents the ring structure.

[0573] The ring structure can be either an aliphatic ring structure or an aromatic ring structure, but an aromatic ring structure is preferred.

[0574] Furthermore, it can be either a hydrocarbon ring structure or a heterocyclic structure, but a hydrocarbon ring structure is preferred. Examples of heteroatoms included in the aforementioned heterocyclic structure include oxygen atoms, sulfur atoms, and nitrogen atoms. Furthermore, examples of the aforementioned heterocyclic structure include aromatic heterocyclic structures, and preferably include pyrrole, indole, furan, benzofuran, thiophene, and benzothiophene.

[0575] From the perspective of alkali production efficiency, Cy is preferably an aliphatic or aromatic hydrocarbon ring structure.

[0576] Examples of aliphatic hydrocarbon ring structures include bicyclopentane rings, borneol rings, isoborneol rings, and adamantane rings, with bicyclopentane rings being preferred.

[0577] The aromatic hydrocarbon ring structure described above is preferably an aromatic hydrocarbon ring structure with 6 to 20 carbon atoms, more preferably a benzene ring structure or a naphthalene ring structure, and even more preferably a benzene ring structure.

[0578] Furthermore, the aforementioned aromatic hydrocarbon ring structure or aliphatic hydrocarbon ring structure can condense with other rings. Examples of this include phthalimide ring structures.

[0579] From the viewpoint of alkali production efficiency, Cy is preferably a dicyclopentane ring structure or a benzene ring structure, and more preferably a benzene ring structure.

[0580] Furthermore, Cy can have substituents.

[0581] Examples of substituents in Cy include hydroxyl, carboxyl, nitrile, and hydroxymethyl groups. From the perspective of base production efficiency, hydroxyl is preferred.

[0582] When Cy is an aromatic ring (preferably an aromatic hydrocarbon ring) and has substituents, from the viewpoint of base production efficiency, the position of the substituents in Cy is preferably the same as that in L. 2 Adjacent positions.

[0583] For example, when Cy is a benzene ring, it is preferable to use it relative to L. 2 It has substituents such as hydroxyl groups in the ortho position.

[0584] -L 3 -

[0585] In equation (1-2), L 3 The linker group represents a single bond or a divalent group, preferably a single bond or a hydrocarbon group or one or more hydrocarbon groups selected from -O-, -S-, -C(=O)-, -S(=O)2- and -NR. N The group represented by a bond of at least one structure selected from -O- and -C(=O)-, more preferably a group represented by a bond of a single bond or a hydrocarbon group or one or more hydrocarbon groups to at least one structure selected from -O- and -C(=O)-. N As stated above.

[0586] The hydrocarbon group described above is preferably an alkylene group, an aromatic hydrocarbon group, or a group represented by such bonding; more preferably an alkylene group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group represented by such bonding; and even more preferably an alkylene group having 1 to 10 carbon atoms.

[0587] Among these, L 3 Preferably, it is a single bond or -C(=O)OR-, -C(=O)NR N -R-, alkylene, (poly)alkoxide (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, especially preferably 2 or 3; the repetition number is preferably 1 to 12, more preferably 1 to 6, especially preferably 1 to 3) or these groups bonded together in two or more. R represents a divalent hydrocarbon group, preferably alkylene, more preferably alkylene with 1 to 10 carbon atoms. Furthermore, -C(=O)OR- or -C(=O)NR... N The direction of -R- is not particularly limited, but from a reactivity point of view, it is preferred that it is bonded to Cy on the R side.

[0588] [The compounds represented by formulas (1-3)]

[0589] The specific polymerizable compound is preferably a compound represented by the following formula (1-3).

[0590] [Chemical Formula 38]

[0591]

[0592] In equation (1-3), R 1 Each of the two Rs can independently represent a hydrogen atom or a monovalent organic group. 1 They can bond together to form a ring structure, L 2 R represents a binary linker base. 2 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, and can be bonded together to form a ring structure.

[0593] -R 1 R 2 L 2 -

[0594] In equation (1-3), R 1 and R 2 respectively with R in equation (1-1) 1 and R 2 The meanings are the same, and the preferred methods are also the same.

[0595] In equation (1-3), L 2 Except for not containing single bonds, it is similar to L in equation (1-2). 2 The meanings are the same, and the preferred methods are also the same.

[0596] [Molecular weight]

[0597] The molecular weight of the specific polymerizable compound is preferably 100 to 1,000, more preferably 100 to 800, and even more preferably 150 to 500.

[0598] If the molecular weight is above the lower limit, a cured film with excellent elongation at break can be easily obtained. Furthermore, if the molecular weight is below the upper limit, film shrinkage of the cured film can be easily suppressed.

[0599] The following compounds can be cited as specific examples of certain polymerizable compounds.

[0600] [Chemical Formula 39]

[0601]

[0602] [Chemical Formula 40]

[0603]

[0604] [Chemical Formula 41]

[0605]

[0606] [Chemical Formula 42]

[0607]

[0608] [Chemical Formula 43]

[0609]

[0610] (Synthesis Method)

[0611] Certain polymeric compounds can be synthesized, for example, by the methods described in the examples described later.

[0612] The content of the specific polymerizable compound is preferably 0.5 to 20% by mass relative to the total solids content of the resin composition of the present invention. The lower limit is more preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0613] A specific polymerizable compound may be used alone or in combination with two or more compounds. When two or more compounds are used simultaneously, it is preferable that their total amount is within the range described above.

[0614] <Organometallic complexes>

[0615] From the viewpoint of chemical resistance, the resin composition of the present invention may contain organometallic complexes.

[0616] Organometallic complexes are any organic complexes containing metal atoms, but are preferably complexes containing metal atoms and organic groups, more preferably compounds in which organic groups coordinate with metal atoms, and even more preferably metallocene compounds.

[0617] In this invention, metallocene compounds refer to organometallic complexes having two cyclopentadienyl anionic derivatives that can have substituents as η5-ligands.

[0618] There are no particular limitations on the aforementioned organic groups, but hydrocarbon groups or groups formed by a combination of hydrocarbon groups and heteroatoms are preferred. As for heteroatoms, oxygen, sulfur, and nitrogen atoms are preferred.

[0619] In this invention, it is preferred that at least one of the organic groups is a cyclic group, and more preferably at least two of them are cyclic groups.

[0620] The aforementioned cyclic group is preferably selected from 5-membered cyclic groups and 6-membered cyclic groups, and more preferably from 5-membered cyclic groups.

[0621] The aforementioned cyclic group can be a hydrocarbon ring or a heterocycle, but it is preferred to be a hydrocarbon ring.

[0622] As a 5-membered ring cyclic group, cyclopentadienyl is preferred.

[0623] Furthermore, the organometallic complexes used in this invention preferably contain 2 to 4 cyclic groups per molecule.

[0624] The metal contained in the organometallic complex is not particularly limited, but it is preferably a metal corresponding to a Group 4 element, more preferably at least one metal selected from titanium, zirconium and hafnium, even more preferably at least one metal selected from titanium and zirconium, and especially preferably titanium.

[0625] Organometallic complexes can contain two or more metal atoms, or they can contain only one metal atom, but it is preferred that they contain only one metal atom. When organometallic complexes contain two or more metal atoms, they can contain only one type of metal atom or two or more types of metal atoms.

[0626] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnium compound, more preferably a titanocene compound, a zirconocene compound, or a hafnium compound, even more preferably a titanocene compound or a zirconocene compound, and especially preferably a titanocene compound.

[0627] The method by which organometallic complexes possess photoradical polymerization initiation energy is also one of the preferred methods of this invention.

[0628] In this invention, having a photoradical polymerization initiation energy indicates the ability to generate free radicals that can initiate free radical polymerization upon light irradiation. For example, when a composition containing a free radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light but the free radical crosslinking agent does not, the presence or absence of a photoradical polymerization initiation energy can be confirmed by checking whether the free radical crosslinking agent disappears. When confirming whether it has disappeared, an appropriate method can be selected based on the type of free radical crosslinking agent; for example, confirmation can be made simply by IR measurement (infrared spectroscopy) or HPLC measurement (high-performance liquid chromatography).

[0629] When the organometallic complex has a photoradical polymerization initiation energy, the organometallic complex is preferably a metallocene compound, more preferably a titanoceramic compound, a zirconium diaceramic compound or a hafnium diaceramic compound, even more preferably a titanoceramic compound or a zirconium diaceramic compound, and especially preferably a titanoceramic compound.

[0630] When the organometallic complex does not have a photoradical polymerization initiation energy, the organometallic complex is preferably selected from at least one compound selected from titanium diacene compounds, tetraalkoxy titanium compounds, acylated titanium compounds, titanium chelates, zirconium diacene compounds, and hafnium diacene compounds, more preferably selected from at least one compound selected from titanium diacene compounds, zirconium diacene compounds, and hafnium diacene compounds, even more preferably selected from at least one compound selected from titanium diacene compounds and zirconium diacene compounds, and especially preferably titanium diacene compounds.

[0631] The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

[0632] As organometallic complexes, compounds represented by the following formula (P) are preferably examples.

[0633] [Chemical Formula 44]

[0634]

[0635] In formula (P), M is a metal atom, and R are independent substituents.

[0636] The R mentioned above is preferably selected independently from aromatic groups, alkyl groups, halogen atoms and alkylsulfonyloxy groups.

[0637] In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom, a zirconium atom, or a hafnium atom, even more preferably a titanium atom or a zirconium atom, and especially preferably a titanium atom.

[0638] As an aromatic group in R of formula (P), examples include aromatic groups with 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups with 6 to 20 carbon atoms, such as phenyl, 1-naphthyl or 2-naphthyl.

[0639] The alkyl group in R of formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl.

[0640] Examples of halogen atoms in R include F, Cl, Br, and I.

[0641] The alkyl group constituting the alkyl sulfonyloxy group in the above-mentioned R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl.

[0642] The R mentioned above can also have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

[0643] Specific examples of organometallic complexes are not particularly limited, but examples include tetraisopropoxy titanium, tetra(2-ethylhexyloxy) titanium, diisopropoxybis(ethyl acetoacetate) titanium, diisopropoxybis(acetylacetone) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium, pentamethylcyclopentadienyltrimethylethanol titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) titanium, and the following compounds.

[0644] [Chemical Formula 45]

[0645]

[0646] In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 may be used, but are not limited thereto.

[0647] The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solids content of the resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.

[0648] One or more organometallic complexes can be used. When using two or more, it is preferable that the total amount is within the range described above.

[0649] <Other polymeric compounds>

[0650] The resin composition of the present invention preferably further comprises a polymeric compound different from the specific polymeric compound described above (hereinafter also referred to as "other polymeric compounds").

[0651] Other polymerizable compounds are compounds having polymerizable groups and do not correspond to the specific polymerizable compounds mentioned above.

[0652] Specifically, other polymerizable compounds include, for example, compounds containing polymerizable groups but no amide bonds, compounds in which polymerizable groups are directly bonded to amide bonds without via linkers, compounds in which polymerizable groups are bonded to amide groups via linkers and amide bonds are bonded to linkers on the amino side, and compounds in which homopolymers synthesized using polymerizable compounds do not exhibit the property of producing a base free from the main chain upon heating to 250°C.

[0653] Other examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0654] Other polymerizable compounds are preferably compounds having two or more polymerizable groups.

[0655] Furthermore, other polymerizable compounds preferably have polyalkene groups (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and especially preferably 2 or 3; the number of repetitions is preferably 2 to 12, more preferably 2 to 10, and especially preferably 2 to 6).

[0656] Among these, other polymeric compounds are compounds having two or more polymeric groups, and preferably have polyalkoxy groups; other polymeric compounds are compounds having two or more polymeric groups, and more preferably have polyalkoxy groups between at least two of the polymeric groups.

[0657] [Free radical crosslinking agent]

[0658] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0659] Free radical crosslinking agents are compounds having free radical polymerizable groups. Preferably, these groups contain vinyl unsaturated bonds. Examples of such groups include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acryloylamino groups.

[0660] Among these, the preferred groups containing ethylene unsaturated bonds are (meth)acryloyl, (meth)acryloylamino, and vinylphenyl, and from the viewpoint of reactivity, (meth)acryloyl is more preferred.

[0661] The free radical crosslinking agent is preferably a compound having one or more vinyl unsaturated bonds, but more preferably a compound having two or more. The free radical crosslinking agent may have three or more vinyl unsaturated bonds.

[0662] As for the above-mentioned compounds having two or more ethylene unsaturated bonds, compounds having 2 to 15 ethylene unsaturated bonds are preferred, compounds having 2 to 10 ethylene unsaturated bonds are more preferred, and compounds having 2 to 6 ethylene unsaturated bonds are even more preferred.

[0663] Furthermore, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably includes a compound having two ethylene unsaturated bonds and the above-mentioned compound having three or more ethylene unsaturated bonds.

[0664] The molecular weight of the free radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the free radical crosslinking agent is preferably 100 or more.

[0665] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. Furthermore, as another example, compounds such as unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, and allyl ethers can be used to replace the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, and these contents are incorporated into this specification.

[0666] Furthermore, the free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl)isocyanurate, glycerol, or trimethylolethane, which are added to polyfunctional alcohols and then subjected to (methyl) crosslinking. Compounds obtained by esterification of acrylate, such as (meth)acrylate amino esters described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth)acrylate, and other polyfunctional acrylates or methacrylates and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Additionally, polyfunctional (meth)acrylates obtained by reacting compounds having cyclic ether groups and vinyl unsaturated bonds, such as glycidyl (meth)acrylate, with polyfunctional carboxylic acids can also be cited.

[0667] Furthermore, as preferred free radical crosslinking agents besides those described above, compounds or calorie resins having a cyclohexane ring and having two or more groups containing ethylene unsaturated bonds, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, can also be used.

[0668] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, can also be used. Furthermore, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Additionally, compounds described as photopolymerizable monomers and oligomers in the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0669] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 may also be used, and these contents are incorporated into this specification.

[0670] Furthermore, in Japanese Patent Application Publication No. 10-062986, the following compound, which is described together with specific examples as formula (1) and formula (2), can also be used as a free radical crosslinking agent. This compound is obtained by (meth)acrylate esterification after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

[0671] In addition, compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and these contents are incorporated into this specification.

[0672] As a free radical crosslinking agent, preferred are dipentaerythritol triacrylate (commercially available as KAYARADD-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and 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.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)) and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0673] Commercially available free radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups, manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, a difunctional methyl acrylate with four ethoxy groups, manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate with six oxopentyl groups, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutylene oxygen groups; amine ester oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.); NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (manufactured by Nippon Kayaku). (manufactured by Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0674] As free radical crosslinking agents, amine ester acrylates as described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, and amine ester compounds having an ethylene oxide backbone as described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418 are also preferred. Furthermore, compounds having an amino or sulfide structure within the molecule as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238 are also suitable as free radical crosslinking agents.

[0675] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent having acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a free radical crosslinking agent that has acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred is a free radical crosslinking agent that has acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound, wherein the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. Commercially available examples include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., such as M-510 and M-520.

[0676] The preferred acid value of the free radical crosslinking agent containing acid groups is 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. As long as the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability, excellent developability, and good polymerizability. The acid value is determined according to the description in JIS K 0070:1992.

[0677] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses a difunctional methacrylate or acrylate.

[0678] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, etc. Diol dimethacrylate, dimethyloltricyclodecane dimethacrylate, dimethyloltricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct dimethacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct dimethacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, cyanuric acid EO-modified dimethacrylate, cyanuric acid-modified dimethacrylate, difunctional acrylates with other amine ester bonds, and difunctional methacrylates with amine ester bonds. Two or more of these can be mixed as needed.

[0679] Additionally, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain weight of approximately 200.

[0680] From the viewpoint of suppressing warping by controlling the elastic modulus of the accompanying pattern (cured product), a monofunctional free radical crosslinking agent can preferably be used as the free radical crosslinking agent for the resin composition of the present invention. As a monofunctional free radical crosslinking agent, preferably used are n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinyl caprolactam, and other N-vinyl compounds, alkenyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, in order to suppress volatilization before exposure, compounds having a boiling point of 100°C or higher at ambient pressure are also preferred.

[0681] In addition, examples of allyl compounds, such as diallyl phthalate and trimellitic acid, can be used as free radical crosslinking agents with two or more functions.

[0682] When a free radical crosslinking agent is included, its content relative to the total solids content of the resin composition of the present invention is preferably more than 0% by mass and less than 60% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0683] A single free radical crosslinking agent can be used alone, or two or more can be used in combination. When two or more are used simultaneously, it is preferable that their combined dosage is within the range described above.

[0684] [Other crosslinking agents]

[0685] The resin composition of the present invention preferably also contains other crosslinking agents different from the free radical crosslinking agents described above.

[0686] In this invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents described above. Preferably, they are compounds having a plurality of groups within the molecule that promote the formation of covalent bonds between the compounds in the composition or their reaction products by the photosensitive acid generator or photobase generator described above. More preferably, they are compounds having a plurality of groups within the molecule that promote the formation of covalent bonds between the compounds in the composition or their reaction products by the action of an acid or base.

[0687] The acid or base mentioned above is preferably an acid or base generated from a photoacid generator or a photoalkali generator during the exposure process.

[0688] As other crosslinking agents, compounds having at least one group selected from acyloxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from acyloxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[0689] Other crosslinking agents include, for example, compounds having a structure in which the hydrogen atoms of the amino groups are replaced by acyloxymethyl, hydroxymethyl, or alkoxymethyl groups through reaction of formaldehyde or formaldehyde and alcohol with melamine, glycourea, urea, alkylene urea, benzoguanamine, or other amino-containing compounds. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds can also be used.

[0690] Crosslinking agents that use melamine as an amino-containing compound are called melamine-based crosslinking agents; crosslinking agents that use urea, urea, or alkylene urea are called urea-based crosslinking agents; crosslinking agents that use alkylene urea are called alkylene urea-based crosslinking agents; and crosslinking agents that use benzoguanidine are called benzoguanidine-based crosslinking agents.

[0691] Among these, the resin composition of the present invention preferably contains at least one compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from urea-based crosslinking agents and melamine-based crosslinking agents described later.

[0692] Examples of compounds containing at least one of the alkoxymethyl and acylmethyl groups described in this invention include compounds in which the alkoxymethyl or acylmethyl group is directly substituted on an aromatic group or on a nitrogen atom of a urea structure described below, or on a triazine atom.

[0693] The alkoxymethyl or acylmethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms.

[0694] The total number of alkoxymethyl and acylmethyl groups in the above-mentioned compounds is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0695] The molecular weight of the above-mentioned compound is preferably below 1500, and more preferably between 180 and 1200.

[0696] [Chemical Formula 46]

[0697]

[0698] R 100 Indicates alkyl or acyl groups.

[0699] R 101 and R 102 Each of these groups independently represents a monovalent organic group and can bond with each other to form a ring.

[0700] As compounds in which alkoxymethyl or acylmethyl groups are directly substituted on aromatic groups, examples include various compounds of the following general formula.

[0701] [Chemical Formula 47]

[0702]

[0703] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each can be independently represented by an alkyl or acyl group, R 103 This refers to a group that represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to produce a base-soluble group (e.g., a group that is removed by the action of an acid, -C(R)). 4 )2COOR 5 The group represented (R) 4 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 5This indicates a group that is released through the action of an acid.

[0704] R 105 Each can independently represent an alkyl or alkenyl group, where a, b, and c are each 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

[0705] Groups that decompose under acidic conditions to produce base-soluble groups, groups that are removed under acidic conditions, and -C(R) groups. 4 )2COOR 5 The R in the represented group 5 For example, -C(R) can be cited. 36 (R) 37 (R) 38 ), -C(R 36 (R) 37 (OR) 39 ), -C(R 01 (R) 02 (OR) 39 )wait.

[0706] In the formula, R 36 ~R 39 Each can be independently represented as alkyl, cycloalkyl, aryl, aralkyl, or alkenyl. R 36 With R 37 They can bond together to form a ring.

[0707] 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.

[0708] The aforementioned alkyl group can be either straight-chain or branched.

[0709] The cycloalkyl group described above is preferably a cycloalkyl group with 3 to 12 carbon atoms, and more preferably a cycloalkyl group with 3 to 8 carbon atoms.

[0710] The aforementioned cycloalkyl groups can be monocyclic structures or polycyclic structures such as condensed rings.

[0711] The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and more preferably a phenyl group.

[0712] The aralkyl group is preferably an aralkyl group with 7 to 20 carbon atoms, and more preferably an aralkyl group with 7 to 16 carbon atoms.

[0713] The aryl group mentioned above refers to an aryl group that has been substituted with an alkyl group, and the preferred methods for these alkyl and aryl groups are the same as those for the alkyl and aryl groups mentioned above.

[0714] The alkenyl group is preferably an alkenyl group with 3 to 20 carbon atoms, and more preferably an alkenyl group with 3 to 16 carbon atoms.

[0715] Furthermore, these groups may also have known substituents within the scope of achieving the effects of the present invention.

[0716] R 01 and R 02 Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group.

[0717] The preferred groups are tertiary alkyl groups, acetal groups, cumyl ester groups, enol ester groups, etc., which are either decomposed by acid to produce a base-soluble group or are removed by acid. Tertiary alkyl ester groups and acetal groups are more preferred.

[0718] Specifically, the following structures can be cited as examples of compounds having an alkoxymethyl group. Regarding compounds having an acylmethyl group, compounds in which the alkoxymethyl group of the following compounds is replaced with an acylmethyl group can be cited. Various compounds can be cited as examples of compounds having an alkoxymethyl group or an acylmethyl group intramolecularly, but are not limited to these.

[0719] [Chemical Formula 48]

[0720]

[0721] [Chemical Formula 49]

[0722]

[0723] For compounds containing at least one of alkoxymethyl and acylmethyl groups, commercially available products can be used, or they can be synthesized using known methods.

[0724] From the viewpoint of heat resistance, compounds in which alkoxymethyl or acylmethyl groups are directly substituted on the aromatic ring or triazine ring are preferred.

[0725] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0726] Specific examples of urea-based crosslinking agents include monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetramethoxymethylated glycourea, monoethoxymethylated glycourea, diethoxymethylated glycourea, triethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea, etc.

[0727] Urea crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea.

[0728] Monohydroxymethylated ethionide or dihydroxymethylated ethionide, monomethoxymethylated ethionide, dimethoxymethylated ethionide, monoethoxymethylated ethionide, diethoxymethylated ethionide, monopropoxymethylated ethionide, dipropoxymethylated ethionide, monobutoxymethylated ethionide or dibutoxymethylated ethionide, etc., are ethionide-based crosslinking agents.

[0729] Propaneide-based crosslinking agents, including monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea.

[0730] 1,3-Di(methoxymethyl)-4,5-dihydroxy-2-imidazolidineone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone, etc.

[0731] Specific examples of benzoguanidine-based crosslinking agents include monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

[0732] In addition, as a compound having at least one group selected from hydroxymethyl and alkoxymethyl, a compound having at least one group selected from hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring) may also be preferred.

[0733] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenylbenzene. Methyl ketone, methoxymethylbenzoic acid methoxymethylphenyl ester, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4”-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0734] Other commercially available crosslinking agents can also be used. Preferred commercially available agents include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0735] Furthermore, the resin composition of the present invention preferably contains at least one compound selected from epoxy compounds, cyclobutane compounds and benzoxazine compounds as other crosslinking agents.

[0736] -Epoxy compounds (compounds containing epoxy groups)-

[0737] As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy groups undergo cross-linking reactions below 200°C and do not produce dehydration reactions caused by cross-linking, thus minimizing film shrinkage. Therefore, the presence of an epoxy compound is effective in suppressing low-temperature curing and warpage of the resin composition of the present invention.

[0738] The epoxy compound preferably contains polyethylene oxide. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide indicates that the number of repeating units in the ethylene oxide is 2 or more, preferably 2 to 15.

[0739] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and silicones with epoxy groups such as polymethyl(glycidyloxypropyl)siloxane, but these are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (these are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, and Rika... Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-30 00-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XI)-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 product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Furthermore, the following compounds may also be used preferably.

[0740] [Chemical Formula 50]

[0741]

[0742] In the formula, n is an integer from 1 to 5 and m is an integer from 1 to 20.

[0743] Following the above structure, from the viewpoint of balancing heat resistance and elongation improvement, it is preferable that n is 1 to 2 and m is 3 to 7.

[0744] -Oxycyclic butane compounds (compounds containing oxycyclic butane groups)-

[0745] Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxybutane, 1,4-bis{[(3-ethyl-3-oxocyclobutane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxocyclobutane)methyl] ester. As specific examples, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. is preferably used; these can be used alone or in combination of two or more.

[0746] -Benzoxazine compounds (compounds containing a benzoxazole group)-

[0747] Since the crosslinking reaction is caused by the ring-opening addition reaction, the benzoxazine compound does not produce degassing during curing, thereby further reducing thermal shrinkage and inhibiting warping, and is therefore preferred.

[0748] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are product names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resin, and phenolic varnish-type dihydrobenzoxazine compounds. These can be used alone or in combination of two or more.

[0749] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other crosslinking agents may be only one type or may be two or more types. When two or more other crosslinking agents are contained, their total content is preferably within the above-mentioned range.

[0750] [Polymerization initiator]

[0751] The resin compositions of the present invention preferably contain a polymerization initiator capable of initiating polymerization by light and / or heat. In particular, a photopolymerization initiator is preferred.

[0752] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible regions is preferred. Furthermore, an active agent that generates active radicals by interacting with a photoexcited sensitizer may also be used.

[0753] The photoradical polymerization initiator preferably contains at least one initiator with a concentration of at least about 50 L / mol in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 / cm -1 Compounds with molar absorptivity. The molar absorptivity of a compound can be determined using known methods. For example, it is preferably determined using a UV-Vis spectrophotometer (Varian Medical Systems, Inc., Cary-5 spectrophotometer) and with ethyl acetate solvent at a concentration of 0.01 g / L.

[0754] As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl diimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron-aromatic complexes. For details, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples can be cited in paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peracid-based initiators described in Japanese Patent Application Publication No. 2019-167313, and these contents are also incorporated into this specification.

[0755] As a ketone compound, examples include the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, and this content is incorporated into this specification. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0756] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and this content is incorporated herein by reference.

[0757] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0758] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0759] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, whose maximum absorption wavelength is matched with light sources of wavelengths such as 365 nm or 405 nm, can also be used, and this content is included in this specification.

[0760] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Furthermore, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, or IRGACURE-TPO (all manufactured by BASF) can be used.

[0761] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0762] Oxime compounds are preferred as photoradical polymerization initiators. Using oxime compounds allows for more effective improvement in exposure latitude. Oxime compounds are particularly preferred because they offer a wide exposure latitude (exposure margin) and also function as photocuring accelerators.

[0763] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science. The compounds described in and Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Publication No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent Application Publication No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Application Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, and the compounds described in International Publication No. 2013 / 167515, etc., are included in this specification.

[0764] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))butane-2-one, 3-(acetoxy(imino))butane-2-one, 3-(propionyloxy(imino))butane-2-one, 2-(acetoxy(imino))pentane-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butane-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In the resin compositions of the present invention, oxime compounds (oxime-based photoradical polymerization initiators) are particularly preferred as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linker group within the molecule.

[0765] [Chemical Formula 51]

[0766]

[0767] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKACORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052) are also preferred. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) are also acceptable. Additionally, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMERARKEMA) are also acceptable. Furthermore, oxime compounds with the following structures can also be used.

[0768] [Chemical Formula 52]

[0769]

[0770] Oxime compounds having a cyclohexane ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a cyclohexane ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, and these contents are incorporated into this specification.

[0771] As photoradical polymerization initiators, oxime compounds having at least one benzene ring in the carbazole ring forming the naphthalene ring skeleton can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0772] Furthermore, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, and these contents are included in this specification.

[0773] Nitro-containing oxime compounds can be used as photopolymerization initiators. Nitro-containing oxime compounds are preferably dimers. Specific examples of nitro-containing oxime compounds include compounds described in paragraphs 0031-0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008-0012 and 0070-0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007-0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKACORPORATION) can also be cited as a nitro-containing oxime compound.

[0774] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 as described in International Publication No. 2015 / 036910.

[0775] Oxime compounds with hydroxyl substituents bonded to the carbazole skeleton can also be used as photoradical polymerization initiators. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, which are incorporated herein by reference.

[0776] As a photopolymerization initiator, Ar aromatic cyclic groups with electron-withdrawing groups introduced onto the aromatic ring can also be used. 0X1 Oxime compounds (hereinafter also referred to as oxime compounds OX). As the above aromatic cyclic group Ar... 0X1Examples of electron-withdrawing groups include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano groups, with acyl and nitro groups being preferred. Acyl groups are more preferred for their ease of forming films with excellent lightfastness, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthio, arylthio, acyl, or amino groups, with alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthio, arylthio, or amino groups being more preferred, and alkoxy, alkylthio, or amino groups being even more preferred.

[0777] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2).

[0778] [Chemical Formula 53]

[0779]

[0780] In the formula, R X1 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphonoyl, carbamoyl, or aminesulfonyl.

[0781] R X2 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy, or amino.

[0782] R X ~R X14 Each can be used to represent a hydrogen atom or a substituent independently.

[0783] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0784] In the above formula, R is preferred. X12 R is an electron-withdrawing group. X10 R 111 R X13 R X14 It is a hydrogen atom.

[0785] As a specific example of the oxime compound OX, the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 are cited, and this content is incorporated into this specification.

[0786] Examples of preferred oxime compounds include oxime compounds with specific substituents as shown in Japanese Patent Application Publication No. 2007-269779 or oxime compounds with thioaryl groups as shown in Japanese Patent Application Publication No. 2009-191061, and these are included in this specification.

[0787] From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0788] Further preferred photoradical polymerization initiators are trihalomethane triazine compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. More preferably, at least one compound is selected from trihalomethane triazine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. More preferably, metallocene compounds or oxime compounds are used.

[0789] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones formed by ring condensation with aromatic rings such as alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkyl benzoin; and benzyl derivatives such as benzyl dimethyl ketal. Compounds represented by formula (I) below can also be used.

[0790] [Chemical Formula 54]

[0791]

[0792] In equation (I), R I00The alkyl group having 1 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, the alkoxy or phenyl group having 1 to 12 carbon atoms, or the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, the halogen atom, the cyclopentyl group, the cyclohexyl group, the alkenyl group having 2 to 12 carbon atoms, the alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and the alkyl group having 1 to 4 carbon atoms, are at least one substituted phenyl or biphenyl group. I0 1 is the group represented by formula (II) or is a group that interacts with R. I00 The same group, R I02 ~R I04 Each is independently an alkyl group, an alkoxy group, or a halogen atom, having 1 to 12 carbon atoms.

[0793] [Chemical Formula 55]

[0794]

[0795] In the formula, R I05 ~R I07 R in equation (I) above I02 ~R I04 same.

[0796] Furthermore, the photoradical polymerization initiator can also be the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, and this content is incorporated into this specification.

[0797] As photoradical polymerization initiators, difunctional or trifunctional or higher photoradical polymerization initiators can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Furthermore, when using compounds with asymmetric structures, crystallinity decreases while solubility in solvents and the like increases, making it less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and (G) described in Japanese Patent Application Publication No. 2013-522445. The oxime ester photoinitiators described in International Publication No. 2016 / 034963, paragraph 0007 of Japanese Patent Publication No. 2017-523465, paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and paragraph 0017-0026 of Japanese Patent Application Publication No. 6469669 are included in this specification.

[0798] When a photopolymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may be only one type or may contain two or more types. When two or more photopolymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0799] In addition, photopolymerization initiators sometimes function as thermal polymerization initiators, and therefore crosslinking based on photopolymerization initiators is sometimes further carried out by heating in an oven or heating plate.

[0800] [Sensitizer]

[0801] The resin composition may include a sensitizer. The sensitizer absorbs specific active radiation to become electronically excited. The electronically excited sensitizer then comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., thereby generating electron transfer, energy transfer, and heat generation. Consequently, the thermal free radical polymerization initiator or photofree radical polymerization initiator undergoes a chemical change and decomposes, generating free radicals, acids, or bases.

[0802] As usable sensitizers, compounds such as benzophenone, milchnerone, coumarin, pyrazole azo, phenylamino azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzylene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthridine, pyrrolopyrazole azomethine, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0803] Examples of sensitizers include milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylenepropyl dihydroindone, and p-dimethylamino Benzylene dihydroindone, 2-(p-dimethylaminophenylbenzylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxy Carbonyl-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 Isoamyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0804] Furthermore, other sensitizing pigments can be used.

[0805] For details regarding the sensitized pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, and this information is incorporated into this specification.

[0806] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used simultaneously.

[0807] [Chain transfer agent]

[0808] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having a thiocarbonyl sulfide group for RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate free radicals by donating hydrogen to low-activity free radicals or by deprotonation after oxidation. In particular, thiols are preferably used.

[0809] Furthermore, the chain transfer agent can also be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219, and this content is incorporated into this specification.

[0810] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids content of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, their total content is preferably within the above-mentioned range.

[0811] <Alkali-generating agents>

[0812] The resin composition of the present invention may contain an alkali-generating agent. The alkali-generating agent is a compound capable of generating alkali through physical or chemical action. Preferred alkali-generating agents for the resin composition of the present invention include thermal alkali-generating agents and photo-alkali-generating agents.

[0813] The compounds corresponding to the specific polymerizable compounds mentioned above do not correspond to the alkali generating agents described in this invention.

[0814] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains an alkali-generating agent. By containing a thermal alkali-generating agent in the resin composition, for example by heating, the cyclization reaction of the precursor can be promoted, resulting in good mechanical properties or chemical resistance of the cured product, and thus good performance as an interlayer insulating film for rewiring layers included in semiconductor packages.

[0815] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from a base-generating agent include secondary and tertiary amines.

[0816] There are no particular limitations on the alkali generating agent of the present invention, and known alkali generating agents can be used. Examples of known alkali generating agents include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0817] Specific compounds that can be cited as nonionic base generating agents include those represented by formulas (B1), (B2), or (B3).

[0818] [Chemical Formula 56]

[0819]

[0820] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3 Each of these can be an organic group, a halogen atom, or a hydrogen atom that does not possess a tertiary amine structure. Specifically, Rb... 1 and Rb 2 It will not simultaneously become a hydrogen atom. Furthermore, Rb 1 、Rb 2 and Rb 3 None of them contain a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of the trivalent nitrogen atom are covalently bonded to carbon atoms in a hydrocarbon system. Therefore, it is not limited to the case where the bonded carbon atoms are carbon atoms that form a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

[0821] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3Preferably, at least one of them contains a cyclic structure, more preferably at least two of them contain a cyclic structure. The cyclic structure can be any of a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring formed by the condensation of two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0822] More specifically, Rb 1 and Rb 2 Preferably, the substituents are hydrogen atoms, alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), or aralkyl groups (preferably with 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). These groups may have substituents within the range that enables the effects of the present invention. Rb 1 With Rb 2 They can bond together to form rings. Preferably, the formed rings are nitrogen-containing heterocycles with 4 to 7 members. In particular, Rb... 1 and Rb 2 Preferably, it is a straight-chain, branched, or cyclic alkyl group that may have substituents (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), more preferably a cycloalkyl group that may have substituents (preferably with 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), and even more preferably a cyclohexyl group that may have substituents.

[0823] As Rb 3 Examples of such compounds include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), aralkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), aryl-alkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or arylalkoxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Preferably, the compounds are cycloalkyl (preferably with 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), aryl, or arylalkoxy. Rb 3Substituents may also be present within the scope of achieving the effects of this invention.

[0824] The compound represented by formula (B1) is preferably the compound represented by formula (B1-1) or formula (B1-2) below.

[0825] [Chemical Formula 57]

[0826]

[0827] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 respectively with Rb in equation (B1) 1 and Rb 2 The meanings are the same.

[0828] Rb 13 The groups are alkyl (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl (preferably with 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or aralkyl (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), and may have substituents within the range that enables the effects of the present invention. Rb 13 Preferably, it is an aryl alkyl group.

[0829] Rb 33 and Rb 34 Each of the following is independently composed of hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen atoms.

[0830] Rb 35 The carbon atoms are alkyl (preferably 1 to 24, more preferably 1 to 12, and even more preferably 3 to 8), alkenyl (preferably 2 to 12, more preferably 2 to 10, and even more preferably 3 to 8), aryl (preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 12), aralkyl (preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 12), and preferably aryl.

[0831] The compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).

[0832] [Chemical Formula 58]

[0833]

[0834] Rb 11 and Rb 12 Rb in equation (B1-1) 11 and Rb 12 The meanings are the same.

[0835] Rb 15 and Rb 16 The atom is hydrogen, alkyl (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3), aryl (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen or methyl.

[0836] Rn 17 The alkyl group is preferably 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 3 to 8, alkenyl group is preferably 2 to 12 carbon atoms, more preferably 2 to 10, and even more preferably 3 to 8, aryl group is preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12, and aralkyl group is preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12, wherein aryl group is preferred.

[0837] [Chemical Formula 59]

[0838]

[0839] In formula (B3), L represents a hydrocarbon group, which is a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the connecting chain linking adjacent oxygen and carbon atoms, and the number of atoms in the connecting chain path is three or more. Furthermore, R... N1 and R N2 Each of these represents a monovalent organic group independently.

[0840] In this specification, a "linking chain" refers to an atomic chain connecting two atoms or groups of atoms in the shortest possible (minimum number of atoms) manner. 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 linking chain consists of 4 carbon atoms, and the number of atoms in the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "linking chain length") is 4.

[0841] [Chemical Formula 60]

[0842]

[0843] The number of carbon atoms in L of formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and especially preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above-described intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and especially preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds as base generating agents include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0844] Furthermore, the alkali generating agent preferably comprises a compound represented by the following formula (N1).

[0845] [Chemical Formula 61]

[0846]

[0847] In equation (N1), R N1 and R N2 Each of the following independently represents a monovalent organic group, R C1 The symbol represents a hydrogen atom or a protecting group, and L represents a divalent linker.

[0848] L is a divalent linker, preferably a divalent organic group. The linker chain length is preferably 1 or more, more preferably 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linker chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0849] In equation (N1), R N1 and R N2 Each organic group independently represents a monovalent organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10). Specifically, examples include aliphatic hydrocarbon groups (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or aromatic hydrocarbon groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), preferably aliphatic hydrocarbon groups. If R N1and R N2 Using aliphatic hydrocarbon groups results in a highly basic base, which is therefore preferred. Furthermore, both aliphatic and aromatic hydrocarbon groups can have substituents, and these substituents can have oxygen atoms in the aliphatic hydrocarbon chain or aromatic ring. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0850] As a component of R N1 and R N2 Examples of aliphatic hydrocarbon groups include straight-chain or branched chain alkyl groups, cyclic alkyl groups, groups relating to combinations of chain alkyl and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. Straight-chain or branched chain alkyl groups preferably have 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl.

[0851] The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0852] The group relating to the combination of chain alkyl and cyclic alkyl groups preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of groups relating to the combination of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0853] The alkyl group having oxygen atoms in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched.

[0854] From the perspective of increasing the boiling point of the alkali produced by the subsequent decomposition, R N1 and R N2 Preferably, the alkyl group has 5 to 12 carbon atoms. In formulations where adhesion with metals (e.g., copper) is important, groups having cyclic alkyl groups or alkyl groups having 1 to 8 carbon atoms are preferred.

[0855] R N1 and R N2 They can connect to each other to form a ring structure. When forming a ring structure, oxygen atoms, etc., can be present in the chain. Furthermore, R... N1 and R N2The formed ring structure can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. The formed ring structure is preferably a 5-membered or 6-membered ring containing a nitrogen atom as in formula (N1), such as pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, pyrazoleidine rings, piperidine rings, piperazine rings, morpholine rings, etc., with pyrroleline rings, pyrrolidine rings, piperidine rings, piperazine rings, and morpholine rings being particularly preferred.

[0856] R C1 It represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0857] As a protecting group, a protecting group that decomposes by the action of an acid or a base is preferred, and a protecting group that decomposes by an acid is a preferred example.

[0858] Specific examples of protecting groups include chain-like or cyclic alkyl groups, or chain-like or cyclic alkyl groups having oxygen atoms in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl. Specifically, examples of chain-like alkyl groups having oxygen atoms in the chain include alkyloxyalkyl groups, and more specifically, examples include methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxycyclobutyl, tetrahydrofuranyl, and tetrahydropyranyl (THP).

[0859] There are no particular restrictions on the divalent linking group constituting L, but it is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have substituents and may also have atoms of any kind other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that may have an oxygen atom in the chain is preferred; more preferably, an aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain is preferred; and even more preferably, an aliphatic hydrocarbon group that may have an oxygen atom in the chain is preferred. These groups preferably do not have an oxygen atom.

[0860] The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group (e.g., arylene alkyl) associated with the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0861] As a linking group L, specifically, it is preferably a linear or branched chain alkylene, a cyclic alkylene, a group relating to a combination of linear and cyclic alkylene, an alkylene having an oxygen atom in the chain, a linear or branched chain alkenyl, a cyclic alkenyl, an aryl, or an arylalkylene.

[0862] The linear or branched alkylene groups preferably have 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4.

[0863] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6.

[0864] The groups associated with the combination of chain alkylene and cyclic alkylene are preferably 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6.

[0865] The alkylene group having oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. Preferably, the alkylene group having oxygen atoms in the chain has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

[0866] The linear or branched chain-like alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds in the linear or branched chain-like alkenyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0867] The cyclic alkenyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The number of C=C bonds in the cyclic alkenyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

[0868] The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10.

[0869] The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11.

[0870] Preferably, the alkylene group is a chain-like alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain-like alkenyl group, an aryl group, an aryl group, or an alkylene group; more preferably, it is 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), or oxyethylene (especially 1,2-ethoxy-1,2-ethylene).

[0871] Examples of alkali-generating agents can be given below, but the present invention is not limited thereto.

[0872] [Chemical Formula 62]

[0873]

[0874] The molecular weight of the nonionic hot alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0875] Specific preferred compounds for generating ionic bases include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0876] Specific examples of ammonium salts include the following compounds, but the invention is not limited to these.

[0877] [Chemical Formula 63]

[0878]

[0879] Specific examples of imine salts include the following compounds, but the present invention is not limited to these.

[0880] [Chemical Formula 64]

[0881]

[0882] When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by weight or more, and even more preferably 0.5 parts by weight or more. The upper limit is more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less, but can be 5 parts by weight or less, or 4 parts by weight or less.

[0883] One or more alkali-generating agents can be used. When using two or more, it is preferable that the total amount is within the above range.

[0884] Solvent

[0885] The resin composition of the present invention preferably contains a solvent.

[0886] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0887] Examples of esters preferably include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.)). Alkyl propionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0888] Examples of ethers include, for instance, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0889] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydroglucanone.

[0890] Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0891] As a sulfoxide, dimethyl sulfoxide is a preferred example.

[0892] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0893] Examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolium ketone.

[0894] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene 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, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

[0895] Regarding solvents, from the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvents.

[0896] In this invention, a solvent preferably selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, L-glucanone, dihydroglucanone, or a mixed solvent consisting of two or more solvents is preferred. Particularly preferred is the simultaneous use of dimethyl sulfoxide and γ-butyrolactone, or the simultaneous use of N-methyl-2-pyrrolidone and ethyl lactate.

[0897] From the viewpoint of coatability, it is preferable to set the solvent content to an amount that is 5 to 80% by mass of the total solids concentration of the resin composition of the present invention, more preferably to an amount that is 5 to 75% by mass, even more preferably to an amount that is 10 to 70% by mass, and even more preferably to an amount that is 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating and the coating method.

[0898] The resin composition of the present invention may contain only one solvent or two or more solvents. When containing two or more solvents, it is preferable that their total number is within the above-mentioned range.

[0899] <Metal Adhesion Modifier>

[0900] The resin composition of the present invention preferably contains a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

[0901] [Silane coupling agent]

[0902] Examples of silane coupling agents include, for example, compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014-041264, compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067-0078 of Japanese Patent Application Publication No. 2018-173573, and these contents are incorporated herein by reference. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Moreover, the following compounds are preferred as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0903] [Chemical Formula 65]

[0904]

[0905] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tri-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0906] [Aluminum-based adhesive additives]

[0907] Examples of aluminum-based adhesive additives include aluminum tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and aluminum diisopropoxide of ethyl acetoacetate.

[0908] Furthermore, as other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are incorporated into this specification.

[0909] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably in the range of 0.01 to 30 parts by weight, more preferably in the range of 0.1 to 10 parts by weight, and even more preferably in the range of 0.5 to 5 parts by weight. By setting the content above the lower limit, the adhesion between the pattern and the metal layer becomes good; by setting the content below the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion modifier can be only one type or two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0910] <Migration Inhibitor>

[0911] The resin composition of the present invention preferably further comprises a migration inhibitor. By comprising a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively suppressed.

[0912] There are no particular limitations on the migration inhibitors, but compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyrazine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acylhydrazine derivative compounds are preferred. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0913] Alternatively, ion trapping agents that capture anions such as halide ions can also be used.

[0914] Other migration inhibitors may be used, including 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 compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, and these contents are incorporated into this specification.

[0915] The following compounds can be cited as specific examples of migration inhibitors.

[0916] [Chemical Formula 66]

[0917]

[0918] 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, relative to the total solid content of the resin composition of the present invention.

[0919] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the range mentioned above.

[0920] <Polymerization Inhibitor>

[0921] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0922] Specific compounds used as polymerization inhibitors include, for example, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallnutol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), cerium salt of N-nitrosophenylhydroxylamine, aluminum salt of N-nitroso-N-phenylhydroxylamine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-8-hydroxyquinoline, etc. Nitro-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 2,2,6,6-tetramethylpiperidine 1-oxy radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-pyrrolidine, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Patent Application Publication No. 2015 / 125469 can also be used, and this content is incorporated into this specification.

[0923] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solids content of the resin composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0924] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, it is preferable that their total number is within the range mentioned above.

[0925] <Other Additives>

[0926] The resin composition of the present invention can be formulated with various additives as needed, within the scope of achieving the effects of the present invention. These additives include, for example, photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymers, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately including these components, the physical properties of the membrane can be adjusted. Regarding these components, reference can be made to paragraphs 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812) and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein by reference. When incorporating these additives, it is preferable that their total amount is set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0927] [surfactants]

[0928] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0929] By including a surfactant in the resin composition of the present invention, the liquid properties (especially flowability) during preparation as a coating liquid are further improved, thereby further improving the uniformity of the coating thickness or the liquid-saving properties. That is, when a film is formed using a coating liquid containing a surfactant composition, the interfacial tension between the coated surface and the coating liquid is reduced, improving the wettability of the coated surface and thus improving the coating properties. Therefore, it is more preferable to form a film with a uniform thickness and small thickness non-uniformity.

[0930] Examples of fluorinated surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (manufactured by 3M Japan Limited), Surflon S-382, and Surflon... SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVASolutions Inc.), etc. Fluorinated surfactants may also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, and these contents are included in this specification. Block polymers can also be used as fluorinated surfactants. For example, compounds described in Japanese Patent Application Publication No. 2011-89090 can be cited, and these contents are incorporated into this specification.

[0931] Fluorinated surfactants can also preferably use fluorinated polymers comprising repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or propyleneoxy groups). Examples of the following compounds as fluorinated surfactants used in this invention are also provided.

[0932] [Chemical Formula 67]

[0933]

[0934] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0935] Fluorinated surfactants can also be used to treat fluoropolymers with vinyl unsaturated groups on their side chains. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Furthermore, commercially available examples include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.

[0936] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of the uniformity of coating thickness or liquid saving, and also have good solubility in the composition.

[0937] Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow CorningToray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0938] Examples of hydrocarbon-based surfactants include PIONIN A-76, Newkalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FATCO., LTD.).

[0939] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. As commercially available products, examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO 0IL&FAT CO., LTD.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., LTD.), etc.

[0940] As cationic surfactants, examples include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), and WO0 1 (manufactured by Yusho Co., Ltd.).

[0941] As anionic surfactants, examples include WO04, WO05, WO17 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0942] Surfactants can be used in single-agent or in combination of two or more.

[0943] The surfactant content is preferably 0.001 to 2.0% by mass relative to the total solids content of the composition, more preferably 0.005 to 1.0% by mass.

[0944] [Higher fatty acid derivatives]

[0945] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoamide can be added to the resin composition of the present invention, so that they are unevenly present on the surface of the resin composition of the present invention during the drying process after coating.

[0946] Furthermore, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 may also be used for higher fatty acid derivatives, and this content is incorporated into this specification.

[0947] When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives is preferably 0.1 to 10% by mass relative to the total solids content of the resin composition of the present invention. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above range.

[0948] [Thermal polymerization initiator]

[0949] The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, polymerization reactions of the resin and the polymerizable compound can also be carried out, thus further improving solvent resistance. Furthermore, sometimes the aforementioned photopolymerization initiators also have the function of initiating polymerization through heat, and can sometimes be added as thermal polymerization initiators.

[0950] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited as thermal free radical polymerization initiators, and this content is incorporated into this specification.

[0951] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0952] [Inorganic particles]

[0953] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0954] The average particle size of the aforementioned inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and especially preferably 0.04 to 0.5 μm.

[0955] The above-mentioned average particle size of inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be determined by dynamic light scattering based on the Nanotrac WAVE II EX-150 (Nikkiso Co., Ltd.).

[0956] In cases where the above measurements are difficult to perform, measurements can also be taken using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0957] [Ultraviolet absorber]

[0958] The compositions of the present invention may contain ultraviolet absorbers. As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.

[0959] Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Furthermore, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0960] Examples of acrylonitrile-based UV absorbers that can be replaced include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. In addition, examples of triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tetrazoloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. Bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, etc.

[0961] In this invention, the various ultraviolet absorbers described above can be used individually or in combination of two or more.

[0962] The composition of the present invention may or may not contain an ultraviolet absorber, but when it does contain an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less, relative to the total solid content of the composition of the present invention.

[0963] [Organotitanium compounds]

[0964] The resin composition of this embodiment may contain an organotitanium compound. Because the resin composition contains an organotitanium compound, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0965] As examples of usable organotitanium compounds, organic groups can be bonded to titanium atoms via covalent or ionic bonds.

[0966] Specific examples of organotitanium compounds are shown in I) to VII) below:

[0967] I) Titanium chelate compounds: Among these, the resin composition exhibits excellent storage stability and can achieve good cured patterns, thus titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples include diisopropanol bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropanol bis(2,4-pentanedione) titanium, diisopropanol bis(tetramethylheptanedione) titanium, diisopropanol bis(ethyl acetoacetate) titanium, etc.

[0968] II) Tetraalkoxy titanium compounds: such as tetra(n-butanol)titanium, tetraethanol titanium, tetra(2-ethylhexanol)titanium, tetraisobutanol titanium, tetraisopropanol titanium, tetramethanol titanium, tetramethoxypropanol titanium, tetramethylphenyl oxytitanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc.

[0969] III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0970] IV) Monoalkoxy titanium compounds: such as titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylphenyl sulfonate) isopropoxide, etc.

[0971] V) Titanium oxide compounds: such as titanium dioxide bis(pentanedione), titanium dioxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc.

[0972] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0973] VII) Titanate coupling agents: such as isopropyltridodecylbenzenesulfonyl titanate, etc.

[0974] Among these, from the viewpoint of exhibiting better chemical resistance, at least one compound selected from the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound, and III I) diacetic titanium compound is preferred as the organotitanium compound. In particular, diisopropanol bis(ethyl acetoacetate) titanium, tetra(n-butanol) titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium are preferred.

[0975] When an organotitanium compound is incorporated, its amount relative to 100 parts by weight of a specific resin is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight. When the amount is 0.05 parts by weight or more, the resulting cured pattern more effectively exhibits good heat resistance and chemical resistance; on the other hand, when the amount is 10 parts by weight or less, the composition exhibits superior storage stability.

[0976] [Antioxidants]

[0977] The compositions of the present invention may include antioxidants. By including antioxidants as additives, the elongation properties of the cured film and its adhesion to metal materials can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds can be mentioned. Compounds having substituents at the site adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the above-mentioned substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, the antioxidant is also preferably a compound having both a phenolic group and a phosphite group within the same molecule. Furthermore, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, and Adekastab A0-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants may also be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, and this content is incorporated herein by reference. Moreover, the compositions of the present invention may contain potential antioxidants as needed. As potential antioxidants, compounds in which the site of antioxidant activity is protected by a protecting group can be cited, and which exert their antioxidant activity by heating at 100–250°C or at 80–200°C in the presence of an acid / base catalyst to remove the protecting group. Compounds described in International Publication Nos. 2014 / 021023, 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 can be cited as potential antioxidants, and these contents are incorporated herein by reference. Commercially available products that are potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

[0978] Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0979] [Chemical Formula 68]

[0980]

[0981] In general formula (3), R 5 R represents an alkyl group having 2 or more hydrogen atoms or carbon atoms (preferably 2 to 10 carbon atoms). 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 It refers to an alkylene group with 2 or more carbon atoms (preferably 2 to 10 carbon atoms) and an organic group with a valence of 1 to 4 containing at least one of an oxygen atom and a nitrogen atom. k represents an integer from 1 to 4.

[0982] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups present in the resin. Furthermore, it can inhibit metal oxidation by preventing rust on metallic materials.

[0983] It can act on both resin and metal materials simultaneously, therefore k is more preferably an integer from 2 to 4. As R 7. Examples of substituents include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof. Substituents may also be present. From the viewpoint of solubility in the developer and metal adhesion, alkyl ether groups and -NH- are preferred; from the viewpoint of interaction with the resin and metal adhesion during metal complex formation, -NH- is more preferred.

[0984] Regarding the compounds represented by general formula (3), the following examples can be given, but are not limited to the following structures.

[0985] [Chemical Formula 69]

[0986]

[0987] [Chemical Formula 70]

[0988]

[0989] [Chemical Formula 71]

[0990]

[0991] [Chemical Formula 72]

[0992]

[0993] The amount of antioxidant added is preferably 0.1 to 10 parts by weight relative to the resin, more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, it is easy to obtain the effect of improving elongation characteristics or adhesion to metal materials, even under high temperature and high humidity environments. Furthermore, by setting the amount added to 10 parts by weight or less, the sensitivity of the resin composition can be improved, for example, through interaction with photosensitizers. Only one type of antioxidant may be used, or two or more types may be used. When using two or more types, it is preferable that the total amount of these antioxidants is within the above-mentioned range.

[0994] [Anticoagulant]

[0995] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0996] In this invention, one type of anti-coagulation agent can be used alone, or two or more types can be used in combination.

[0997] The compositions of the present invention may or may not contain anti-coagulants, but when they do contain anti-coagulants, the content of anti-coagulants is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, relative to the total solid content of the compositions of the present invention.

[0998] [Phenolic compounds]

[0999] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, BisRS-26X (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION).

[1000] In this invention, phenolic compounds can be used alone or in combination of two or more.

[1001] The compositions of the present invention may or may not contain phenolic compounds, but when they do contain phenolic compounds, the content of phenolic compounds is preferably 0.01% by mass or more and 30% by mass or less relative to the total solid content of the compositions of the present invention, more preferably 0.02% by mass or more and 20% by mass or less.

[1002] [Other polymers]

[1003] Other examples of polymeric compounds include siloxane resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, phenolic varnish resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may be modified forms incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[1004] In this invention, other polymer compounds can be used alone or in combination of two or more.

[1005] The compositions of the present invention may or may not contain other polymeric compounds, but when they are included, the content of other polymeric compounds is preferably 0.01% by mass or more and 30% by mass or less relative to the total solid content of the compositions of the present invention, more preferably 0.02% by mass or more and 20% by mass or less.

[1006] <Characteristics of Resin Compositions>

[1007] The viscosity of the resin composition of the present invention can be adjusted by the concentration of the solid components of the resin composition. From the viewpoint of coating film thickness, 1,000 mm is preferred. 2 / s~12,000mm 2 / s, more preferably 2,000 mm 2 / s~10,000mm 2 / s, further preferably 2,500mm 2 / s~8,000mm 2 / s. As long as it remains within the above range, a highly uniform coating film can be easily obtained. For 1,000 mm... 2 If the thickness is above / s, it is easy to coat the film with the thickness required for reinsertion insulation, for example, 12,000 mm. 2 When the speed is below a certain value, a coating with excellent surface treatment can be obtained.

[1008] <Restrictions on the Contents of Substances in Resin Compositions>

[1009] The moisture content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. As long as it is less than 2.0%, the storage stability of the resin composition is improved.

[1010] Methods for maintaining moisture content include adjusting the humidity in storage conditions and reducing the porosity of the storage container.

[1011] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, it is preferable that the total amount of these metals is within the above-described range.

[1012] Furthermore, as a method to reduce metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention using a filter; and lining the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible.

[1013] Considering the use of the resin composition of the present invention as a semiconductor material, from the viewpoint of wiring corrosion resistance, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. Of this, the content existing in the form of halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. Preferably, the total amount of chlorine atoms and bromine atoms, or the total amount of chloride ions and bromide ions, is within the above-mentioned ranges.

[1014] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[1015] As a container for the resin composition of the present invention, conventionally known containers can be used. Furthermore, to prevent impurities from contaminating the raw materials or the resin composition of the present invention, multi-layer bottles with an inner wall composed of six layers of six different resins, or bottles with a seven-layer structure formed from the six resins, are preferred as containers. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[1016] <Cure of the resin composition>

[1017] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[1018] The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.

[1019] The curing of the resin composition is preferably carried out by heating, with the heating temperature more preferably in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C. The cured form of the resin composition is not particularly limited, and can be in the form of a film, rod, sphere, or granules, depending on the application. In this invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the shape of the cured product can be selected according to applications such as forming a protective film on a wall surface, forming holes for conduction, adjusting impedance or capacitance or internal stress, or imparting heat dissipation. The film thickness of the cured product (the film formed by the cured product) is preferably 0.5 μm or more and 150 μm or less.

[1020] The shrinkage rate during curing of the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Herein, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula.

[1021] Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[1022] <Characteristics of cured resin compositions>

[1023] The imidization reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. As long as it is 70% or more, it sometimes results in a cured product with excellent mechanical properties.

[1024] The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[1025] The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[1026] <Preparation of Resin Compositions>

[1027] The resin composition of the present invention can be prepared by mixing the above-described components. The mixing method is not particularly limited and can be carried out using previously known methods.

[1028] Mixing can be achieved through methods such as mixing based on stirring blades, mixing based on ball mills, and mixing by rotating the tank itself.

[1029] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[1030] Furthermore, in order to remove foreign matter such as dust or particles from the resin composition of the present invention, filtration using a filter is preferred. Regarding the filter pore size, for example, a pore size of 5 μm or less is preferred, 1 μm or less is more preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is even more preferred. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be pre-cleaned with an organic solvent. In the filtration process, multiple filters can be used in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, an HDPE filter with a pore size of 1 μm can be connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage. Furthermore, various materials can be filtered multiple times. In the case of multiple filtrations, it can be a circulating filtration. Furthermore, filtration can also be performed after pressurization. When pressurizing and filtering, the pressurizing pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[1031] In addition to filtration using filters, impurity removal can also be performed using adsorption materials. A combination of filtration and impurity removal using adsorption materials can also be used. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[1032] In addition, after filtration using a filter, a process can be performed where the resin composition filled in the bottle is placed under reduced pressure and degassed.

[1033] (Method for manufacturing solidified products)

[1034] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

[1035] Furthermore, the method for manufacturing the cured product of the present invention more preferably includes the above-described film forming step, an exposure step for selectively exposing the film formed by the film forming step, and a developing step for developing the film exposed by the exposure step using a developing solution to form a pattern.

[1036] The method for manufacturing the cured product of the present invention preferably includes at least one of the above-described film forming step, the above-described exposure step, the above-described developing step, a heating step for heating the pattern obtained by the developing step, and a post-developing exposure step for exposing the pattern obtained by the developing step.

[1037] Furthermore, the manufacturing method of the present invention preferably includes the above-described film formation step and the step of heating the above-described film.

[1038] The following is a detailed explanation of each process.

[1039] <Membrane Formation Process>

[1040] The resin composition of the present invention can be used in a film forming process applicable to a substrate to form a film.

[1041] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

[1042] [Substrate]

[1043] The type of substrate can be appropriately selected according to the application, but there are no particular limitations. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, any of the substrates formed of metal and substrates in which metal layers are formed, for example, by electroplating or vapor deposition); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In this invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[1044] Furthermore, layers such as an adhesive layer and an oxide layer made of hexamethyldisilazane (HMDS) can be provided on the surface of these substrates.

[1045] Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular.

[1046] For the dimensions of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, the length of the shorter side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

[1047] Furthermore, as a substrate, a plate-shaped substrate (substrate) can be used, preferably a panel-shaped substrate.

[1048] Furthermore, when a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer formed by curing) or a metal layer, the resin layer or the metal layer becomes the substrate.

[1049] As a method for applying the resin composition of the present invention to a substrate, coating is preferred.

[1050] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating is more preferred. From the viewpoints of film thickness uniformity and productivity, spin coating and slot coating are preferred. By adjusting the solid content concentration of the resin composition or the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[1051] Furthermore, it is also possible to apply a method for transferring a coating film formed by pre-applying it to a temporary support through the above-described application method onto a substrate.

[1052] Regarding the transfer method, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can preferably be used in this invention.

[1053] Furthermore, a process can be performed to remove excess film from the ends of the substrate. Examples of such processes include edge bead rinsing (EBR) and back rinse.

[1054] Alternatively, a pre-wetting process can be used, in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[1055] <Drying Process>

[1056] After the membrane formation process (layer formation process), the above-mentioned membrane can be used in the process of drying the formed membrane (layer) (drying process) in order to remove the solvent.

[1057] That is, the method for manufacturing the cured product of the present invention may include a drying step, which dries the film formed by the film forming step.

[1058] Furthermore, the aforementioned drying process is preferably performed after the film formation process and before the exposure process.

[1059] The drying temperature of the membrane in the drying process is preferably 50–150°C, more preferably 70–130°C, and even more preferably 90–110°C. Furthermore, drying can also be performed under reduced pressure. The drying time can be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[1060] <Exposure Process>

[1061] The above-mentioned film can be used in the exposure process of selectively exposed films.

[1062] That is, the method for manufacturing the cured material of the present invention may include an exposure step, which selectively exposes the film formed by the film forming step.

[1063] Selective exposure means exposing a portion of the film. Furthermore, through selective exposure, exposed areas (exposed regions) and unexposed areas (unexposed regions) are formed on the film.

[1064] Regarding the exposure amount, there are no particular requirements as long as it is sufficient to cure the resin composition of the present invention. For example, it is preferably 50 to 10,000 mJ / cm based on the exposure energy at a wavelength of 365 nm. 2 More preferably 200–8,000 mJ / cm 2 .

[1065] The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[1066] Regarding the exposure wavelength, examples related to the light source include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), and wide wavelengths (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet (EUV) (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm. For the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is even more preferred. This allows for particularly high exposure sensitivity.

[1067] Furthermore, the exposure method is not particularly limited, as long as it is an exposure of at least a portion of the film formed by the resin composition of the present invention, but examples include exposure using a photomask, exposure based on direct laser imaging, etc.

[1068] <Post-exposure heating process>

[1069] The above-mentioned film can be used in a process where heating is performed after exposure (post-exposure heating process).

[1070] That is, the method for manufacturing the cured material of the present invention may include a post-exposure heating step, which heats the film exposed by the exposure step.

[1071] The post-exposure heating process can be performed after the exposure process and before the development process.

[1072] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[1073] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[1074] Regarding the heating rate in the post-exposure heating process, the rate from the initial heating temperature to the maximum heating temperature is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[1075] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[1076] There are no particular limitations on the heating mechanism used in the post-exposure heating process; commonly known heating plates, ovens, infrared heaters, etc., can be used.

[1077] Furthermore, it is preferable to conduct the process in a low-oxygen environment by allowing inactive gases such as nitrogen, helium, or argon to flow through the gas during heating.

[1078] <Developing Process>

[1079] The exposed film can be used in the developing process to form a pattern by developing with a developing solution.

[1080] That is, the method for manufacturing the cured material of the present invention may include a developing step, which uses a developing solution to develop a film exposed by an exposure step to form a pattern.

[1081] The exposed and unexposed portions of the film are removed by developing, thus forming a pattern.

[1082] The development process that removes the non-exposed portions of the film is called negative development, while the development process that removes the exposed portions of the film is called positive development.

[1083] [Developing solution]

[1084] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[1085] When the developing solution is an alkaline aqueous solution, examples of alkaline compounds that can be included in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is preferred. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass of the total mass of the developer, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[1086] When the developer contains an organic solvent, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3- Methyl 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) Esters, such as ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMFA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as... Ketones, such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., are preferably included; as cyclic hydrocarbons, ...

Claims

1. A resin composition comprising: At least one resin selected from cyclized resins and their precursors; and Polymerizable compounds having polymerizable groups and amide bonds bonded together via linking groups. The content of at least one resin selected from cyclized resins and their precursors is 20% by mass or more and 99.5% by mass or less relative to the total solids content of the resin composition. The content of the polymeric compound is 0.5% to 20% by mass relative to the total solids content of the resin composition. The cyclized resin is a resin whose main chain structure includes an imide ring structure or an oxazole ring structure. The amide bond is bonded to the linker on the carbonyl side. The polymerizable compound is a compound represented by the following formula (1-1). When a homopolymer was synthesized using the aforementioned polymeric compound, the homopolymer exhibited the property of producing a base freed from the main chain upon heating to 250°C. In equation (1-1), R 1 Each can be independently a hydrogen atom or a hydrocarbon group, with two R atoms. 1 Optional bonding to form a ring structure, R 2 Each is independently a hydrogen atom, a halogen atom, a methyl group, an ethyl group, or a hydroxymethyl group, L 1 L represents a trivalent organic group. 1 -OH is selected from the following structures, wherein... * indicates the bonding site with the carbonyl group in formula (1-1), and # indicates the bonding site with the R group in formula (1-1). 2 The bonding sites of the bonded carbon atoms. 。 2. The resin composition according to claim 1, wherein, The resin has polymerizable groups.

3. The resin composition according to claim 1 or 2, further comprising a photopolymerization initiator.

4. The resin composition according to claim 1 or 2, further comprising a polymeric compound different from the polymeric compound.

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

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

7. A laminate comprising two or more layers formed of the cured material of claim 6, and wherein the layers formed of the cured material include metal layers between each other at will.

8. A method for manufacturing a cured product, comprising a film forming step of applying the resin composition of any one of claims 1 to 5 onto a substrate to form a film.

9. The method for manufacturing a cured material according to claim 8, comprising an exposure step of selectively exposing the film and a development step of developing the film using a developing solution to form a pattern.

10. The method for manufacturing a cured product according to claim 8, comprising a heating step of heating the film at 50°C to 450°C.

11. A semiconductor device comprising the cured material of claim 6.

12. A compound represented by the following formula (1-1), In equation (1-1), R 1 Each can be independently a hydrogen atom or a hydrocarbon group, with two R atoms. 1 Optional bonding to form a ring structure, R 2 Each is independently a hydrogen atom, a halogen atom, a methyl group, an ethyl group, or a hydroxymethyl group, L 1 L represents a trivalent organic group. 1 -OH is selected from the following structures, wherein... * indicates the bonding site with the carbonyl group in formula (1-1), and # indicates the bonding site with the R group in formula (1-1). 2 The bonding sites of the bonded carbon atoms. 。

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