Resin composition and method for manufacturing interlayer insulating film for rewiring layer

Abstract

A resin composition and a method for producing an interlayer insulating film for a rewiring layer using the resin composition, the resin composition comprising: at least one resin selected from the group consisting of polyimides and polyimide precursors; and a compound having an N-O structure.

Description

TECHNICAL FIELD

[0001] The present application relates to a resin composition and a method for manufacturing an interlayer insulating film for a rewiring layer. BACKGROUND

[0002] Polyimides are excellent in heat resistance and insulating properties, and are thus used for insulating films of electronic components and the like.

[0003] In Patent Literature 1, a photosensitive resin composition containing a polyimide precursor having a specific structure and a photosensitizer is described.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: International Publication No. 2017 / 170600 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] A cured film (for example, an interlayer insulating film for a rewiring layer and the like) formed by curing a resin composition containing at least one resin selected from the group consisting of a polyimide and a polyimide precursor, is sometimes further coated with a different composition to form a laminate, and thus is required to have drug resistance. Also, when the cured film has sufficient drug resistance, it is possible to selectively remove only a portion that has become poorly cured with a drug, and it is possible to reform the cured film again, and thus it is possible to improve the yield of a finished product of a semiconductor package.

[0009] The present application relates to a resin composition and a method for manufacturing an interlayer insulating film for a rewiring layer.

[0010] MEANS FOR SOLVING THE PROBLEMS

[0011] Examples of representative embodiments of the present application are shown below. [1]

[0013] A resin composition containing: at least one resin selected from the group consisting of a polyimide and a polyimide precursor; and a compound (A) represented by the following formula (al).

[0014] [Chemical Formula 1]

[0015]

[0016] In formula (al), R 1 represents an organic group. R 2 and R 3 each independently represents a hydrogen atom or an organic group. R1 R 2 and R 3 Any two of them can be bonded together to form a ring. [2]

[0018] The resin composition as described in [1], wherein,

[0019] R in the above formula (a1) 1 It represents an aromatic group. [3]

[0021] The resin composition as described in [1] or [2], wherein,

[0022] R in the above formula (a1) 1 R represents an aromatic group having a phenolic hydroxyl group. 2 and R 3 Each organic group can be represented independently. [4]

[0024] The resin composition of any one of [1] to [3] further comprises a photopolymerization initiator and a polymerizable compound. [5]

[0026] The resin composition of any one of [1] to [4] further comprises an organometallic compound. [6]

[0028] The resin composition of any one of [1] to [5] further comprises a urea compound. [7]

[0030] The resin composition of any one of [1] to [6] further comprises a solvent having at least one of an amide group and a hydroxyl group. [8]

[0032] The resin composition as described in any one of [1] to [7], wherein,

[0033] The content of the above-mentioned compound (A) contained in the above-mentioned resin composition is 0.0001% by mass or more and 10.0% by mass or less, relative to the total solid content of the above-mentioned resin composition. [9]

[0035] The resin composition as described in any one of [1] to [8], wherein,

[0036] The content of the above-mentioned compound (A) contained in the above-mentioned resin composition is 0.0001% by mass or more and 15.0% by mass or less, relative to the above-mentioned resin.

[10]

[0038] The resin composition as described in any one of [1] to [9] is used to form an insulating film for a redistribution layer.

[11]

[0040] A method for manufacturing an interlayer insulating film for a rewiring layer, comprising:

[0041] The photosensitive film forming process involves coating a substrate with the resin composition described in any one of [1] to

[10] to form a photosensitive film;

[0042] The exposure process involves exposing the aforementioned photosensitive film to form an exposed film; and

[0043] In the pattern forming process, the above-mentioned exposure film is developed with a developing solution to form an insulating pattern.

[0044] Invention Effects

[0045] According to the present invention, a resin composition capable of forming a film with excellent chemical resistance and a method for manufacturing an interlayer insulating film for a rewiring layer using the above-described resin composition are provided. Detailed Implementation

[0046] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown.

[0047] In this specification, the numerical range indicated by the symbol “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0048] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the expected function of the process can be achieved.

[0049] In this specification, the descriptions of groups (atomic groups) without indicating whether they are substituted or unsubstituted include both unsubstituted groups (atomic groups) 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).

[0050] In this instruction manual, unless otherwise specified, "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 in exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation.

[0051] In this specification, "(meth)acrylate" means either "acrylate" or "methacrylate", "(meth)acrylic acid" means either "acrylic acid" or "methacrylic acid", and "(meth)acryloyl" means either "acryloyl" or "methacryloyl".

[0052] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0053] In this specification, total solids content refers to the total mass of the components after removing the solvent from all components of the composition. 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.

[0054] In this specification, unless otherwise specified, 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, by using an HLC-8420 GPC (manufactured by TOSOH CORPORATION) and connecting guard columns SuperAW-H, TSKgel SuperAWM-H, and TSKgel SuperAWM-H (all manufactured by TOSOH CORPORATION) in series. Unless otherwise specified, these molecular weights are determined using NMP (N-methyl-2-pyrrolidone) as the eluent. When NMP is unsuitable as the eluent, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise specified, a 254 nm UV (ultraviolet) detector is used in the GPC determination.

[0055] In this specification, when referring to the positional relationship of the layers constituting the laminate, "upper" or "lower" simply means that there are other layers above or below the reference layer among the layers of interest. That is, a third layer or element may be further inserted between the reference layer and the other layers, without the reference layer needing to be in contact with the other layers. Unless otherwise specified, the direction of the stacked layers relative to the substrate is referred to as "upper," or, when a resin composition layer is present, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction as "lower." Furthermore, this vertical direction is provided for convenience in this specification; in practice, the "upper" direction in this specification may differ from the vertical direction.

[0056] In this specification, unless otherwise specified, each component in the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to that component.

[0057] Unless otherwise specified, the temperature in this manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH.

[0058] In this specification, the preferred combination of methods is a more preferred method.

[0059] [Resin Composition]

[0060] The resin composition of the present invention comprises: at least one resin selected from the group consisting of polyimides and polyimide precursors; and compound (A) represented by the following formula (a1).

[0061] [Chemical Formula 2]

[0062]

[0063] In equation (a1), R 1 Indicates an organic group. R 2 and R 3 Each can be used independently to represent a hydrogen atom or an organic group. R 1 R 2 and R 3 Any two of them can be bonded together to form a ring.

[0064] 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 or an aqueous solution.

[0065] 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.

[0066] Furthermore, the resin composition of the present invention can be used to form a photosensitive film for negative or positive development.

[0067] In this invention, negative development refers to the development of non-exposed areas by developing during exposure and development, while positive development refers to the development of exposed areas by developing.

[0068] As the above-described exposure method, developer, and developing method, for example, the exposure method described in the exposure step, the developer described in the developing step, and the developing method described in the following description of the method for manufacturing a cured product can be used.

[0069] The resin composition according to the present invention can form a film with excellent chemical resistance. The mechanism by which the above-mentioned effects are obtained by the present invention is not yet clear, but the inventors infer the following. However, the present invention is not limited to the following inferred mechanism.

[0070] The compound (A) represented by formula (a1) contained in the resin composition of the present invention is a compound with a highly polar NO structure. Compound (A) is miscible with highly polar polyimides and polyimide precursors; therefore, in a film containing at least one resin selected from the group consisting of polyimides and polyimide precursors, compound (A) can be uniformly dispersed and localized aggregation suppressed. It is believed that, as a result, the overall polarity of the film is improved, and the drug resistance becomes better.

[0071] Moreover, for example, as is known in nitroxide-mediated radical polymerization (NMP), depending on the structure of compound (A), it is possible to decompose during the heating process to generate free radicals, thereby promoting thermal radical polymerization, and this effect is expected to also contribute to high drug resistance.

[0072] That is, it is believed that both the case where compound (A) remains in the membrane without decomposition and the case where decomposition promotes free radical polymerization have the effect of improving the drug resistance of the membrane.

[0073] The components contained in the resin composition of the present invention will be described in detail below.

[0074] <Compound (A)>

[0075] The resin composition of the present invention comprises compound (A) represented by formula (a1) (also simply referred to as "compound (A)").

[0076] [Chemical Formula 3]

[0077]

[0078] In equation (a1), R 1 Indicates an organic group. R 2 and R 3 Each can be used independently to represent a hydrogen atom or an organic group. R 1 R 2 and R 3 Any two of them can be bonded together to form a ring.

[0079] R in equation (a1) 1The organic group represented is not particularly limited. For example, it can be an organic group with 1 to 50 carbon atoms, an organic group with 1 to 40 carbon atoms, or an organic group with 1 to 30 carbon atoms.

[0080] As R 1 The organic group represented is preferably an alkyl, alkenyl, alkynyl, cycloalkyl, aromatic group, non-aromatic heterocyclic group, acyl, thioyl, carbamoyl, or a combination of two or more of these. The organic group may have substituents.

[0081] R 1 The alkyl group and R are represented 1 The alkyl group represented may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited; for example, 1 to 20 is preferred, more preferably 1 to 15, and even more preferably 1 to 10. The alkyl group may have substituents. Furthermore, the alkyl group may contain an ether bond (-O-). Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl.

[0082] R 1 The alkenyl group and R represented 1 The alkenyl group contained in the represented organic group can be linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited; for example, 2 to 20 is preferred, more preferably 2 to 15, and even more preferably 2 to 10. The alkenyl group can have substituents. Furthermore, the alkenyl group can contain ether bonds in the chain. Examples of alkenyl groups include vinyl and allyl groups.

[0083] R 1 The alkynyl group and R are represented 1 The alkynyl group contained in the represented organic group can be linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited; for example, 2 to 20 is preferred, more preferably 2 to 15, and even more preferably 2 to 10. The alkynyl group can have substituents. Furthermore, the alkynyl group can contain ether bonds in the chain. Examples of alkynyl groups include ethynyl groups.

[0084] R 1 The cycloalkyl group and R are represented 1The cycloalkyl group represented may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited; for example, 3 to 20 is preferred, more preferably 4 to 15, and even more preferably 5 to 10. The cycloalkyl group may have substituents. For example, one of the methylene groups constituting the ring of the cycloalkyl group may be replaced by a heteroatom such as an oxygen atom, a group with a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylides constituting the cycloalkane ring of the cycloalkyl group may be replaced by vinylides. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl.

[0085] R 1 The non-aromatic heterocyclic group and R represented 1 The non-aromatic heterocyclic group contained in the represented organic group preferably contains at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms. The number of cyclic atoms in the non-aromatic heterocyclic group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 12. The number of carbon atoms in the non-aromatic heterocyclic group is not particularly limited, but is preferably 1 to 18, more preferably 2 to 15, and even more preferably 2 to 10.

[0086] Non-aromatic heterocyclic groups can be monocyclic or polycyclic groups.

[0087] Examples of non-aromatic heterocyclic groups include those formed by removing one hydrogen atom from five-membered ring non-aromatic heterocyclic compounds such as pyrrolidine, pyrrololine, 2-oxazolidinone, tetrahydrofuran, and tetrahydrothiophene, and those formed by removing one hydrogen atom from six-membered ring non-aromatic heterocyclic compounds such as morpholin, piperidine, piperazine, and tetrahydropiperan.

[0088] Furthermore, the non-aromatic heterocyclic group can also be a group formed by removing one hydrogen atom from a fused ring compound having the above-mentioned five-membered ring non-aromatic heterocyclic compound or the above-mentioned six-membered ring non-aromatic heterocyclic compound and at least one of the following structures: cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes with 3 to 12 carbon atoms such as cyclopentane and cyclohexane), cycloolefins (e.g., monocyclic or polycyclic cycloolefins with 3 to 12 carbon atoms such as cyclohexene), the above-mentioned five-membered ring non-aromatic heterocyclic compound, and the above-mentioned six-membered ring non-aromatic heterocyclic compound.

[0089] Non-aromatic heterocyclic groups can have substituents.

[0090] One or more of the methylene groups in the ring constituting a non-aromatic heterocyclic group may be substituted with carbonyl groups.

[0091] When the bond between adjacent atoms in a non-aromatic heterocyclic group is a single bond, the single bond can be replaced by a multiple bond (e.g., a double bond).

[0092] R 1 The aromatic groups and R represented 1 The aromatic groups contained in the organic groups represented can be aromatic hydrocarbon groups (aryl groups) or aromatic heterocyclic groups.

[0093] R 1 The aryl and R represented 1 The number of carbon atoms in the aryl group represented by the organic group is not particularly limited; for example, it is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may have substituents. Examples of aryl groups include phenyl, naphthyl, and anthracene.

[0094] R 1 The aromatic heterocyclic group and R are represented 1 The aromatic heterocyclic group contained in the represented organic group preferably contains at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms. The number of cyclic atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20. The number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15.

[0095] Aromatic heterocyclic groups can be monocyclic or polycyclic.

[0096] As aromatic heterocyclic groups, examples include groups formed by removing one hydrogen atom from five-membered ring aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazolium, and tetrazolium, or from six-membered ring aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine.

[0097] Furthermore, the aromatic heterocyclic group can also be a five-membered ring aromatic heterocyclic compound or a six-membered ring aromatic heterocyclic compound selected from the above-mentioned five-membered ring aromatic heterocyclic compound, the above-mentioned six-membered ring aromatic heterocyclic compound, aromatic hydrocarbons (e.g., aromatic hydrocarbons with 6 to 15 carbon atoms, such as benzene and naphthalene), cycloalkanes (e.g., cyclopentane, cyclohexane, etc., with 3 to 12 carbon atoms, such as cyclopentane and cyclohexane), cycloalkenes (e.g., cyclohexene, etc., with 3 to 12 carbon atoms). A group formed by removing one hydrogen atom from at least one condensed structure of a fused-ring compound (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnamoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) in the group consisting of monocyclic or polycyclic cyclic alkenes with 3 to 12 members, and non-aromatic heterocyclic compounds (e.g., the above-mentioned five-membered ring non-aromatic heterocyclic compounds, the above-mentioned six-membered ring non-aromatic heterocyclic compounds, etc.).

[0098] Aromatic heterocyclic groups can have substituents.

[0099] R 1 The acyl group and R are represented 1 The acyl group contained in the organic group represented by R C1 -C (=O)- indicates that R is preferred. C1 Indicates an organic group. R C1 The organic group represented is preferably alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heterocyclic (aromatic and non-aromatic heterocyclic). R C1 The descriptions, specific examples, and preferred ranges of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heterocyclic groups represented are respectively consistent with those of the aforementioned R. 1 The same as in.

[0100] R 1 The thioyl group and R are represented 1 The thioyl group contained in the organic group represented by R C2 -C (=S)- indicates that R is preferred. C2 Indicates an organic group. R C2 The organic group represented is preferably alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heterocyclic (aromatic and non-aromatic heterocyclic). R C2 The descriptions, specific examples, and preferred ranges of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and heterocyclic groups represented are respectively consistent with those of the aforementioned R. 1 The same as in.

[0101] R in equation (a1) 2 and R 3 The organic group represented is not particularly limited. For example, it can be an organic group with 1 to 50 carbon atoms, an organic group with 1 to 40 carbon atoms, or an organic group with 1 to 30 carbon atoms.

[0102] As R 2 and R 3 The organic group represented is preferably, for example, an alkyl, alkenyl, alkynyl, cycloalkyl, aromatic, non-aromatic heterocyclic, acyl, thioyl, carbamoyl, or a combination of two or more of these. The organic group may have substituents.

[0103] R 2 and R 3 The alkyl, alkenyl, alkynyl, cycloalkyl, aromatic, non-aromatic heterocyclic, acyl and thioyl groups, and R are represented. 2 and R 3The descriptions, specific examples, and preferred ranges of the alkyl, alkenyl, alkynyl, cycloalkyl, aromatic, non-aromatic heterocyclic, acyl, and thioyl groups contained in the represented organic groups are respectively consistent with the aforementioned R. 1 The same as in.

[0104] R in equation (a1) 1 R 2 and R 3 Any two of them can be bonded together to form a ring.

[0105] As R 1 R 2 and R 3 A ring formed by the bonding of any two atoms in the ring (also called "ring X") can be a non-aromatic nitrogen-containing heterocycle or an aromatic nitrogen-containing heterocycle.

[0106] The case where ring X is a non-aromatic nitrogen-containing heterocycle is explained.

[0107] Non-aromatic nitrogen-containing heterocycles can be saturated or unsaturated.

[0108] The number of cyclic atoms in the non-aromatic nitrogen-containing heterocycle is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 12. The number of carbon atoms in the non-aromatic nitrogen-containing heterocycle is not particularly limited, but is preferably 1 to 18, more preferably 2 to 15, and even more preferably 2 to 10.

[0109] Non-aromatic nitrogen-containing heterocycles can be monocyclic or polycyclic.

[0110] Examples of non-aromatic nitrogen-containing heterocycles include five-membered ring non-aromatic nitrogen-containing heterocycles such as pyrrolidine, pyrrolline, and 2-oxazolidinone, and six-membered ring non-aromatic nitrogen-containing heterocycles such as mofolin, piperidine, and piperazine.

[0111] Furthermore, the non-aromatic nitrogen-containing heterocycle can also be a fused ring having a structure formed by condensation of at least one of the following: a five-membered non-aromatic nitrogen-containing heterocycle or a six-membered non-aromatic nitrogen-containing heterocycle; a cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes with 3 to 12 carbon atoms, such as cyclopentane or cyclohexane); a cycloalkene (e.g., monocyclic or polycyclic cycloalkenes with 3 to 12 carbon atoms, such as cyclohexene); a five-membered non-aromatic nitrogen-containing heterocycle; or a six-membered non-aromatic nitrogen-containing heterocycle.

[0112] Non-aromatic nitrogen-containing heterocycles can have substituents.

[0113] One or more of the methylene groups constituting the non-aromatic nitrogen-containing heterocycle may be substituted by at least one group selected from the group consisting of carbonyl bonds, ester bonds, amide bonds and sulfone bonds.

[0114] When the bond between adjacent atoms in a non-aromatic nitrogen-containing heterocycle is a single bond, the single bond can be replaced by a multiple bond (e.g., a double bond).

[0115] The case where ring X is an aromatic nitrogen-containing heterocycle is explained.

[0116] The number of cyclic atoms in the aromatic nitrogen-containing heterocycle is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20. The number of carbon atoms in the aromatic nitrogen-containing heterocycle is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15.

[0117] Aromatic nitrogen-containing heterocycles can be monocyclic or polycyclic.

[0118] Examples of aromatic nitrogen-containing heterocycles include, for example, five-membered aromatic nitrogen-containing heterocycles such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole, thiadiazole, dioxazole, dithiazolium, and tetrazolium, or six-membered aromatic nitrogen-containing heterocycles such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine.

[0119] Furthermore, the aromatic nitrogen-containing heterocycle may also be a fused ring (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnaphthalene, etc.) having at least one condensed structure selected from the group consisting of the above-mentioned five-membered aromatic nitrogen-containing heterocycle, the above-mentioned six-membered aromatic nitrogen-containing heterocycle, aromatic hydrocarbons (e.g., aromatic hydrocarbons with 6 to 15 carbon atoms such as benzene and naphthalene), cycloalkanes (e.g., cyclopentane, cyclohexane, etc. with 3 to 12 carbon atoms such as cyclopentane), cycloalkenes (e.g., cyclohexene, etc. with 3 to 12 carbon atoms such as cyclohexene), and non-aromatic nitrogen-containing heterocycles (e.g., the above-mentioned five-membered non-aromatic nitrogen-containing heterocycle, the above-mentioned six-membered non-aromatic nitrogen-containing heterocycle, etc.).

[0120] Aromatic nitrogen-containing heterocycles can have substituents.

[0121] R in equation (a1) 1 Preferably, it represents an aromatic group, and more preferably, it represents an aryl group.

[0122] When R 1 When representing an aromatic group, the aromatic group may have substituents. Substituents are not particularly limited, but hydroxyl groups (i.e., phenolic hydroxyl groups) are preferred.

[0123] The preferred option is R in formula (a1) 1 R represents an aromatic group having a phenolic hydroxyl group. 2 and R 3 Each organic group is represented independently, more preferably R. 1R represents an aryl group having a phenolic hydroxyl group. 2 and R 3 Each organic group can be represented independently.

[0124] The compound (A) represented by formula (a1) can be synthesized by known methods.

[0125] [Molecular weight]

[0126] The molecular weight of compound (A) is not particularly limited, but is preferably 50 to 4000, more preferably 80 to 3000, and even more preferably 100 to 2000. If the molecular weight is 50 or higher, it is less likely to volatilize during film formation of the resin composition of the present invention, and compound (A) is more likely to remain in the film, thus easily achieving the effect of improving drug resistance. Furthermore, if the molecular weight is 4000 or lower, the plasticity of the film will not become too high, and it is easier to achieve the effect of improving drug resistance.

[0127] As specific examples of compound (A), examples such as A-1 to A-22 used in the examples described later can be listed, but are not limited to these.

[0128] 〔content〕

[0129] The content of compound (A) in the resin composition of the present invention is not particularly limited relative to the total solids content of the resin composition, but is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and even more preferably 0.0010% by mass or more. Furthermore, the content of compound (A) in the resin composition of the present invention is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, and even more preferably 5.0% by mass or less, relative to the total solids content of the resin composition.

[0130] The content of compound (A) in the resin composition of the present invention is preferably 0.0001% by mass or more and 10.0% by mass or less, relative to the total solids content of the resin composition.

[0131] The content of compound (A) in the resin composition of the present invention is preferably 0.0001% by mass or more, more preferably 0.0006% by mass or more, and even more preferably 0.0013% by mass or more, relative to at least one resin selected from the group consisting of polyimides and polyimide precursors. Furthermore, the content of compound (A) in the resin composition of the present invention is preferably 15.0% by mass or less, more preferably 13.5% by mass or less, and even more preferably 10.0% by mass or less, relative to at least one resin selected from the group consisting of polyimides and polyimide precursors.

[0132] The content of compound (A) in the resin composition of the present invention is preferably 0.0001% by mass or more and 15.0% by mass or less, relative to at least one resin selected from the group consisting of polyimide and polyimide precursor.

[0133] The resin composition of the present invention may contain only one compound (A) or two or more compounds. When two or more compounds (A) are contained, the total amount of all compounds (A) is preferably within the range described above.

[0134] Furthermore, the content of compound (A) contained in the resin composition of the present invention can be quantified by methods such as NMR (Nuclear Magnetic Resonance), HPLC (High Performance Liquid Chromatography), and GC (Gas Chromatography). In particular, if LC-MS (mass detector), a type of HPLC, is used, the content can be quantified in the state of the resin composition.

[0135] <Specific Resins>

[0136] The resin composition of the present invention comprises at least one resin selected from the group consisting of polyimides and polyimide precursors (also referred to as "specific resin").

[0137] The specific resin is preferably one having polymerizable groups, and more preferably containing free radical polymerizable groups.

[0138] When a particular resin has free radical polymerizable groups, the resin composition of the present invention preferably contains a free radical polymerization initiator, more preferably a free radical polymerization initiator and a free radical crosslinking agent. Furthermore, a sensitizer may be included as needed. Such a resin composition can, for example, form a negative photosensitive film.

[0139] Furthermore, certain resins may have polar conversion groups such as acid-decomposing groups.

[0140] When a particular resin has acid-degrading groups, the resin composition preferably contains a photoacid-generating agent. Such a resin composition can, for example, form a chemically amplified positive or negative photosensitive film.

[0141] [Polyimide precursor]

[0142] The types of polyimide precursors used in this invention are not particularly limited, but preferably contain repeating units represented by the following formula (2).

[0143] [Chemical Formula 4]

[0144]

[0145] In equation (2), A 1 and A 2 Each independently represents an oxygen atom or -NR. z -, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 R represents either a hydrogen atom or a monovalent organic group independently. z It represents a hydrogen atom or an organic group with a valence of 1.

[0146] A in equation (2) 1 and A 2 Each independently represents an oxygen atom or -NR. z - Preferably, it contains oxygen atoms.

[0147] R z It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0148] R in equation (2) 111 This indicates a divalent organic group. Examples of divalent organic groups include groups comprising straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups; 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; and more preferably groups comprising aromatic groups with 6 to 20 carbon atoms. The hydrocarbon group in the chain of the above-mentioned straight-chain or branched aliphatic group may be substituted with a group containing a heteroatom, and the cyclic hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted with a group containing a heteroatom. R in formula (2) 111 Examples include groups represented by -Ar- and -Ar-L-Ar-, with the group represented by -Ar-L-Ar- being preferred. Here, Ar is independently an aromatic group, and L is 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 group composed of two or more of the above. The preferred ranges are as described above.

[0149] R 111 Preferably, the diamine is derived from a diamine. Examples of diamines used as precursors for manufacturing polyimide include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one diamine may be used, or two or more may be used.

[0150] Specifically, R 111Preferably, the diamine comprises a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof; more preferably, a diamine comprises an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the aforementioned straight-chain or branched aliphatic group may be substituted with a group containing a heteroatom, and the cyclic hydrocarbon group of the aforementioned cyclic aliphatic group and aromatic group may be substituted with a group containing a heteroatom. Examples of groups comprising aromatic groups are listed below.

[0151] [Chemical Formula 5]

[0152]

[0153] In the formula, A is preferably a single bond or a divalent linking group. The single bond is a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof. More preferably, it is a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-. Further preferably, it is -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0154] In the formula, * indicates the bonding site with other structures.

[0155] Specifically, as a diamine, at least one diamine selected from the following can be listed:

[0156] 1,2-Diaminoethane, 1,2-Diaminopropane, 1,3-Diaminopropane, 1,4-Diaminobutane or 1,6-Diaminohexane; 1,2- or 1,3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-Diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine;

[0157] m-Phenylenediamine or p-Phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl) Propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-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'-diaminodiphenyl sulfone, 1,3-bis( 4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis( 4-Aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminoisocumene, 2,5-dimethyl-p-phenylenediamine, ethylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, 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)benzene, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0158] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0159] Furthermore, the diamine having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may also be preferred.

[0160] From the viewpoint of the flexibility of the obtained organic membrane, R is preferred. 111 Represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted with a fluorine atom, or a group consisting of -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, or a group consisting of -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably alkylene.

[0161] Furthermore, from the perspective of 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).

[0162] [Chemical Formula 6]

[0163]

[0164] 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.

[0165] 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).

[0166] [Chemical Formula 7]

[0167]

[0168] 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).

[0169] Examples of diamines that give rise to 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, 4,4'-diaminooctafluorobiphenyl, etc. These can be used in one or in combination of two or more.

[0170] R in equation (2) 115 The term represents a tetravalent organic group. Preferably, the tetravalent organic group is a tetravalent organic group containing an aromatic ring, and more preferably, it is a group represented by formula (5) or formula (6) below. In formula (5) or formula (6), * independently represents the bonding site with other structures.

[0171] [Chemical Formula 8]

[0172]

[0173] In equation (5), R 112Preferably, it is a single bond or a divalent linking group, which is a single bond or a group selected from aliphatic hydrocarbon groups, aromatic groups, -O-, -CO-, -S-, -SO2- and -NHCO-, and combinations thereof, that can be substituted by fluorine atoms. More preferably, it is a single bond or a group selected from alkylene groups, aromatic hydrocarbon groups, -O-, -CO-, -S- and -SO2-, that can be substituted by fluorine atoms, that are 1 to 3 carbon atoms, or aromatic hydrocarbon groups, -O-, -CO-, -S- and -SO2-. More preferably, it is a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0174] Specifically, R 115 Examples include the tetracarboxylic acid residues remaining after the anhydride group is removed from a tetracarboxylic dianhydride. As a counterpart to R... 115 The structure of the polyimide precursor can contain only one tetracarboxylic acid dianhydride residue or more than two.

[0175] Tetracarboxylic acid dianhydride is preferably represented by the following formula (O).

[0176] [Chemical Formula 9]

[0177]

[0178] In equation (O), R 115 R represents a tetravalent organic group. 115 The preferred range is the same as R in equation (2). 115 They have the same meaning and the same preferred range.

[0179] 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)propane dianhydride. 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 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 alkyl derivatives of these having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

[0180] 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.

[0181] In equation (2), R can also be used. 111 and R 115 At least one of them has an OH group. More specifically, as R 111 The residues of bisaminophenol derivatives can be listed.

[0182] R in equation (2) 113 and R 114 Each organic group can be independently represented by a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group comprises 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. Preferably, the polymerizable group is a free radical polymerizable group capable of undergoing a cross-linking reaction through the action of heat, free radicals, etc. Specific examples of polymerizable groups include groups having olefinic unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetyl, benzoxazolyl, terminal isocyanate, and amino groups. The free radical polymerizable group in the polyimide precursor is preferably a group having olefinic unsaturated bonds.

[0183] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, and groups represented by formula (III) below, with groups represented by formula (III) below being preferred.

[0184] [Chemical Formula 10]

[0185]

[0186] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0187] In equation (III), * indicates the bonding site with other structures.

[0188] In equation (III), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0189] 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.

[0190] In this invention, polyalkoxide refers to a group formed by the direct bonding of two or more alkoxide groups. The alkylene groups in the multiple alkoxide groups contained in the polyalkoxide group may be the same or different.

[0191] When polyalkoxides contain multiple alkoxides of different alkylene groups, the arrangement of the alkoxides in the polyalkoxides can be random, block-shaped, or alternating.

[0192] The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent when 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, even more preferably 2 or 3, and particularly preferably 2.

[0193] Furthermore, the aforementioned alkylene group may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0194] 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.

[0195] From the viewpoint of solvent solubility and solvent resistance, polyethoxy, polypropoxy, polytrimethyleneoxy, polytetramethoxy, or groups formed by the bonding of multiple ethoxy groups and multiple propoxy groups are preferred as polyethoxy groups. Polyethoxy or polypropoxy groups are more preferred, and polyethoxy groups are even more preferred. In the groups formed by the bonding of multiple ethoxy groups and multiple propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, can form blocks, or can be arranged in an alternating pattern. The preferred manner for the number of repetitions of the ethoxy groups, etc., in these groups is as described above.

[0196] In equation (2), when R 113 When it is a hydrogen atom or when R 114 When the hydrogen atom is present, the polyimide precursor can form a conjugate base with a tertiary amine compound having an olefinically unsaturated bond. N,N-dimethylaminopropyl methacrylate is an example of such a tertiary amine compound.

[0197] 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, it is not particularly limited as long as it is an alkali-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 methyl alkyl group, a silyl ether group, a tertiary alkyl ester group, etc. From the viewpoint of exposure sensitivity, it is more preferred to be an acetal group or a ketal group.

[0198] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropiperanyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0199] 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.

[0200] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc., as diamines.

[0201] 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 range of exposure latitude can be further expanded.

[0202] Equation (2-A)

[0203] [Chemical Formula 11]

[0204]

[0205] 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.

[0206] A 1 A 2 R 111 R 113 and R 114 Independently with A in equation (2) 1 A 2 R 111 R 113 and R 114 The meanings are the same, and the preferred ranges are also the same. R 112 R in equation (5) 112 They have the same meaning and the same preferred range.

[0207] The polyimide precursor may contain one repeating unit represented by formula (2), or more than two repeating units. Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit represented by formula (2), the polyimide precursor may also contain other types of repeating units.

[0208] As one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) can be 50 mol% or more of all repeating units. The above total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and especially preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the end units can be the repeating units represented by formula (2).

[0209] 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. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0210] 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, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0211] In this specification, the molecular weight dispersion is a value calculated from weight-average molecular weight / number-average molecular weight.

[0212] When the resin composition contains 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 above-mentioned ranges. Furthermore, 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 above-mentioned ranges.

[0213] [Polyimide]

[0214] The polyimide used in this invention can be an alkali-soluble polyimide or a polyimide soluble in a developer solution whose main component is an organic solvent.

[0215] 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. The upper limit of the above-mentioned dissolution amount is not particularly limited, but it is preferably 100 g or less.

[0216] From the viewpoint of the strength and insulation of the obtained organic membrane, it is preferable that the polyimide is a polyimide having multiple imide structures in the main chain.

[0217] -Fluorine atom-

[0218] From the viewpoint of the membrane strength of the obtained organic membrane, it is also preferable that the polyimide has fluorine atoms.

[0219] The fluorine atom is preferably, for example, R contained in the repeating unit represented by formula (4) described later. 132 R in the repeating unit represented by equation (4) mentioned in the middle or later 131 More preferably, R is included as a fluorinated alkyl group in the repeating unit represented by formula (4) described later. 132 R in the repeating unit represented by equation (4) mentioned in the middle or later 131 middle.

[0220] 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.

[0221] -Silicon atom-

[0222] From the viewpoint of the strength of the obtained organic membrane, it is also preferable that the polyimide has silicon atoms.

[0223] Silicon atoms are preferably, for example, included 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.

[0224] The aforementioned silicon atoms or the aforementioned organically modified (poly)siloxane structure may also be included in the side chain of the polyimide, but preferably in the main chain of the polyimide.

[0225] 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.

[0226] -ene unsaturated bond-

[0227] From the viewpoint of the strength of the obtained organic membrane, it is preferable that the polyimide has olefinic unsaturated bonds.

[0228] Polyimide may have olefinic unsaturated bonds at the end of the main chain or in the side chain, but preferably in the side chain.

[0229] The aforementioned olefinic unsaturated bonds are preferably those with free radical polymerization properties.

[0230] The olefinic unsaturated bond is preferably R contained in the repeating unit represented by formula (4) described later. 132 Or R 131 More preferably, it is included in R as a group having an olefinic unsaturated bond. 132 Or R 131 middle.

[0231] In these, the olefinic unsaturated bond is preferably R contained in the repeating unit represented by formula (4) described later. 131 More preferably, it is included in R as a group having an olefinic unsaturated bond. 131 middle.

[0232] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, etc., which have vinyl groups that are directly bonded to the aromatic ring and can be substituted, (meth)acrylamido, (meth)acryloyloxy, and groups represented by the following formula (IV).

[0233] [Chemical Formula 12]

[0234]

[0235] In equation (IV), R 20 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0236] In equation (IV), R 21 The group refers to 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, and especially preferably 2 or 3. The number of repetitions of the alkoxide group is preferably 1 to 12, more preferably 1 to 6, and especially preferably 1 to 3) or a group formed by combining two or more of these.

[0237] As the aforementioned alkylene groups having 2 to 12 carbon atoms, they can be any of the following: linear, branched, cyclic, or a combination thereof.

[0238] The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0239] 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).

[0240] [Chemical Formula 13]

[0241]

[0242] In formulas (R1) to (R3), L represents a single bond or an alkylene group with 2 to 12 carbon atoms, a (poly)alkoxide group with 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.

[0243] 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, and is also R in formula (IV). 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.

[0244] In formula (R1), X is preferably an oxygen atom.

[0245] In equations (R1) to (R3), * has the same meaning as * in equation (IV), and the preferred method is also the same.

[0246] 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 olefinic unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate).

[0247] The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having hydroxyl and olefinic unsaturated bonds (e.g., 2-hydroxyethyl methacrylate, etc.).

[0248] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having phenolic hydroxyl groups with a compound having glycidyl and olefinic unsaturated bonds (e.g., glycidyl methacrylate).

[0249] In formula (IV), * indicates a bonding site with other structures, preferably a bonding site with the main chain of polyimide.

[0250] The amount of olefinic 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.

[0251] - Polymerizable groups other than those with olefinic unsaturated bonds-

[0252] Polyimides may contain polymeric groups other than those with olefinic unsaturated bonds.

[0253] Examples of polymerizable groups other than those with olefinic unsaturated bonds include cyclic ether groups such as epoxy and oxobutyl groups, alkoxymethyl groups such as methoxymethyl, and hydroxymethyl groups.

[0254] Polymerizable groups other than those having olefinic unsaturated bonds are preferably, for example, R contained in the repeating unit represented by formula (4) described later. 131 middle.

[0255] The amount of polymerizable groups other than those having olefinic unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0256] -Polar conversion group-

[0257] Polyimides can possess polar conversion groups such as acid-degradable groups. The acid-degradable 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.

[0258] The polarity conversion base is, for example, R contained in the repeating unit represented by equation (4) described later. 131 R 132 In the end of polyimide, etc.

[0259] -Acid Value-

[0260] 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.

[0261] The acid value is preferably below 500 mg KOH / g, more preferably below 400 mg KOH / g, and even more preferably below 200 mg KOH / g.

[0262] When polyimide is supplied for development using a developer solution with organic solvent as the main component (e.g., "solvent development"), 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.

[0263] The acid value mentioned above is determined by known methods, such as those described in JIS K 0070:1992.

[0264] From the viewpoint of balancing storage stability and developability, the acid groups contained in polyimide preferably have a pKa of 0 to 10, and more preferably a pKa of 3 to 8.

[0265] pKa is the numerical value of the equilibrium constant Ka, expressed as its negative common logarithm, pKa, taking into account the dissociation reaction that releases hydrogen ions from an acid. In this specification, unless otherwise specified, pKa is set as a calculated value based on ACD / ChemSketch (registered trademark). pKa can also be referenced to the value published in the "5th Revised Edition of the Handbook of Chemistry: Fundamentals" edited by the Chemical Society of Japan.

[0266] When the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0267] As such an acid group, the polyimide is preferably composed of at least one group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0268] -Phenolic hydroxyl-

[0269] From the viewpoint of making the development speed of alkaline developing solution appropriate, it is preferable that the polyimide has phenolic hydroxyl groups.

[0270] Polyimide can have phenolic hydroxyl groups at the end of the main chain or in the side chain.

[0271] Phenolic hydroxyl groups are preferably, for example, R contained in the repeating unit represented by formula (4) described later. 132 Or R 131 middle.

[0272] 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.

[0273] 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).

[0274] [Chemical Formula 14]

[0275]

[0276] In equation (4), R 131 R represents a divalent organic group. 132 This indicates a tetravalent organic group.

[0277] When it has 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.

[0278] Equation (4-1)

[0279] [Chemical Formula 15]

[0280]

[0281] In equation (4-1), R 133 The group is a polymerizable group, and the other groups have the same meaning as in formula (4).

[0282] Equation (4-2)

[0283] [Chemical Formula 16]

[0284]

[0285] R 134 and R 135 At least one of them is a polymeric group, and when it is not a polymeric group, it is an organic group. The other groups have the same meaning as in formula (4).

[0286] As polymerizable groups, the groups containing olefinic unsaturated bonds mentioned above or crosslinking groups other than those containing olefinic unsaturated bonds can be listed.

[0287] 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.

[0288] As R 131 Examples of diamine residues remaining after removing the amino group from a diamine can be listed. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. As a specific example, R in formula (2) of a polyimide precursor can be listed. 111 Examples.

[0289] From the perspective of more effectively suppressing warping during calcination, R 131 Preferably, it is a diamine residue having at least two alkylene glycol units in the main chain. More preferably, it is a diamine residue containing a total of two or more ethylene glycol chains, propylene glycol chains, or both in a molecule. Even more preferably, it is a diamine residue that does not contain an aromatic ring.

[0290] Examples of diamines that contain a total of two or more ethylene glycol chains or propylene glycol chains in a single 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 (trade 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.

[0291] 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.

[0292] For example, as R 115 The four bonds of the exemplified tetravalent organic group are bonded to the four -C (=O)- portions in formula (4) to form a fused ring.

[0293] R 132 Examples include the tetracarboxylic acid residues remaining after the anhydride group is removed from a tetracarboxylic dianhydride. As a specific example, R in formula (2) of the polyimide precursor can be cited. 115 Examples. From the perspective of the strength of organic membranes, R 132 Preferably, it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0294] It is also preferred to be in R 131 and R 132 At least one of them contains 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, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above-mentioned (DA-1) to (DA-18). 132 The examples (DAA-1) to (DAA-5) mentioned above can be cited as better examples.

[0295] The polyimide also preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, more preferably 20% by mass or less.

[0296] 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.

[0297] To improve the storage stability of the resin composition, the main chain ends of the polyimide are preferably sealed with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds. Among these, monoamines are more preferred. 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-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl... 5-Aminonaphthalene, 2-Carboxy-7-Aminonaphthalene, 2-Carboxy-6-Aminonaphthalene, 2-Carboxy-5-Aminonaphthalene, 2-Aminobenzoic acid, 3-Aminobenzoic acid, 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2-Aminobenzenesulfonic acid, 3-Aminobenzenesulfonic acid, 4-Aminobenzenesulfonic acid, 3-Amino-4,6-Dihydroxypyrimidine, 2-Aminophenol, 3-Aminophenol, 4-Aminophenol, 2-Aminobenzenethiophenol, 3-Aminobenzenethiophenol, 4-Aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different end groups can be introduced by reacting various end-capping agents.

[0298] -Imidization rate (ring-closure rate)-

[0299] From the viewpoint of the obtained organic film's strength, insulation, etc., the imidization rate (also referred to as "ring-closing rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0300] The upper limit of the imidization rate is not particularly limited, as long as it is below 100%.

[0301] The imidization rate described above can be determined, for example, by the following method.

[0302] The infrared absorption spectrum of polyimide was measured, and the absorption peak originating from the imide structure was determined to be 1377 cm⁻¹. -1 The peak intensity P1 near the target was determined. 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 at 1377 cm⁻¹. -1 The peak intensity P2 is nearby. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated according to the following formula.

[0303] Imidification rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0304] Polyimide can contain all repeating units of R 131 and R 132 The repeating units represented by the same formula (4) above can also include R. 131 and R 132 The polyimide may contain two or more repeating units represented by the above formula (4) in different combinations. In addition to the repeating units represented by the above formula (4), the polyimide may also contain other types of repeating units. For example, the repeating units represented by the above formula (2) can be listed as other types of repeating units.

[0305] 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.

[0306] 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.

[0307] 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.

[0308] 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 above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the above-mentioned multiple polyimides are used as a single resin are each within the above-mentioned ranges.

[0309] [Precursor to polyimide and method for manufacturing polyimide]

[0310] Polyimide precursors and polyimides (hereinafter also referred to as "polyimide precursors, etc.") can be obtained, for example, by reacting tetracarboxylic dianhydride with a diamine under low-temperature conditions; by reacting tetracarboxylic dianhydride with a diamine under low-temperature conditions to obtain polyamic acid, and then esterifying it using a condensing agent or an alkylating agent; by obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting it in the presence of a diamine and a condensing agent; by obtaining a diester from tetracarboxylic dianhydride and an alcohol, then acylhalogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine, etc. In the above manufacturing methods, a more preferred method is to obtain a diester from tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine.

[0311] Furthermore, polyimides can also be synthesized using methods such as: fully imidizing the polyimide precursor using known imidization reactions, or introducing a partial imide structure by stopping the imidization reaction midway; and introducing a partial imide structure by mixing the fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0312] 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.

[0313] 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.

[0314] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0315] In methods for manufacturing polyimide precursors, etc., an organic solvent is preferably used during the reaction. The organic solvent can be one type or two or more.

[0316] As organic solvents, examples include pyridine, diethylene glycol dimethyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone, depending on the appropriate specifications of the raw materials.

[0317] 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.

[0318] Basic compounds can be appropriately specified according to the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0319] -End- Capping Agent-

[0320] 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 monools, phenols, thiols, benzenethiophenols, monoamines, etc. From the viewpoint of reactivity and film stability, monools, phenols, or monoamines are more preferred. Preferred monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, 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 phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds as monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminenaphthalene, 1-hydroxy-6-aminenaphthalene, 1-hydroxy-5-aminenaphthalene, 1-hydroxy-4-aminenaphthalene, 2-hydroxy-7-aminenaphthalene, 2-hydroxy-6-aminenaphthalene, 2-hydroxy-5-aminenaphthalene, 1-carboxy-7-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-5-aminenaphthalene, 2 ...6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminena Examples of amino compounds include 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, and 4-aminobenzenethiophenol. Two or more of these can be used, or multiple different end groups can be introduced by reacting various end-capping agents.

[0321] 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 anhydride, carboxylic acid chloride, carboxylic bromide, sulfonyl chloride, sulfonic anhydride, and sulfonic acid carboxylic anhydride, with carboxylic anhydride and carboxylic acid chloride 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, pivaloyl chloride, cyclohexane carbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0322] -Solid precipitation-

[0323] The manufacturing method of polyimide precursors, etc., may include a step of precipitating a solid. 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 to precipitate the polymer component, thereby precipitating it as a solid and drying it to obtain the polyimide precursor, etc. To improve the purification degree, the polyimide precursor, etc., may be repeatedly subjected to operations such as re-dissolving, re-precipitating, and drying. A further step may be included to remove ionic impurities using an ion exchange resin.

[0324] 〔content〕

[0325] 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 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.

[0326] The resin composition of the present invention may contain only one specific resin, or it may contain two or more resins. When it contains two or more resins, the total amount is preferably within the range described above.

[0327] The resin composition of the present invention preferably contains at least two resins.

[0328] 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, preferably two or more specific resins.

[0329] When the resin composition of the present invention contains two or more specific resins, it is preferably, for example, to contain a structure derived from dianhydride (R mentioned in formula (2) above). 115 Two or more different polyimide precursors.

[0330] <Other Resins>

[0331] The resin composition of the present invention may contain a specific resin and other resins different from the specific resin (hereinafter also referred to as "other resins").

[0332] Other resins that can be listed include polybenzoxazole, polybenzoxazole precursor, polyamide-imide, polyamide-imide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyraldehyde resin, styrene resin, polyether resin, polyester resin, etc.

[0333] 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.

[0334] For example, by replacing or other polymeric compounds described below, a polymeric 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 (more than mol / g) of (meth)acrylic resin to a resin composition can improve the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc.

[0335] When the resin composition of the present invention contains other resins, the content of 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.

[0336] 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 solids content of the resin composition.

[0337] As a preferred embodiment of the resin composition of the present invention, it is also possible to configure the content of other resins to be low. 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.

[0338] The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, the total amount is preferably within the range described above.

[0339] <Polymerizing compounds>

[0340] The resin composition of the present invention preferably further comprises a polymerizable compound.

[0341] As polymerizable compounds, free radical crosslinking agents or other crosslinking agents can be listed.

[0342] [Free radical cross-linking agent]

[0343] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0344] A free radical crosslinking agent is a compound having a free radical polymerizable group. Preferably, the free radical polymerizable group is a group containing an olefinic unsaturated bond. Examples of such groups containing an olefinic unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0345] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0346] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, but more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may also have three or more olefinic unsaturated bonds.

[0347] The compounds having two or more olefinic unsaturated bonds are preferably compounds having 2 to 15 olefinic unsaturated bonds, more preferably compounds having 2 to 10 olefinic unsaturated bonds, and even more preferably compounds having 2 to 6 olefinic unsaturated bonds.

[0348] From the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention is preferably a compound having two olefinic unsaturated bonds and a compound having three or more of the above-mentioned olefinic unsaturated bonds.

[0349] 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.

[0350] 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 nucleophilic substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids, are also preferred. Additionally, 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 are also preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Furthermore, as another example, compounds that replace the aforementioned unsaturated carboxylic acids with unsaturated phosphonic acids, styrene or other vinylbenzene derivatives, vinyl ethers, allyl ethers, etc., can also be used. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0351] The free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include those described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated into this specification.

[0352] Preferred free radical crosslinking agents, other than those mentioned above, include free radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0353] As a free radical crosslinking agent, preferred are dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) 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.

[0354] Commercially available free radical crosslinking agents include, for example, tetrafunctional acrylates SR-494 with four ethoxy groups, difunctional methacrylates SR-209, 231, and 239 with four ethoxy groups (manufactured by Sartomer Company, Inc.), hexafunctional acrylates DPCA-60 with six pentylioxy groups, trifunctional acrylates TPA-330 with three isobutyryloxy groups (manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.). (Manufactured by Kyoisha Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOFCORPORATION.), etc.

[0355] As a free radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, or urethane 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. Compounds having an amino or thioether structure within the molecule as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238 can also be used as a free radical crosslinking agent.

[0356] The free radical crosslinking agent can also 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 that, in the 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, 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.

[0357] The acid value of the free radical crosslinking agent containing acid groups is preferably 0.1 to 300 mg KOH / g, more preferably 1 to 100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and developability. Furthermore, it demonstrates good polymerizability. The above acid value is determined according to the description in JIS K 0070:1992.

[0358] As a free radical crosslinking agent, it is also preferred to be a free radical crosslinking agent having at least one of the groups selected from urea bonds and urethane bonds (hereinafter, also referred to as "crosslinking agent U").

[0359] In this invention, the urea bond is *-NR. N -C(=O)-NR N -* represents the key, R N Each symbol represents a hydrogen atom or a monovalent organic group, and * represents the bonding site with a carbon atom.

[0360] In this invention, the carbamate bond is *-OC(=O)-NR. N -* represents the key, RN The symbol represents a hydrogen atom or a monovalent organic group, and * indicates the bonding site with a carbon atom, respectively.

[0361] Including crosslinking agent U in the resin composition can sometimes improve chemical resistance, resolution, etc.

[0362] The mechanism by which the above effects are obtained is not yet clear, but it is believed that, for example, during curing by heating, a portion of the crosslinking agent U is thermally decomposed to produce amines, etc., which promote the cyclization of heterocyclic polymer precursors such as polyimide precursors.

[0363] The crosslinking agent U may have only one urea bond or a carbamate bond, or it may have more than one urea bond and more than one carbamate bond, or it may have no carbamate bond but have more than two urea bonds, or it may have no urea bond but have more than two carbamate bonds.

[0364] The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0365] When the crosslinking agent U does not have urethane bonds, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0366] When the crosslinking agent U does not have urea bonds, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0367] The free radical polymerizable groups in the crosslinking agent U are not particularly limited, and can include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0368] When the crosslinking agent U has two or more free radical polymerizable groups, the structures of each free radical polymerizable group can be the same or different.

[0369] The number of free radical polymerizable groups in the crosslinking agent U can be only 1 or more than 2, preferably 1 to 10, more preferably 1 to 6, and especially preferably 1 to 4.

[0370] The free radical polymerizable group value (mass of compound in 1 mole of free radical polymerizable group) in crosslinking agent U is preferably 150-400 g / mol.

[0371] From the viewpoint of the chemical resistance of the cured product, the lower limit of the free radical polymerizability group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and especially preferably 250 g / mol or more.

[0372] From the viewpoint of radioactivity, the upper limit of the above-mentioned free radical polymerizability group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, and especially preferably 300 g / mol or less.

[0373] The polymerizability of the crosslinking agent U is preferably 210–400 g / mol, more preferably 220–400 g / mol.

[0374] The following are specific examples of crosslinking agent U, but crosslinking agent U is not limited to these.

[0375] [Chemical Formula 17]

[0376]

[0377] From the viewpoint of pattern resolution and film elasticity, it is preferable to use a difunctional methacrylate or acrylate resin composition.

[0378] 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, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentylene glycol diacrylate, and 1,6-hexanediol diacrylate can be used. 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane dimethacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct dimethacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, cyanuric acid (EO) modified dimethacrylate, cyanuric acid modified dimethacrylate, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. These can be mixed in combination for use as needed.

[0379] Additionally, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate, and the molecular weight of the polyethylene glycol chain is around 200.

[0380] When a free radical crosslinking agent is present, the content of the free radical crosslinking agent relative to the total solids content of the resin composition 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.

[0381] Free radical crosslinking agents can be used alone or in combination of two or more. When two or more are used together, the total amount is preferably within the range described above.

[0382] [Other crosslinking agents]

[0383] The resin composition of the present invention is also preferably composed of other crosslinking agents different from the free radical crosslinking agents described above.

[0384] Other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents mentioned above. Preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds in the composition or their reaction products by photosensitization by the photoacid generator or photoalkali generator mentioned above. They are also preferably compounds having multiple 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 acid or base.

[0385] The acid or base mentioned above is preferably an acid or base generated by a photoacid generator or a photoalkali generator during the exposure process.

[0386] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0387] When the resin composition of the present invention contains a polymerizable compound, the content of the polymerizable compound relative to the total solids content of the resin composition 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.

[0388] The polymerizable compound can be used alone, or in combination with two or more. When two or more are used together, the total amount is preferably within the range described above.

[0389] [Polymerization initiator]

[0390] The resin composition of the present invention contains a polymerization initiator.

[0391] The polymerization initiator can be a thermal polymerization initiator or a photopolymerization initiator, and is particularly preferred to include a photopolymerization initiator.

[0392] 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 photosensitizing to light from the ultraviolet region to the visible region is preferred. Furthermore, an active agent that generates active free radicals by interacting with a photoexcited sensitizer can also be used.

[0393] The photoradical polymerization initiator preferably contains at least one component having a wavelength of at least about 50 L·mol⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 ·cm -1 The molar absorptivity of a compound can be determined using known methods. For example, it is preferred to use a UV-Vis spectrophotometer (a Cary-5 spectrophotometer manufactured by Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0394] As photoradical polymerization initiators, any known compounds 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, iron aromatic hydrocarbon complexes, etc. For detailed information on these, 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, the following can be cited as examples: paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173; compounds described in Japanese Patent Publication 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 peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313. These contents are incorporated into this specification.

[0395] Examples of ketone compounds include, for instance, those described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0396] 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 as described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators as described in Japanese Patent No. 4225898 can be used, as these contents are incorporated herein by reference.

[0397] 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.

[0398] 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.

[0399] As an aminoacetophenone-based initiator, an acylphosphine oxide-based initiator, or a metallocene compound, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 may also be used, for example. This content is incorporated herein by reference.

[0400] Oxime compounds are more preferably used as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they offer a wide exposure latitude (exposure margin) and also function as photocuring accelerators.

[0401] 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 andTechnology (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.

[0402] Preferred oxime compounds include, for example, compounds with the following structures, or 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pent-3-one, 2-(acetoxy(imino))-1-phenylprop-1-one, 2-(benzoyloxy(imino))-1-phenylprop-1-one, 3-((4-toluenesulfonyloxy)imino)but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylprop-1-one, etc. In resin compositions, oxime compounds are particularly preferred as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=NOC (=O)- linking group within the molecule.

[0403] [Chemical Formula 18]

[0404]

[0405] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKACORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New ElectronicMaterials CO.,LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Co.,Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Furthermore, oxime compounds with the following structures can also be used.

[0406] [Chemical Formula 19]

[0407]

[0408] [Chemical Formula 20]

[0409]

[0410] When the resin composition contains a photopolymerization initiator, its content relative to the total solids content of the resin composition 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 one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[0411] In addition, photopolymerization initiators sometimes also function as thermal polymerization initiators, and therefore crosslinking based on photopolymerization initiators can sometimes be further carried out by heating in an oven or heating plate.

[0412] <Alkali generating agent>

[0413] The resin composition of the present invention may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of generating alkali through physical or chemical action.

[0414] Examples of alkali-generating agents include paragraphs 0015-0057 of International Publication No. 2015 / 199219, paragraphs 0054-0070 of International Publication No. 2018 / 025738, paragraphs 0060-0072 of International Publication No. 2019 / 189110, paragraphs 0013-0028 of International Publication No. 2019 / 189111, and paragraphs 0013-0039 of International Publication No. 2020 / 054226. The compounds described in International Publication No. 2020 / 066244 (paragraphs 0101-0146), International Publication No. 2020 / 066315 (paragraphs 0014-0049), International Publication No. 2020 / 066416 (paragraphs 0102-0159), International Publication No. 2020 / 066435 (paragraphs 0013-0050), and International Publication No. 2020 / 170997 (paragraphs 0089-0100), etc., are included in this specification.

[0415] When the resin composition 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 resin in the resin composition. 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, even more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less, and particularly preferably 4 parts by weight or less.

[0416] One or more alkali-generating agents can be used. When two or more are used, the total amount is preferably within the range described above.

[0417] <Solvent>

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

[0419] 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.

[0420] Examples of esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, 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., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, ethyl 3-ethoxypropionic acid)). Esters, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred esters.

[0421] Examples of preferred ethers include 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 celusone acetate, ethyl celusone 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.

[0422] Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydro L-glucanone.

[0423] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred examples of cyclic hydrocarbons.

[0424] As a sulfoxide, dimethyl sulfoxide can be listed as a preferred sulfoxide.

[0425] Preferred 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-formylmorphofolin, and N-acetylmorphofolin.

[0426] Examples of preferred urea types include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolium ketone.

[0427] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

[0428] From the perspective of improving the properties of the coating surface, it is also preferable that the solvent is a mixture of two or more forms.

[0429] The resin composition of the present invention preferably contains a solvent having at least one of an amide group and a hydroxyl group.

[0430] In this invention, the solvent is preferably selected from one or more of the following: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celusone acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucosidone, and dihydroL-glucosidone. Particularly preferred methods include the use of dimethyl sulfoxide with γ-butyrolactone, dimethyl sulfoxide with γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone with ethyl lactate. Further addition of approximately 1 to 10% by mass relative to the total mass of these solvents is also a preferred method of the invention.

[0431] In particular, from the viewpoint of the storage stability of the resin composition, including γ-valerolactone as a solvent is one of the preferred embodiments of the present invention. In this embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and can be 100% by mass. The above content can be determined by considering the solubility of components such as resin (A) contained in the resin composition.

[0432] Furthermore, when dimethyl sulfoxide and γ-valerolactone are used together, the total mass of the solvent preferably contains 60-90% by mass of γ-valerolactone and 10-40% by mass of dimethyl sulfoxide, more preferably 70-90% by mass of γ-valerolactone and 10-30% by mass of dimethyl sulfoxide, and even more preferably 75-85% by mass of γ-valerolactone and 15-25% by mass of dimethyl sulfoxide.

[0433] From the viewpoint of coatability, the solvent content is preferably set to a total solids concentration of 5 to 80% by mass in the resin composition of the present invention, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating and the coating method. When two or more solvents are contained, their total content is preferably within the above range.

[0434] <Metal Adhesion Modifier>

[0435] From the viewpoint of improving adhesion to metal materials used in electrodes or wiring, the resin composition of the present invention preferably contains a metal adhesion modifier. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilane 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.

[0436] (Silane coupling agent)

[0437] As silane coupling agents, examples include compounds described in paragraph 0316 of International Patent Publication No. 2021 / 112189 and compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which 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. The following compounds are also preferred as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0438] [Chemical Formula 21]

[0439]

[0440] <Migration Inhibitor>

[0441] The resin composition of the present invention preferably further comprises a migration inhibitor. By comprising a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0442] There are no particular limitations on the migration inhibitors, and examples include 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, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, mofolin ring, 2H-piperanone ring and 6H-piperanone ring, triazine ring), thioureas and compounds having hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0443] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[0444] Other migration inhibitors, for example, include 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, etc., which are incorporated herein by reference.

[0445] The following compounds can be listed as specific examples of migration inhibitors.

[0446] [Chemical Formula 22]

[0447]

[0448] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% 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.

[0449] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, their total number is preferably within the range described above.

[0450] <Polymerization Inhibitor>

[0451] 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.

[0452] Specific compounds that can be used as polymerization inhibitors include those described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, phenoxazine, etc. This content is included in this specification.

[0453] 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 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.

[0454] The polymerization inhibitor may be only one type or two or more types. When there are two or more polymerization inhibitors, their total amount is preferably within the range described above.

[0455] <Other Additives>

[0456] The resin composition of the present invention may contain various additives as needed within the scope of achieving the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organometallic compounds (preferably organotitanium compounds), antioxidants, anticoagulants, phenolic compounds, urea compounds without free radical polymerizable groups, carbodiimide compounds, isourea compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the physical properties of the membrane can be adjusted. These components can be described, for example, by referring to paragraphs 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 in U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 in Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are used, it is preferable to set their total content to less than 3% by mass of the solid components of the resin composition of the present invention.

[0457] [surfactants]

[0458] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0459] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially flowability) during the preparation of the coating liquid composition can be 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, the interfacial tension between the coated surface and the coating liquid decreases, the wettability of the coated surface is improved, and the coating properties of the coated surface are enhanced. Therefore, it is more preferable to form a uniform film with small thickness non-uniformity.

[0460] As fluorinated surfactants, compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which is incorporated herein by reference, can be listed.

[0461] As a fluorinated surfactant, a fluorinated polymer compound can also be preferably used, which comprises: 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 ethoxide or propoxide groups), for example, the following compounds can be listed.

[0462] [Chemical Formula 23]

[0463]

[0464] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0465] Regarding fluorinated surfactants, fluorinated polymers having olefinically unsaturated groups in their side chains can also be used as fluorinated surfactants. 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 products include, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0466] 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. From the viewpoint of uniformity of coating film thickness or liquid saving, fluorinated surfactants with fluorine content in this range are effective and have good solubility in the composition.

[0467] As silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants, the compounds described in paragraphs 0329 to 0334 of International Publication No. 2021 / 112189 are listed respectively, and this content is incorporated into this specification.

[0468] Surfactants can be used in single-use or in combination of two or more.

[0469] The content of surfactant 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.

[0470] [Higher fatty acid derivatives]

[0471] To prevent polymerization hindrance caused by oxygen, the resin composition of the present invention may contain higher fatty acid derivatives such as docosanoic acid or docosanoamide, which are unevenly distributed on the surface of the resin composition of the present invention during the drying process after coating.

[0472] Furthermore, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0473] When the resin composition contains higher fatty acid derivatives, the content of the higher fatty acid derivatives relative to the total solids content of the resin composition is preferably 0.1% to 10% by mass. There may be only one type of higher fatty acid derivative or two or more types. When there are two or more types of higher fatty acid derivatives, their total content is preferably within the above range.

[0474] [Thermal polymerization initiator]

[0475] Examples of thermal polymerization initiators include thermal free radical polymerization initiators. Thermal free radical polymerization initiators are compounds that generate free radicals through thermal energy to initiate or promote the polymerization reaction of polymerizable compounds. By adding thermal free radical polymerization initiators, polymerization reactions of resins and polymerizable compounds can be carried out, thus further improving solvent resistance. Furthermore, photopolymerization initiators sometimes also have the function of initiating polymerization through heat, and therefore can sometimes be added as thermal polymerization initiators.

[0476] As thermal free radical polymerization initiators, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated herein by reference, can be listed.

[0477] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition 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 be one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[0478] [Inorganic particles]

[0479] Specifically, inorganic particles include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0480] The average particle size of the 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.

[0481] The aforementioned average particle size of the inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be determined, for example, by dynamic light scattering based on the Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO.,LTD.).

[0482] When the above measurements are difficult to perform, centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method can also be used for measurement.

[0483] [Ultraviolet absorber]

[0484] Examples of UV absorbers include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based UV absorbers.

[0485] Specific examples of ultraviolet absorbers include compounds described in paragraphs 0341 to 0342 of International Publication No. 2021 / 112189, the contents of which are incorporated herein by reference.

[0486] Ultraviolet absorbers can be used alone or in combination of two or more.

[0487] When the resin composition contains a UV absorber, the content of the UV 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 resin composition.

[0488] [Organometallic compounds]

[0489] The organometallic compound is preferably an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even after curing at low temperatures.

[0490] As usable organotitanium compounds, examples include compounds in which organic groups are covalently or ionicly bonded to titanium atoms.

[0491] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0492] I) Titanium chelate compounds: From the viewpoint of excellent storage stability of the resin composition and the ability to obtain good cured patterns, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples include bis(triethanolamine)diisopropoxy titanium, bis(2,4-glutarate)di(n-butoxy) titanium, bis(2,4-glutarate)diisopropoxy titanium, bis(tetramethylheptidine)diisopropoxy titanium, bis(ethyl acetoacetate)diisopropoxy titanium, etc.

[0493] II) Tetraalkoxy titanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoyloxytitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc.

[0494] 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.

[0495] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecylbenzenesulfonate) isopropoxy titanium, etc.

[0496] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0497] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0498] VII) Titanate coupling agents: such as isopropyltris(dodecyl)benzenesulfonyl titanate, etc.

[0499] From the viewpoint of better drug resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dicarboxylated titanium compounds is preferred as the organotitanium compound. Particularly preferred are bis(ethyl acetoacetate)diisopropoxy titanium, tetra(n-butoxy) titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium.

[0500] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of a specific resin. When the content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when it is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0501] When the resin composition of the present invention contains an organometallic compound, the content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of a particular resin.

[0502] [Antioxidants]

[0503] By including antioxidants as additives, the elongation properties of the cured film or its adhesion to metallic materials can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. Specific examples of antioxidants include compounds described in paragraphs 0348 to 0357 of International Publication No. 2021 / 112189, which are incorporated herein by reference.

[0504] The antioxidant content is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of a specific resin. By setting the addition amount to 0.1 parts by weight or more, elongation characteristics or improved adhesion to metal materials can be easily obtained even under high temperature and high humidity environments. Furthermore, by setting it to 10 parts by weight or less, the sensitivity of the resin composition can be improved, for example, through interaction with the photosensitizer. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, their total amount is preferably within the above-mentioned range.

[0505] [Anticoagulant]

[0506] Examples of anti-coagulants include sodium polyacrylate.

[0507] Anti-coagulants can be used alone or in combination of two or more.

[0508] When the resin composition contains an anti-coagulant, the content of the anti-coagulant 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 solids content of the resin composition.

[0509] [Phenolic compounds]

[0510] 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 (these are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (these are product names, manufactured by ASAHI YUKIZAICORPORATION).

[0511] Phenolic compounds can be used alone or in combination of two or more.

[0512] When the resin composition contains phenolic compounds, the content of phenolic compounds is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, relative to the total solid content of the resin composition.

[0513] [Urea compounds, carbodiimide compounds, and isourea compounds that do not possess free radical polymerizable groups]

[0514] From the viewpoint of elongation at break and adhesion to metal or resin layers, the resin composition of the present invention may further comprise at least one compound selected from the group consisting of urea compounds (also referred to as "urea compounds (UX)") that do not have free radical polymerizable groups, compounds having a carbodiimide structure (carbodiimide compounds), and compounds having an isourea bond (isourea compounds) (hereinafter also referred to as "urea compounds (UX) etc.").

[0515] Among these, the resin composition of the present invention preferably contains a urea compound (UX).

[0516] The urea compounds (UX) mentioned herein do not include compounds corresponding to the aforementioned compound (A), polymeric compounds, or silane coupling agents.

[0517] Examples of urea compounds (UX) include those described in paragraphs 0334 to 0339 of International Publication No. 2022 / 070730.

[0518] Specific examples of urea compounds (UX) include dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, diisopropylisourea, etc., but are not limited to these.

[0519] The total content of urea compounds (UX) and the like is preferably 0.001 to 10.0 parts by weight relative to 100 parts by weight of a specific resin, more preferably 0.002 to 8.0 parts by weight, and even more preferably 0.008 to 6.0 parts by weight.

[0520] Urea compounds (UX) can be used alone or in combination with two or more. When two or more are used in combination, the total content of these compounds is preferably within the range described above.

[0521] The resin composition of the present invention preferably contains a urea compound. As described above, the "urea compound (compound having a urea bond)" can be a urea compound having a free radical polymerizable group (described as a crosslinking agent U) or a urea compound (urea compound (UX)) not having a free radical polymerizable group.

[0522] [Other polymers]

[0523] Other examples of polymeric compounds include siloxane resins, (meth)acrylic acid polymers copolymerized from (meth)acrylic acid, phenolic varnish resins, soluble phenolic resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may also be modified forms incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0524] Other polymer compounds can be used alone or in combination of two or more.

[0525] When the resin composition contains other polymeric compounds, the content of the other polymeric compounds is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, relative to the total solid content of the resin composition.

[0526] <Characteristics of the Resin Composition>

[0527] The viscosity of the resin composition of the present invention can be adjusted by utilizing the concentration of the solid components in 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. If within the above range, a highly uniform coating film can be easily obtained. For example, if it is 1,000 mm... 2 If the speed is above 12,000 mm, it is easy to coat with the film thickness required for reinsertion insulation. 2 When the speed is below / s, a coating film with excellent surface finish can be obtained.

[0528] <Restrictions on the Contents of Substances in Resin Compositions>

[0529] 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. If it is less than 2.0%, the storage stability of the resin composition is improved.

[0530] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container.

[0531] 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 in the form of complexes of organic compounds and metals. When multiple metals are included, the total amount of these metals is preferably within the above-mentioned range.

[0532] Furthermore, as a method for reducing unintentionally contained metallic impurities in the resin composition of the present invention, the following methods can be listed: 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 performing distillation in an apparatus with a lining such as polytetrafluoroethylene to suppress contamination as much as possible.

[0533] In the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, the content of halogen atoms 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. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is preferably within the above-mentioned ranges.

[0534] Methods for adjusting the content of halogen atoms can preferably include ion exchange treatment, etc.

[0535] As a container for the resin composition of the present invention, conventionally known containers can be used. For the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, multi-layered bottles with an inner wall composed of six layers of six different resins or bottles with a seven-layer structure formed by six different resins are preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0536] <Cure of Resin Composition>

[0537] By curing the resin composition of the present invention, a cured resin composition can be obtained.

[0538] The cured product of the present invention is a cured product obtained by curing a resin composition.

[0539] The curing of the resin composition is preferably carried out by heating, with a heating temperature more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The morphology of the cured resin composition is not particularly limited, and can be film-shaped, rod-shaped, spherical, granular, etc., depending on the application. In this invention, the cured product is preferably film-shaped. The shape of the cured product can also be selected according to applications such as forming a protective film on a wall surface through pattern processing of the resin composition, forming conductive through-holes, adjusting impedance or electrostatic capacitance or internal stress, or imparting heat dissipation function. The film thickness of the cured product (the film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less.

[0540] 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. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, which can be calculated by the following formula.

[0541] Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0542] <Characteristics of cured resin compositions>

[0543] 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. If it is 70% or more, it may sometimes result in a cured product with excellent mechanical properties.

[0544] 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.

[0545] 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.

[0546] <Preparation of Resin Compositions>

[0547] 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 conventionally known methods.

[0548] Examples of mixing methods include mixing based on stirring blades, mixing based on ball mills, and mixing by rotating a tank.

[0549] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0550] For the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration using a filter is preferred. For details regarding filtration using a filter, please refer to paragraph 0277 of International Publication No. 2023 / 120059, which is incorporated herein by reference.

[0551] In addition to filtration using filters, impurities can also be removed using adsorption materials. Filtration and impurity removal using adsorption materials can also be combined. Known adsorption materials can be used. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0552] After filtration using a filter, a process can be performed whereby the resin composition filled in the bottle is placed under reduced pressure for degassing.

[0553] <Method for manufacturing solidified products>

[0554] 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.

[0555] The method for manufacturing the cured material is more preferably a film forming step described above, 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 (the exposed film) using a developing solution to form a pattern.

[0556] The method for manufacturing the cured material is particularly preferred to include 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.

[0557] Furthermore, the method for manufacturing the cured material is preferably to include the above-described film formation process and the process of heating the above-described film.

[0558] Furthermore, the method for manufacturing the cured material is preferably a heating step that heats the film formed in the above-mentioned film forming step at a temperature of 150°C to 450°C and a grinding step that grinds the heated film.

[0559] The following is a detailed explanation of each process.

[0560] (Membrane formation process)

[0561] The resin composition of the present invention can be used in a film forming process applicable to a substrate for forming a film.

[0562] 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.

[0563] [Substrate]

[0564] The type of substrate can be appropriately specified according to the application and is not particularly limited. Examples of substrates include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any of the substrates formed of metal and substrates with metal layers formed by plating, deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). Semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred.

[0565] On the surface of these substrates, a layer such as a sealing layer or an oxide layer formed of hexamethyldisilazane (HMDS) can be provided.

[0566] The shape of the substrate is not particularly limited; it can be circular or rectangular.

[0567] Regarding the dimensions of the substrate, for a circular shape, the diameter is preferably 100–450 mm, more preferably 200–450 mm. For a rectangular shape, the length of the shorter side is preferably 100–1000 mm, more preferably 200–700 mm.

[0568] As a substrate, for example, a plate-shaped substrate (substrate) can be used, preferably a panel-shaped substrate.

[0569] When a resin composition is applied to the surface of a resin layer (e.g., a layer composed of cured material) or a metal layer to form a film, the resin layer or the metal layer becomes a substrate.

[0570] As a method for applying the resin composition to a substrate, coating is preferred.

[0571] 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 preferred. From the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are more preferred. By adjusting the solid content concentration of the resin composition or the coating conditions according to the applicable 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 3500 rpm can be used for about 10 seconds to 3 minutes.

[0572] 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.

[0573] Regarding the transfer method, the production 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 is preferably used.

[0574] Furthermore, a process for removing excess film can be performed at the ends of the substrate. Examples of such processes include edge beaded residue rinsing (EBR) and back rinse.

[0575] Alternatively, a pre-wetting process can be used: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve its wettability, and then the resin composition is applied.

[0576] (Drying process)

[0577] After the film formation process (layer formation process), in order to remove the solvent, the above-mentioned film can be used for a process of drying the formed film (layer) (drying process).

[0578] That is, the method for manufacturing the cured product of the present invention may include a drying step of drying the film formed by the film forming step.

[0579] The drying process described above is preferably performed after the film formation process and before the exposure process.

[0580] 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. Examples of drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0581] (Exposure process)

[0582] The above-mentioned film can be used in an exposure process that selectively exposes the film.

[0583] Methods for manufacturing cured materials may include an exposure process that selectively exposes a film formed by a film forming process.

[0584] Selective exposure refers to exposing only a portion of the film. Furthermore, through selective exposure, exposed areas (exposed areas) and unexposed areas (non-exposed areas) are formed on the film.

[0585] Regarding the exposure amount, it is not particularly limited as long as it is sufficient to cure the resin composition of the present invention. For example, it is preferably 50 to 10000 mJ / cm based on the exposure energy at a wavelength of 365 nm. 2 More preferably, it is 200–8000 mJ / cm². 2 .

[0586] The exposure wavelength can be appropriately specified in the range of 190 to 1000 nm, preferably 240 to 550 nm.

[0587] Regarding the exposure wavelength, in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 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), broadband (gamma, h, and i-ray wavelengths), (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, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. For the resin composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and from the viewpoint of exposure sensitivity, exposure based on i-rays is more preferred.

[0588] The exposure method is not particularly limited, as long as at least a portion of the film composed of the resin composition of the present invention is exposed. Examples include exposure using a photomask and exposure based on direct laser imaging.

[0589] (Heating process after exposure)

[0590] The above-mentioned film can be used in the post-exposure heating process (post-exposure heating process).

[0591] That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.

[0592] The post-exposure heating process can be performed after the exposure process and before the development process.

[0593] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0594] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0595] From the initial heating temperature to the maximum heating temperature, the heating rate during the post-exposure heating process is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[0596] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0597] As a heating mechanism in the post-exposure heating process, it is not particularly limited and can use known heating plates, ovens, infrared heaters, etc.

[0598] Furthermore, heating is preferably carried out in a low-oxygen environment by circulating inert gases such as nitrogen, helium, or argon.

[0599] (Developing process)

[0600] The exposed film can be used in the developing process to form a pattern by developing it with a developing solution.

[0601] That is, the method for manufacturing the cured product of the present invention may include a developing step of developing a film exposed by an exposure step to form a pattern using a developing solution.

[0602] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[0603] Here, the development process that removes the non-exposed portions of the film is called negative development, and the development process that removes the exposed portions of the film is called positive development.

[0604] [Developing solution]

[0605] Examples of developing solutions used in the developing process include alkaline aqueous solutions and developing solutions containing organic solvents.

[0606] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained 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. In the total mass of the developer, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0607] When the developer contains an organic solvent, compounds described in paragraph 0387 of International Publication No. 2021 / 112189 may be used as the organic solvent. This content is incorporated into this specification. Furthermore, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., may be preferably listed as alcohols, and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., may be preferably listed as amides.

[0608] When the developer contains an organic solvent, one or more organic solvents can be used. In this invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, more preferably a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide, and especially preferably a developer containing cyclopentanone.

[0609] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content may also be 100% by mass.

[0610] When the developer contains an organic solvent, the developer may further contain at least one of an alkaline compound and an alkali-generating agent. The alkaline compound and alkali-generating agent may be selected from at least one group consisting of an amide-containing alkaline compound, other alkaline compounds, an amide-containing alkali-generating agent, and other alkali-generating agents as described in paragraphs 0030 to 0044 of International Publication No. 2023 / 032545. This content is incorporated herein by reference.

[0611] When the developer contains at least one of an alkaline compound and an alkali-generating agent, the content of the alkaline compound or the alkali-generating agent relative to the total mass of the developer is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit of the above content is not particularly limited, but is preferably, for example, 0.1% by mass or more.

[0612] When the alkaline compound or alkali-generating agent is solid in the environment of using the developer, the content of the alkaline compound or alkali-generating agent is preferably 70 to 100% by mass relative to the total solid content of the developer.

[0613] The developer may contain only one alkaline compound and at least one alkali-generating agent, or it may contain two or more. When there are two or more alkaline compounds and alkali-generating agents, their total amount is preferably within the range described above.

[0614] The developer may further contain other ingredients.

[0615] Other components include, for example, well-known surfactants or well-known defoamers.

[0616] [Method for supplying developer]

[0617] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the developer. Methods include immersing the substrate with the film formed in the developer, swirling immersion development using a nozzle to supply the developer to the film formed on the substrate, or continuous supply of developer. There are no particular restrictions on the type of nozzle, such as straight nozzles, spray nozzles, and mist nozzles.

[0618] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, a method of supplying developer using a straight nozzle or a method of continuous supply using a spray nozzle is preferred. From the viewpoint of developer penetration into the image area, a method of supplying using a spray nozzle is more preferred.

[0619] Furthermore, the process can be performed by continuously supplying developer using a straight nozzle, rotating the substrate to remove the developer from the substrate, performing rotary drying, and then continuously supplying developer again using a straight nozzle, rotating the substrate to remove the developer from the substrate. This process can be repeated multiple times.

[0620] Methods for supplying developer in the developing process include processes such as continuously supplying developer to a substrate, maintaining developer on a substrate in a roughly static state, using ultrasound or the like to vibrate developer on a substrate, and combining these methods.

[0621] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution during development is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0622] In the developing process, after treatment with the developer, the pattern can be further cleaned (rinsed) using a rinsing solution. Furthermore, methods such as supplying the rinsing solution while the developer in contact with the pattern is not completely dry can be employed.

[0623] [Rinse solution]

[0624] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0625] Regarding the rinsing fluid, please refer to paragraphs 0300 to 0303 of International Publication No. 2023 / 120059, which is incorporated in this specification.

[0626] [Method for supplying flushing fluid]

[0627] For the method of supplying the flushing fluid, please refer to paragraphs 0304-0305 of International Publication No. 2023 / 120059, which is incorporated herein by reference.

[0628] The preferred rinsing time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0629] In the developing process, after treatment with the developing solution or after cleaning the pattern based on the rinsing solution, a step may be included to bring the processing solution into contact with the pattern. Furthermore, methods such as supplying the processing solution while the developing solution or rinsing solution in contact with the pattern is not completely dry may also be employed.

[0630] Examples of treatment solutions include at least one of water and an organic solvent, and at least one of an alkaline compound and an alkali-generating agent.

[0631] The preferred methods for at least one of the above-mentioned organic solvents, alkaline compounds, and alkali-generating agents are the same as the preferred methods for the organic solvents, alkaline compounds, and alkali-generating agents used in the above-mentioned rinsing solutions.

[0632] The method of supplying the treatment liquid to the pattern can be the same as the method of supplying the rinsing liquid described above, and the preferred method is also the same.

[0633] The content of alkaline compounds or alkali-generating agents in the treatment solution is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment solution. The lower limit of the above content is not particularly limited, but is preferably, for example, 0.1% by mass or more.

[0634] Furthermore, when the alkaline compound or alkali generating agent is solid in the environment of the treatment liquid, the content of the alkaline compound or alkali generating agent is preferably 70 to 100% by mass relative to the total solid content of the treatment liquid.

[0635] When the treatment solution contains at least one of an alkaline compound and an alkali-generating agent, the treatment solution may contain only one of the alkaline compound and the alkali-generating agent, or it may contain two or more. When there are two or more alkaline compounds and alkali-generating agents, their total amount is preferably within the above-mentioned range.

[0636] (Heating process)

[0637] The pattern obtained by the developing process (or the washed pattern in the case of the washing process) can be used in a heating process for heating the pattern obtained by the developing process described above.

[0638] That is, the method for manufacturing the cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.

[0639] Furthermore, the method for manufacturing the cured product of the present invention may also include a heating step of heating a pattern obtained by other methods without a developing step or a film obtained by a film forming step.

[0640] During the heating process, resins such as polyimide precursors undergo cyclization to become polyimide resins.

[0641] Furthermore, crosslinking of unreacted crosslinking groups in resin (A) or crosslinking agents other than resin (A) is also performed.

[0642] The heating temperature (maximum heating temperature) in the heating process is preferably 50℃ to 450℃, more preferably 150℃ to 450℃, even more preferably 150℃ to 350℃, even more preferably 150℃ to 250℃, particularly preferably 160℃ to 250℃, and most preferably 160℃ to 230℃.

[0643] The heating process is preferably a process in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of an alkali or the like generated by the alkali generating agent through heating.

[0644] From the initial heating temperature to the maximum heating temperature, the heating process is preferably carried out at a heating rate of 1 to 12°C / minute. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. Setting the heating rate to 1°C / minute or higher ensures productivity and prevents excessive evaporation of acid or solvent; setting the heating rate to 12°C / minute or lower helps to mitigate residual stress in the cured product.

[0645] Furthermore, in the case of an oven capable of rapid heating, the heating rate from the initial temperature to the maximum heating temperature is preferably 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0646] Regarding the heating process, please refer to paragraphs 0309 to 0313 of International Publication No. 2023 / 120059, which is incorporated into this specification.

[0647] (Post-development exposure process)

[0648] The pattern obtained by the developing process (or the washed pattern in the case of the washing process) can also replace the heating process described above or, in addition to the heating process described above, be used for a post-developing exposure process to expose the pattern after the developing process.

[0649] That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for manufacturing the cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.

[0650] In the post-development exposure process, it can promote, for example, the cyclization reaction of polyimide precursors by photo-alkali-generating agents, or the removal of acid-degrading groups by photo-acid-generating agents.

[0651] In the post-development exposure process, it is sufficient for at least a portion of the pattern obtained in the development process to be exposed, but preferably all of the pattern is exposed.

[0652] Based on the exposure energy conversion at the wavelength where the photosensitive compound is sensitive, the exposure amount in the post-development exposure process is preferably 50–20000 mJ / cm. 2 More preferably, it is 100–15000 mJ / cm 2 .

[0653] The post-development exposure process can be performed using the light source described in the above-mentioned exposure process, preferably using broadband light.

[0654] (Metal layer formation process)

[0655] The pattern obtained by the developing process (preferably a pattern for at least one of the heating process and the post-development exposure process) can be used in the metal layer forming process for forming a metal layer on the pattern.

[0656] That is, the method for manufacturing the cured product of the present invention preferably includes a metal layer forming step that forms a metal layer on a pattern obtained by a developing step (preferably at least one of a heating step and a post-developing exposure step).

[0657] There are no particular limitations on the metal layer; any existing metal can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0658] There are no particular limitations on the method for forming the metal layer, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electroplating can be listed. As a preferred method of plating, electroplating using copper sulfate or copper cyanide plating solutions can be listed.

[0659] The thickness of the metal layer is preferably 0.01 to 50 μm in the thickest part, and more preferably 1 to 10 μm.

[0660] <Manufacturing Method of Interlayer Insulating Film for Rewiring Layers>

[0661] The method for manufacturing the interlayer insulating film for the rewiring layer of the present invention includes:

[0662] In the photosensitive film formation process, the resin composition of the present invention is coated onto a substrate to form a photosensitive film;

[0663] The exposure process involves exposing the aforementioned photosensitive film to form an exposed film; and

[0664] In the pattern forming process, the above-mentioned exposure film is developed with a developing solution to form an insulating pattern.

[0665] The photosensitive film forming process is the same as the film forming process in the aforementioned "Method for Manufacturing Cured Materials". Furthermore, the exposure process and the pattern forming process are also the same as the exposure process and the development process in the aforementioned "Method for Manufacturing Cured Materials".

[0666] <Laminated bodies and methods for manufacturing laminated bodies>

[0667] The laminate of the present invention refers to a structure having multiple layers composed of the cured material of the present invention.

[0668] A laminate is a laminate consisting of two or more layers made of a solidified material, or it can be a laminate consisting of three or more layers.

[0669] In the above-described laminate, at least one of the two or more layers composed of the above-described cured material is a layer composed of the cured material of the present invention. From the viewpoint of suppressing the shrinkage of the cured material or the deformation of the cured material accompanying the shrinkage, it is also preferable that all the layers composed of the cured material included in the above-described laminate are layers composed of the cured material of the present invention.

[0670] That is, the manufacturing method of the laminate of the present invention preferably includes the manufacturing method of the cured product of the present invention, and more preferably includes the manufacturing method of the cured product of the present invention repeatedly.

[0671] The laminate of the present invention preferably comprises two or more layers made of cured material, with a metal layer between any of the aforementioned layers made of cured material. The metal layer is preferably formed by the aforementioned metal layer forming process.

[0672] That is, the method for manufacturing the laminate of the present invention preferably includes, between multiple methods for manufacturing cured products, a metal layer forming step in which a metal layer is formed on the layer composed of the cured product. The preferred embodiment of the metal layer forming step is as described above.

[0673] As an example of the aforementioned laminate, a preferred laminate may include at least the following layer structure, which is formed by sequentially stacking three layers: a first cured material layer, a metal layer, and a second cured material layer.

[0674] The layers formed by the first cured product and the layers formed by the second cured product are preferably both layers formed by the cured products of the present invention. The resin composition of the present invention used to form the layer formed by the first cured product and the resin composition of the present invention used to form the layer formed by the second cured product may be the same composition or may be different compositions. The metal layer in the laminate of the present invention can preferably be used as a metal wiring layer such as a rewiring layer.

[0675] (Layering process)

[0676] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0677] The lamination process includes a series of steps comprising performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step on the surface of a pattern (resin layer) or a metal layer. However, it may also be a process of repeatedly performing at least one of (a) the film formation step, (d) the heating step, and the post-development exposure step. Furthermore, (e) the metal layer formation step may be included after at least one of (d) the heating step and the post-development exposure step. The lamination process may, of course, further appropriately include the aforementioned drying step, etc.

[0678] When a further lamination process is performed after the lamination process, a surface activation treatment process can be performed after the aforementioned exposure process, the aforementioned heating process, or the aforementioned metal layer formation process. Plasma treatment can be cited as an example of a surface activation treatment. Details regarding surface activation treatment will be described later.

[0679] The above-mentioned lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0680] For example, as in the configuration of resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, the resin layer is preferably configured to have 2 or more layers and 20 or fewer layers, and more preferably configured to have 2 or more layers and 9 or fewer layers.

[0681] The composition, shape, and film thickness of each of the above layers can be the same or different.

[0682] In this invention, particularly after the metal layer is formed, it is preferable to further form a cured product (resin layer) of the resin composition of the present invention by covering the metal layer. Specifically, examples include repeating at least one of (a) a film forming step, (b) an exposure step, (c) a development step, (d) a heating step and a post-development exposure step, and (e) a metal layer forming step, or repeating at least one of (a) a film forming step, (d) a heating step and a post-development exposure step, and (e) a metal layer forming step. By alternately performing the lamination step of the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

[0683] (Surface activation treatment process)

[0684] The preferred method for manufacturing the laminate of the present invention includes a surface activation treatment step of surface activating at least a portion of the metal layer and the resin composition layer.

[0685] The surface activation treatment process is usually performed after the metal layer formation process, but it can also be performed after the development process (preferably after at least one of the heating process and the post-development exposure process) or after the surface activation treatment process of the resin composition layer.

[0686] The surface activation treatment can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. Preferably, the surface activation treatment is performed on at least a portion of the metal layer, and more preferably, on a portion or all of the region of the metal layer on which the resin composition layer is formed. Thus, by performing surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on that surface can be improved.

[0687] Preferably, part or all of the exposed resin composition layer (resin layer) is also surface-activated. In this way, by surface-activating the surface of the resin composition layer, the adhesion to the metal layer or resin layer disposed on the surface-activated surface can be improved. In particular, when the resin composition layer has been cured, such as in the case of negative development, it is less susceptible to damage caused by surface treatment, and adhesion is easily improved.

[0688] Regarding surface activation treatment, it can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0689] <Semiconductor Devices and Methods for Manufacturing Semiconductor Devices>

[0690] The present invention also discloses a semiconductor device comprising the cured material or laminate of the present invention.

[0691] Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product or the method for manufacturing a laminate of the present invention.

[0692] As a specific example of using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer in a semiconductor device, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description in FIG1, which are incorporated herein by reference.

[0693] Example

[0694] The following examples provide a more detailed description of the present invention. The materials, amounts, proportions, processing methods, and processing order shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" refer to mass measurements.

[0695] <Examples and Comparative Examples>

[0696] In each of the embodiments and comparative examples, the components described in Tables 2 to 10 below were mixed to obtain each resin composition.

[0697] Specifically, the content of each component other than the solvent recorded in Tables 2 to 10 is set as the amount (parts by mass) recorded in the "parts by mass" row.

[0698] When two or more compounds are used as resins, the columns for "Resin Structure," "Condensing Agent," "Mw (weight-average molecular weight) of Resin," "Imidification Rate (%)," and "Parts by Mass" are separated by " / ". The order in which these columns are separated by " / " corresponds accordingly. When two or more components other than resins are included, the amount of the component listed in the "Type" line is the "Parts by Mass" listed in the next line (i.e., the line immediately following the "Type" line).

[0699] The amount of solvent used is adjusted to match the solid component concentration recorded in the "Solid Component Concentration (mass%)" section of each table.

[0700] Each table lists the "type" and "proportion" of the solvents used. The "proportion" of a solvent is the content (mass %) of each type of solvent relative to the total solvent volume. When more than two solvents are included, the proportion of the solvent listed in the "type" row is the same as the proportion listed in the next row (i.e., the row immediately following the "type" row).

[0701] In each table, a "-" indicates that the resin composition does not contain the corresponding component.

[0702] The obtained resin composition was pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm.

[0703] The detailed information of each component recorded in each table is as follows.

[0704] [Resin]

[0705] The structure of the resins used is shown below (resin structure). Each resin contains a repeating unit enclosed in [ ]. For resins containing two repeating units, the content of each repeating unit (the molar percentage relative to all repeating units (mol%)) is indicated by a subscript to the right of its respective [ ].

[0706] In the structural formula of resin 3, R is a group represented by RX1 or RX2, and the molar ratio of RX1 / RX2 is 50 / 50. * indicates a bonding position.

[0707] The Mw and imidization rate of the resins used in each example and comparative example are described in Tables 2 to 10. Mw was determined by using a guard column SuperAW-H, TSKgel SuperAWM-H, and TSKgel SuperAWM-H (all manufactured by TOSOH CORPORATION) connected in series as a column. NMP (N-methyl-2-pyrrolidone) was used as the eluent for determination.

[0708] The resins used in Examples 57-60 and later were obtained by using carboxylic anhydrides and diamines corresponding to the described structures as raw materials, and by using the "condensing agents" listed in Tables 2-10 as activators for the amidation reaction. The DCC used as the condensing agent was dicyclohexylcarbodiimide. Furthermore, the SOCl2 used in Examples 39-43, 61, and 113 was thionyl chloride. SOCl2 is a halogenating agent rather than a condensing agent, but it is conveniently listed in the "condensing agent" column in Tables 2-10.

[0709] [Chemical Formula 24]

[0710]

[0711] [Chemical Formula 25]

[0712]

[0713] [Chemical Formula 26]

[0714]

[0715] [Chemical Formula 27]

[0716]

[0717] [Chemical Formula 28]

[0718]

[0719] [Chemical Formula 29]

[0720]

[0721] [Chemical Formula 30]

[0722]

[0723] [Chemical Formula 31]

[0724]

[0725] [Chemical Formula 32]

[0726]

[0727] [Chemical Formula 33]

[0728]

[0729] [Chemical Formula 34]

[0730]

[0731] [Chemical Formula 35]

[0732]

[0733] [Chemical Formula 36]

[0734]

[0735] [Chemical Formula 37]

[0736]

[0737] [Chemical Formula 38]

[0738]

[0739] [Chemical Formula 39]

[0740]

[0741] [Compound (A)]

[0742] The structure of the compound (A) used is shown below. The molecular weights of each compound are shown in Table 1 below.

[0743] [Chemical Formula 40]

[0744]

[0745] [Chemical Formula 41]

[0746]

[0747] [Table 1]

[0748]

[0749] Furthermore, the structures of the components other than those described above are shown below.

[0750] [Chemical Formula 42]

[0751]

[0752] [Chemical Formula 43]

[0753]

[0754] [Chemical Formula 44]

[0755]

[0756] [Chemical Formula 45]

[0757]

[0758] [Chemical Formula 46]

[0759]

[0760] [Chemical Formula 47]

[0761]

[0762] [Chemical Formula 48]

[0763]

[0764] “DPHA” stands for dipentaerythritol hexaacrylate (KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)).

[0765] “E-7” is an ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirodi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid.

[0766] "E-8" is a diazonoquinone compound synthesized by the following method.

[0767] <Synthesis of E-8>

[0768] 29.72 g (70 mmol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene) bisphenol (manufactured by Honshu Chemical Industry Co., Ltd.: Tris-PA) was added to a flask. Next, 46.93 g (174.9 mmol) of 1,2-diazonaphthoquinone-5-sulfonyl chloride and 17.9 g of triethylamine were dissolved in 300 g of acetone by stirring. The solution was then added dropwise to the flask over 30 minutes using a dropping funnel, and the mixture was stirred at an internal temperature of 30°C for 30 minutes. Hydrochloric acid was then added dropwise, and the mixture was stirred for another 30 minutes. Next, a solution of 1640 g of pure water and 30 g of hydrochloric acid was prepared in a beaker. The filtrate obtained by filtering the hydrochloride salt from the reaction solution was added dropwise to the solution. The precipitate was filtered, washed with water, and dried under vacuum at 40°C for 50 hours to obtain the diazononaphthoquinone compound (E-8).

[0769] [Solvent]

[0770] NMP: N-methyl-2-pyrrolidone

[0771] ·EL: Ethyl lactate

[0772] ·DMSO: Dimethyl sulfoxide

[0773] GBL: γ-Butyrolactone

[0774] GVL: γ-valerolactone

[0775] • MDMPA: 3-Methoxy-N,N-Dimethylpropionamide (KJCMPA-100 (manufactured by KJ Chemicals Corporation))

[0776] Toluene: Toluene

[0777] ·CP: Cyclopentanone

[0778] CH: Cyclohexanone

[0779] [Evaluation of drug resistance]

[0780] The resin compositions prepared in the various examples or comparative examples were coated onto a silicon wafer using a spin-coating method. The silicon wafer was then dried on a hot plate at 100°C for 5 minutes, thereby forming a resin composition layer of uniform thickness as described in the "Film Thickness (μm)" column of the table on the silicon wafer.

[0781] In the example where the exposure conditions are specified as "M", the resin composition layer on the silicon wafer was exposed using a stepper. Light of the wavelength listed in the "Exposure Wavelength (nm)" table was used, and the entire surface of the resin composition layer was exposed without a photomask. The exposure dose was set to 500 mJ / cm². 2 In the example where the exposure conditions are specified as "D", exposure was performed using a direct exposure apparatus (ADTEC DE-6UH III). The entire surface of the resin composition layer was exposed using light at the wavelengths specified in the "Exposure Wavelength (nm)" table. The exposure dose was set to 500 mJ / cm². 2 .

[0782] After the resin composition layer exposed under the above exposure conditions was left for 1 hour, the obtained wafer was spray-developed with cyclopentanone for 35 seconds, rinsed with a cyclopentanone / propylene glycol monomethyl ether acetate (PGMEA) mixture for 5 seconds, and then rinsed with PGMEA as a rinsing solution for 15 seconds.

[0783] Next, in the examples where a value is recorded in the "Curing Temperature (°C)" column, a heating plate was used to heat the resin film (resin composition layer) obtained in each embodiment or comparative example at a heating rate of 10°C / min under a nitrogen atmosphere. After reaching the temperature recorded in the "Curing Temperature (°C)" column, this temperature was maintained for the time (minutes) recorded in the "Curing Time (min)" column to form a cured film. In the examples where "IR" is recorded in the "Curing Temperature (°C)" column, an infrared lamp heating device (manufactured by ADVANCE RIKO, Inc., RTP-6) was used to heat the resin film obtained in each example at a heating rate of 10°C / min under a nitrogen atmosphere. After reaching 230°C, this temperature was maintained for the time (minutes) recorded in the "Curing Time (min)" column to form a cured film.

[0784] In the following pharmaceutical products, the obtained cured film was impregnated under the conditions described in the following evaluation conditions, and the dissolution rate was calculated.

[0785] Chemical: A mixture of dimethyl sulfoxide (DMSO) and a 25% (w / w) aqueous solution of tetramethylammonium hydroxide (TMAH) in a 90:10 (w / w) ratio.

[0786] Evaluation criteria: The cured film was immersed in the above-mentioned drug at 75°C for 15 minutes. The film thickness of the cured film before and after immersion was compared, and the dissolution rate (nm / min) was calculated.

[0787] The obtained dissolution rate values ​​were evaluated according to the following criteria, and the evaluation results were recorded in the "Drug Resistance" column. Generally speaking, the lower the dissolution rate, the better the drug resistance.

[0788] -Evaluation Criteria-

[0789] A: The dissolution rate is less than 250 nm / min.

[0790] B: The dissolution rate is above 250 nm / min and less than 500 nm / min.

[0791] C: The dissolution rate is above 500 nm / min and less than 750 nm / min.

[0792] D: The dissolution rate is above 750 nm / min.

[0793]

[0794]

[0795]

[0796]

[0797]

[0798]

[0799]

[0800]

[0801]

[0802] The results above show that the cured film made of the resin composition of the present invention has excellent chemical resistance.

[0803] <Example 101>

[0804] The resin composition used in Example 5 was spin-coated onto the copper layer surface of a resin substrate on which a copper layer was formed. After drying at 100°C for 4 minutes to form a 20 μm thick film, exposure was performed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm using a mask (a binary mask with a 1:1 line-to-gap pattern and a linewidth of 10 μm). After exposure, the film was heated at 100°C for 4 minutes. Following the heating, the film was developed in cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern.

[0805] Next, under nitrogen atmosphere, the temperature was increased at a rate of 10°C / min, and after reaching 230°C, it was maintained at 230°C for 3 hours, thereby forming an interlayer insulating film for the rewiring layer. This interlayer insulating film for the rewiring layer exhibits excellent insulation properties.

[0806] Furthermore, semiconductor devices were fabricated using these rewiring layers with interlayer insulating films, and as a result, they were confirmed to operate without any problems.

[0807] Industrial availability

[0808] According to the present invention, a resin composition capable of forming a film with excellent chemical resistance and a method for manufacturing an interlayer insulating film for a rewiring layer using the above-described resin composition are provided.

[0809] The present invention has been described in detail with reference to specific embodiments, but it will be apparent to those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the invention.

[0810] This application is based on Japanese Patent Application No. 2023-139970, filed on August 30, 2023, the contents of which are incorporated herein by reference.

Claims

1. A resin composition comprising: at least one resin selected from the group consisting of polyimides and polyimide precursors; and a compound (A) represented by the following formula (a1). In equation (a1), R 1 R represents an organic group. 2 and R 3 Each can independently represent a hydrogen atom or an organic group, R 1 R 2 and R 3 Any two of them can be optionally bonded to form a ring.

2. The resin composition according to claim 1, wherein, R in equation (a1) 1 It represents an aromatic group.

3. The resin composition according to claim 1, wherein, R in equation (a1) 1 R represents an aromatic group having a phenolic hydroxyl group. 2 and R 3 Each organic group can be represented independently.

4. The resin composition according to claim 1, further comprising a photopolymerization initiator and a polymerizable compound.

5. The resin composition according to claim 1, further comprising an organometallic compound.

6. The resin composition according to claim 1, further comprising a urea compound.

7. The resin composition according to claim 1, further comprising a solvent having at least one of an amide group and a hydroxyl group.

8. The resin composition according to claim 1, wherein, The content of compound (A) contained in the resin composition is 0.0001% by mass or more and 10.0% by mass or less relative to the total solids content of the resin composition.

9. The resin composition according to claim 1, wherein, The content of compound (A) contained in the resin composition is 0.0001% by mass or more and 15.0% by mass or less, relative to the resin.

10. The resin composition according to claim 1, used for forming an insulating film for a rewiring layer.

11. A method for manufacturing an interlayer insulating film for a rewiring layer, comprising: The photosensitive film forming process involves coating a substrate with the resin composition according to any one of claims 1 to 10 to form a photosensitive film; The exposure process involves exposing the photosensitive film to form an exposed film; and In the pattern forming process, the exposed film is developed with a developing solution to form an insulating pattern.

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