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

Abstract

The present invention provides a resin composition, a cured product obtained by curing the resin composition, a laminate comprising the cured product, a method for producing the cured product, and a method for producing the laminate. A method for manufacturing a semiconductor device including a method for manufacturing a cured product, a semiconductor device including the cured product, and a diamine compound having a specific structure, the resin composition containing: a resin that contains a specific repeating unit, contains a group having an ethylenically unsaturated bond, and has a phenolic hydroxyl group content of 0.250 mmol / g or less; and a polymerizable compound having an ethylenically unsaturated bond.

Description

Technical Field

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

[0002] Today, resin materials made from resin compositions containing resins are being used in a wide variety of fields.

[0003] For example, cyclized resins such as polyimide have excellent heat resistance and insulation properties, and are therefore used in a wide variety of applications. There are no particular limitations to these applications; for example, in mounting semiconductor devices, they can be used as insulating films, sealing materials, or protective films. Furthermore, they can also be used as base films or cover films for flexible substrates.

[0004] For example, in the above-described applications, cyclized resins such as polyimide are used in the form of resin compositions containing cyclized resins.

[0005] This resin composition is applied to a substrate, for example, by coating, to form a photosensitive film, which is then exposed, developed, heated, etc., as needed, thereby forming a cured product on the substrate.

[0006] The resin composition can be applied using known coating methods, thus exhibiting excellent manufacturing adaptability. For example, the applicable resin composition offers a high degree of design freedom in terms of shape, size, and application location. Considering this excellent manufacturing adaptability, in addition to the high performance of polyimide, there is growing anticipation for the expansion of industrial applications of the aforementioned resin composition.

[0007] For example, Patent Document 1 describes a photosensitive polyimide siloxane and a composition containing the photosensitive polyimide siloxane, wherein the photosensitive polyimide siloxane is characterized by being polymerized and imidized by (a) 85-99 mol% of a diamine compound having at least two or more photosensitive groups and (b) 15-1 mol% of a diamino polysiloxane having a specific structure and (c) a tetracarboxylic dianhydride having a specific structure.

[0008] Patent Document 2 describes a negative photosensitive resin composition containing (A) a polyimide having double bonds on its side chain, (B) a crosslinking agent comprising a (meth)acrylate compound having a fluorene backbone, and (C) a polymerization initiator.

[0009] Previous technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Publication No. 2006-083307

[0012] Patent Document 2: Japanese Patent Application Publication No. 2022-135427 Summary of the Invention

[0013] The technical problem to be solved by the invention

[0014] For cured products obtained from resin compositions, it is required that they maintain insulation over a long period of time. In this invention, the ability to maintain adhesion over a long period of time is also referred to as "excellent reliability".

[0015] The present invention aims to provide a resin composition that yields a cured product with excellent reliability, a cured product obtained by curing the above composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product.

[0016] Furthermore, the purpose of this invention is to provide a novel diamine compound.

[0017] means for solving technical problems

[0018] The following are examples of representative embodiments of the present invention.

[0019] <1> A resin composition comprising:

[0020] A resin comprising repeating units represented by formula (1-1), including groups having olefinic unsaturated bonds, and having a phenolic hydroxyl content of 0.250 mmol / g or less; and

[0021] Polymers that have olefinic unsaturated bonds.

[0022] [Chemical Formula 1]

[0023]

[0024] In equation (1-1), X 1 Y represents a tetravalent organic group. 1 This indicates a divalent organic group.

[0025] <2> according to <1> The resin composition, wherein,

[0026] The resin described above is a resin that contains repeating units represented by the formula (1-2) as repeating units represented by the formula (1-1).

[0027] [Chemical Formula 2]

[0028]

[0029] In equation (1-2), X 1 Y represents a tetravalent organic group. 2 This refers to a group that contains the group represented by the following formula (2-1).

[0030] [Chemical Formula 3]

[0031]

[0032] In equation (2-1), R 1 and R 2 Each group independently represents a group with an olefinic unsaturated bond, L represents a single bond or a divalent linking group that does not contain an imide bond, and * represents a bonding site with other structures.

[0033] <3> according to <1> or <2> The resin composition, wherein,

[0034] The resin described above contains a vinylphenyl group as a group having an olefinic unsaturated bond.

[0035] <4> A resin composition comprising:

[0036] A resin comprising repeating units represented by formulas (1-3) below and comprising vinylphenyl; and

[0037] Polymers that have olefinic unsaturated bonds.

[0038] [Chemical Formula 4]

[0039]

[0040] In equation (1-3), X 1 Y represents a tetravalent organic group. 3 This refers to a group that contains the group represented by the following formula (2-2).

[0041] [Chemical Formula 5]

[0042]

[0043] In equation (2-2), R 1 and R 2 Each group independently represents a group with an olefinic unsaturated bond, L represents a single bond, -C(CH3)2- or -C(CF3)2-, and * represents the bonding site with other structures.

[0044] <5> according to <1> to <4> The resin composition described in any one of the following statements, wherein,

[0045] The above-mentioned resin has a structure represented by any of the following formulas (3-1) to (3-3).

[0046] [Chemical Formula 6]

[0047]

[0048] In equation (3-1), X 31 Y represents a tetravalent organic group. 31 R represents a divalent organic group. 31 The symbol indicates a group with an olefinic unsaturated bond, and * indicates a bonding site with other structures.

[0049] In equation (3-2), X 31 Y represents a tetravalent organic group. 31 R represents a divalent organic group. 31 The symbol indicates a group with an olefinic unsaturated bond, and * indicates a bonding site with other structures.

[0050] In equation (3-3), X 31 Y represents a tetravalent organic group. 31 R represents a divalent organic group. 32 and R 33 R represents an organic group that is either -OH or monovalent, respectively. 32 and R 33 At least one of them is a group with an olefinic unsaturated bond, and * indicates a bonding site with other structures.

[0051] <6> according to <1> to <5> The resin composition described in any one of the following statements, wherein,

[0052] The resin mentioned above is a resin in which the change rate of the imide group value calculated by the following formula is less than 25% before and after heating at 350°C and 1 atmosphere for 1 hour.

[0053] Change rate (%) = (Im2 - Im1) × 100 / Im1

[0054] Im1: Imine group value before heating (mmol / g)

[0055] Im2: Imine group value (mmol / g) after heating at 350℃ and 1 atm for 1 hour.

[0056] <7> according to <1> to <6> The resin composition described in any one of the following statements, wherein,

[0057] The above X 1 An organic group having a structure formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-4).

[0058] [Chemical Formula 7]

[0059]

[0060] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0061] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0062] <8> according to <1> to <7> The resin composition described in any one of the following statements contains an azole compound.

[0063] <9> A diamine compound, represented by the following formula (4-1).

[0064] [Chemical Formula 8]

[0065]

[0066] In equation (4-1), R 3 and R 4 Each group independently represents a group having an olefinic unsaturated bond, R 3 and R 4 At least one of them has an aromatic hydrocarbon group, where L represents a single bond, -C(CH3)2- or -C(CF3)2-.

[0067] <10> according to <9> The diamine compound, wherein,

[0068] The above R 3 and R 4 Each has a vinylphenyl group independently.

[0069] <11> A resin composition comprising:

[0070] Resin, which is <9> or <10> The reaction products of the diamine compound with a compound or its derivative having a total of two or more carboxyl groups and carboxylic anhydride groups; and

[0071] Polymers that have olefinic unsaturated bonds.

[0072] <12> according to <1> ~ <11> The resin composition described in any one of the following is used to form an interlayer insulating film for a rewiring layer.

[0073] <13> A solidified substance, which is... <1> to <12> It is formed by curing the resin composition described in any one of the above statements.

[0074] <14> A laminate containing two or more layers of material. <13> The cured material forms a layer, and a metal layer is included between any layers formed by the cured material.

[0075] <15> A method for manufacturing a cured material, comprising: <1> to <12> The resin composition described in any one of the above statements is suitable for a film forming process in which a film is formed on a substrate.

[0076] <16> according to <15> The method for manufacturing the solidified material includes:

[0077] The exposure process selectively exposes the aforementioned film; and

[0078] In the developing process, the above film is developed using a developing solution to form a pattern.

[0079] <17> according to <15> or <16> The method for manufacturing the cured material includes a heating step of heating the film at 50 to 450°C.

[0080] <18> A method for manufacturing a laminate, comprising: <15> to <17> The method for manufacturing the cured product as described in any one of the above.

[0081] <19> A method for manufacturing a semiconductor device, comprising: <15> to <17> The method for manufacturing the cured product as described in any one of the above.

[0082] <20> A semiconductor device comprising <13> The solidified product mentioned above.

[0083] Invention Effects

[0084] According to the present invention, a resin composition that yields a cured product with excellent reliability is provided, a cured product obtained by curing the above composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product are provided.

[0085] Furthermore, according to the present invention, a novel diamine compound is provided. Detailed Implementation

[0086] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0087] In this specification, the numerical range represented by the symbol “~” refers to the range including the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0088] In this specification, the term "process" refers not only to independent processes, but also to processes that cannot be clearly distinguished from other processes as long as they can achieve the intended function of the process.

[0089] In the designation of groups (atomic groups) in this specification, the designations without substitution and without substitution include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0090] In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and activated light or radiation such as electron beams.

[0091] In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either one; “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid” or either one; and “(meth)acryloyl” means “acryloyl” and “methacryloyl” or either one.

[0092] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0093] 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 refers to the mass percentage of components other than the solvent relative to the total mass of the composition.

[0094] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined by gel permeation chromatography (GPC) and are defined as polystyrene conversion values. In this specification, for example, an HLC-8220 GPC (manufactured by TOSOH CORPORATION) is used, with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series as a column, from which the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined. Unless otherwise specified, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. In cases where THF is unsuitable as an eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, the detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm.

[0095] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer among the layers of interest. That is, a third layer or element may be further interposed between the reference layer and the other layers, and the reference layer does not need 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, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." In addition, this setting of up and down directions is for the convenience of explaining this specification; in practice, the "upper" direction in this specification may also differ from the vertically upward direction.

[0096] 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.

[0097] 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.

[0098] In this specification, the preferred combination of methods is a more preferred method.

[0099] (Resin Composition)

[0100] The resin composition according to the first aspect of the present invention (hereinafter also simply referred to as the "first resin composition") comprises: a resin containing repeating units represented by formula (1-1), containing groups having olefinic unsaturated bonds, and having a phenolic hydroxyl content of 0.250 mmol / g or less; and a polymerizable compound having olefinic unsaturated bonds.

[0101] The resin composition according to the second aspect of the present invention (hereinafter also simply referred to as the "second resin composition") comprises: a resin containing repeating units represented by formulas (1-3) and containing vinylphenyl; and a polymerizable compound having olefinic unsaturated bonds.

[0102] The resin composition according to the third aspect of the present invention (hereinafter also simply referred to as the "third resin composition") comprises: a resin, which is a reaction product of a diamine compound represented by formula (4-1) and a compound having a total of two or more carboxyl groups and carboxylic anhydride groups; and a polymerizable compound having olefinic unsaturated bonds.

[0103] Hereinafter, the first resin composition, the second resin composition, and the third resin composition will also be collectively referred to as "resin compositions".

[0104] Hereinafter, the resin contained in the first resin composition, which includes the repeating unit represented by formula (1-1), contains groups having olefinic unsaturated bonds, and has a content of phenolic hydroxyl groups of 0.250 mmol / g or less, is also referred to as the "first specific resin".

[0105] Hereinafter, the resin contained in the second resin composition, which includes repeating units represented by formulas (1-3) and contains vinylphenyl, is also referred to as the "second specific resin".

[0106] Hereinafter, the resin containing the diamine compound represented by formula (4-1) in the third resin composition and the compound having a total of two or more carboxyl groups and carboxylic anhydride groups is also referred to as the "third specific resin".

[0107] Hereinafter, when simply referred to as "specific resin", it refers to all of the first specific resin, the second specific resin, and the third specific resin.

[0108] 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.

[0109] The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form insulating components.

[0110] An insulating component is a component formed between parts for the purpose of insulating them from electrical conductivity, such as in wiring. The volume resistivity of the insulating component is preferably 1×10⁻⁶. 8 Ω·cm or more, more preferably 1×10 10 Ω·cm or higher, and more preferably 1×10 12 Ω·cm or higher.

[0111] In particular, using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer is also one of the preferred embodiments of the present invention.

[0112] Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative development.

[0113] In this invention, negative development refers to development in which non-exposed areas are removed by development during exposure and development, while positive development refers to development in which exposed areas are removed by development.

[0114] As the above-described exposure method, developer, and developing method, for example, the exposure method described in the exposure step of the description of the method for manufacturing cured material described later, and the developer and developing method described in the developing step can be used.

[0115] The resin composition according to the present invention yields cured products with excellent reliability.

[0116] The mechanism by which these effects are achieved is not yet clear, but the following is a hypothesis.

[0117] The resin composition involved in the first method contains a small amount of phenolic hydroxyl groups.

[0118] It is believed that the resin in the resin composition involved in the second method contains vinylphenyl, which has low mobility compared to polymerizable groups such as acryloyloxy. Therefore, even if L in formula (2-2) is a short structure, it can be easily introduced into the adjacent structure.

[0119] It is believed that the resin composition involved in the third approach uses a specific diamine, thereby reducing the content of phenolic hydroxyl groups in the resin compared to the case where polymerizable groups are introduced after the phenolic hydroxyl groups derived from the structure of a diamine having phenolic hydroxyl groups.

[0120] The reason for achieving excellent reliability by using these resins is uncertain, but it can be speculated that the low content of phenolic hydroxyl groups in the resin inhibits the presence of sites where the movement of groups with olefinic unsaturated bonds in the resin is hindered by the phenolic hydroxyl groups, and the polymerization of groups with olefinic unsaturated bonds in the phenolic hydroxyl groups is hindered due to the polymerization inhibition effect of the phenolic hydroxyl groups.

[0121] As a result, it is believed that polymerization occurs in a nearly uniform state in the film formed from the resin composition, and that there are fewer unpolymerized sites of phenolic hydroxyl groups in the cured product obtained after polymerization.

[0122] That is, it is believed that the cured product obtained from the resin composition of the present invention can suppress the penetration of water and the like from such unpolymerized areas, thus resulting in excellent reliability.

[0123] Furthermore, it is believed that by reducing the unpolymerized portions, the elongation at break of the obtained cured product is improved.

[0124] Furthermore, by using resins with specific structures, it is possible to reduce the dielectric loss tangent of the obtained cured product.

[0125] Furthermore, sometimes by having a low content of phenolic hydroxyl groups in the resin, it is also possible to improve the chemical resistance of the obtained cured product and improve the developability of the film formed from the resin composition during exposure and development.

[0126] Here, no resin composition corresponding to the resin composition of the present invention is described in Patent Documents 1 and 2.

[0127] The following is a detailed description of the components contained in this invention.

[0128] <Specific Resin>

[0129] The first specific resin and the second specific resin are preferably polyimide resins.

[0130] Polyimide resin refers to a resin containing multiple repeating units with imide bonds.

[0131] In this invention, the imide bond is represented by the structure -C(=O)N(-*)C(=O)-. * indicates the bonding site with other structures.

[0132] Furthermore, the polyimide resin is preferably a resin having imide bonds in its main chain structure, and more preferably a resin containing an imide ring structure in its main chain structure. An imide ring structure refers to a ring structure in which all two carbon atoms and one nitrogen atom of the imide bond serve as ring-forming atoms. The imide ring structure is preferably a five-membered ring structure.

[0133] In this invention, "main chain" refers to the longest bonded chain in the resin molecule, and "side chain" refers to the bonded chain other than the main chain.

[0134] Furthermore, the third specific resin is preferably a polyimide resin, a polyamide resin, or a polyamide-imide resin, more preferably a polyimide resin.

[0135] Polyamide resin refers to a resin containing multiple repeating units with amide bonds.

[0136] In this invention, the amide bond is *-NR. N The key represented by -C(=O)-*, R N Represents a hydrogen atom or a monovalent organic group; * indicates the bonding site with a carbon atom, respectively. R N Preferably, it is a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom.

[0137] Polyamide-imide resin refers to a resin containing multiple repeating units with imide and amide bonds.

[0138] [Content of phenolic hydroxyl groups]

[0139] The content of phenolic hydroxyl groups in the first specific resin is less than 0.250 mmol / g.

[0140] The content of phenolic hydroxyl groups in the second and third specific resins is preferably 0.250 mmol / g or less.

[0141] In this invention, a phenolic hydroxyl group refers to a hydroxyl group that is bonded to an aromatic ring structure by a single bond without a linking group. The aforementioned aromatic ring structure can be an aromatic hydrocarbon ring structure or an aromatic heterocyclic structure.

[0142] The content of phenolic hydroxyl groups in a particular resin is preferably 0.200 mmol / g or less, more preferably 0.180 mmol / g or less, even more preferably 0.150 mmol / g or less, and especially preferably 0.120 mmol / g or less.

[0143] Here, there is no particular limitation on the lower limit of the content of the above-mentioned phenolic hydroxyl groups, which can be 0 mmol / g (i.e., below the quantitative limit).

[0144] The content of the aforementioned phenolic hydroxyl groups can be determined by the amount of resin passing through a specific flow rate relative to 1 mole of resin. 1 The amount of phenolic hydroxyl groups (mmol) measured by H-NMR is calculated by dividing by the number-average molecular weight of the resin.

[0145] The amount (mmol) of the aforementioned phenolic hydroxyl groups can be calculated using known quantitative NMR.

[0146] Specifically, the measurement can be performed under the following conditions.

[0147] -Determination Conditions-

[0148] · 1 H-NMR (BRUKER, AVANCE NEO 400)

[0149] • Analysis software: TopSpin 4.0.7

[0150] Solvent: DMSO-d6

[0151] Internal standard: 1,3,5-trimethoxybenzene

[0152] exist 1 In ¹H NMR, the protons of the phenolic hydroxyl groups were detected by a specific peak near δ(DMSO-d6) = 10 ppm. Furthermore, 1,3,5-trimethoxybenzene, serving as an internal standard, was detected by a specific peak at 6.1 ppm.

[0153] The above number-average molecular weights were obtained as conversion values ​​for polystyrene determined by gel permeation chromatography (GPC).

[0154] Furthermore, in cases where the above determination is difficult to perform, the following calculation can be made: after determining the acid value of the resin (mgKOH / g) by acid value titration, the above acid value is converted to mol / g, and the proportion of phenolic hydroxyl groups in the acid groups contained in a specific resin is quantified by NMR, and the above acid value is accumulated.

[0155] In acid value titration, the neutralization point can be distinguished and detected because of the difference between carboxylic acids and pKa.

[0156] [Groups containing olefinic unsaturated bonds]

[0157] The first specific resin contains groups having olefinically unsaturated bonds.

[0158] The first specific resin may contain groups having olefinic unsaturated bonds in any part of the resin. These groups are preferably contained in the repeating units represented by formula (1-1), and more preferably in the Y group within the repeating units represented by formula (1-1). 1 middle.

[0159] As a group having an olefinic unsaturated bond, examples include groups comprising at least one group selected from the group consisting of vinyl, allyl, isoallyl, 2-methylallyl, a group having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, and (meth)acryloyloxy.

[0160] In this invention, direct bonding of one structure to another means that one structure is bonded to another without a linking group.

[0161] From a reactivity point of view, the first specific resin preferably contains a group having an olefinic unsaturated bond, which is preferably a group having at least one group selected from the group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, and a (meth)acryloyloxy group.

[0162] From the viewpoint of reducing dielectric loss tangent, in the first specific resin, the group having an olefinic unsaturated bond is preferably a group having an aromatic ring directly bonded to a vinyl group, and more preferably a group having a vinylphenyl group.

[0163] The content of groups with olefinic unsaturated bonds in a specific resin is preferably 0.1 to 3.0 mmol / g, more preferably 0.15 to 2.75 mmol / g, and even more preferably 0.2 to 2.5 mmol / g.

[0164] Furthermore, when a particular resin contains vinylphenyl, the content of vinylphenyl in the particular resin is preferably 0.1 to 3.0 mmol / g, more preferably 0.15 to 2.75 mmol / g, and even more preferably 0.2 to 2.5 mmol / g.

[0165] [The repeating unit represented by equation (1-1)]

[0166] The first specific resin includes the repeating unit represented by formula (1-1).

[0167] The third specific resin is preferably a repeating unit represented by formula (1-1). In this case, X in formula (1-1) 1 Y is derived from the structure of a specific carboxylic acid compound described later. 1 The structure of the diamine compound derived from this invention is shown.

[0168] [Chemical Formula 9]

[0169]

[0170] In equation (1-1), X 1 Y represents a tetravalent organic group. 1 This indicates a divalent organic group.

[0171] -X 1 -

[0172] In equation (1-1), X 1 Preferably, it represents an organic group containing a structure formed by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-9), and more preferably, it represents an organic group containing a structure formed by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-4).

[0173] The chemical resistance and flatness of the cured material are improved by using an organic group containing a structure formed by removing two or more hydrogen atoms from the structure represented by any of the formulas (V-1) to (V-9).

[0174] Here, by using an organic group containing a structure formed by removing two or more hydrogen atoms from the structure represented by any of formulas (V-1) to (V-4), effects such as suppressing the generation of developing residue, reducing the dielectric constant of the cured product, and decreasing the coefficient of thermal expansion can also be obtained.

[0175] Here, by using an organic group containing a structure formed by removing two or more hydrogen atoms from the structure represented by any of formulas (V-5) to (V-9), it is also possible to obtain effects such as making the pattern of the cured material less likely to become conical and having a wide tolerance for exposure by improving the transmittance of ultraviolet light.

[0176] [Chemical Formula 10]

[0177]

[0178] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0179] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0180] In equation (V-7), R X5 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0181] In equation (V-2), R X1 Each of the components is preferably an alkyl or haloalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom. The halogen atom is preferably F or Cl, more preferably F.

[0182] In equation (V-3), R X2 and R X3 Hydrogen atoms are preferred individually.

[0183] R X2 With R X3 In the case of bonding to form a ring structure, R X2 With R X3 The structure formed by bonding is preferably a single bond, -O- or -C(R)2-, more preferably -O- or -C(R)2-, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, alkyl or aryl, and even more preferably a hydrogen atom.

[0184] In equation (V-7), RX5 Each of the components is preferably an alkyl or haloalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom. The halogen atom is preferably F or Cl, more preferably F.

[0185] In X 1 In the case of a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), X 1 Preferably, it is a group represented by the following formula (V-1-1). In the following formula, * represents X in formula (1-1). 1 In the bonding sites of the four carbonyl groups, n1 represents an integer from 0 to 5, and is preferably an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0186] [Chemical Formula 11]

[0187]

[0188] In X 1 In the case of a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), X 1 Preferably, the group represented by formula (V-2-1) or formula (V-2-2) is preferred. From the viewpoint of reducing the amine value in the resin, the group represented by formula (V-2-2) is preferred. In this specification, the bond that crosses the edge of the ring structure refers to any one of the hydrogen atoms that replaces the ring structure. In the following formula, L X1 The asterisk (*) represents a single bond or -O-, and the asterisk (*) represents the X in equation (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, R X1 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0189] [Chemical Formula 12]

[0190]

[0191] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), X 1 Preferably, the group represented by formula (V-3-1) or formula (V-3-2) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-2) is preferred. In the following formulas, * represents X in formula (1-1). 1The bonding sites of the four carbonyl groups. Furthermore, R X2 and R X3 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0192] [Chemical Formula 13]

[0193]

[0194] In X 1 In the case of a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), X 1 Preferably, it is a group represented by the following formula (V-4-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups are denoted by n1, which is an integer from 0 to 5. Furthermore, the hydrogen atoms in the structure described below can be further substituted with known substituents such as hydrocarbon groups. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) are substituted.

[0195] [Chemical Formula 14]

[0196]

[0197] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-5), X 1 Preferably, it is a group represented by the following formula (V-5-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0198] [Chemical Formula 15]

[0199]

[0200] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-6), X 1 Preferably, it is a group represented by the following formula (V-6-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0201] [Chemical Formula 16]

[0202]

[0203] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-7), X 1 Preferably, it is a group represented by the following formula (V-7-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0204] [Chemical Formula 17]

[0205]

[0206] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-8), X 1 Preferably, it is a group represented by the following formula (V-8-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0207] [Chemical Formula 18]

[0208]

[0209] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-9), X 1 Preferably, it is a group represented by the following formula (V-9-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0210] [Chemical Formula 19]

[0211]

[0212] In addition, X 1 It can be the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic acid dianhydride as described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0213] And, X 1 Preferably, the structure does not contain imide bonds.

[0214] And, X 1 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0215] In this invention, the carbamate bond is *-OC(=O)-NR. N -* represents the key, R N Represents a hydrogen atom or a monovalent organic group; * indicates the bonding site with a carbon atom, respectively. R N The preferred method is as described above.

[0216] 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 * indicates a bonding site with a carbon atom. R N The preferred method is as described above.

[0217] Additionally, X 1 Preferably, the structure does not contain ester bonds.

[0218] In this invention, the ester bond is represented by the bond represented by *-OC(=O)-*.

[0219] Among these, X 1 Preferably, it is free of imide bonds, urethane bonds, urea bonds and amide bonds, and more preferably, it is free of imide bonds, urethane bonds, urea bonds, amide bonds and ester bonds.

[0220] -Y 1 -

[0221] In equation (1-1), Y 1 Preferably, it is a group containing a group represented by formula (2-1), and more preferably, it is a group represented by formula (2-1).

[0222] [Chemical Formula 20]

[0223]

[0224] In equation (2-1), R 1 and R 2 Each group independently represents a group with an olefinic unsaturated bond, L represents a single bond or a divalent linking group that does not contain an imide bond, and * represents a bonding site with other structures.

[0225] In equation (2-1), R 1 and R 2 Each group is preferably represented by the group indicated by the following formula (R1-1).

[0226] [Chemical Formula 21]

[0227]

[0228] In equation (R1-1), L R1 R represents the linking group with an n+1 valence. R1 Each of these groups independently represents an aromatic group, (meth)acryloyloxy group, or (meth)acrylamide group that is directly bonded to a vinyl group, where n represents an integer from 1 to 10, and * represents the bonding site with the oxygen atom in formula (2-1).

[0229] R R1 Each of the aromatic groups is preferably directly bonded to the vinyl group, and more preferably vinylphenyl.

[0230] L R1 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by the bonding of at least one group in the group, preferably a hydrocarbon group or * 1 -C(=O)NR N -L R2 -* 2 The group to be represented.

[0231] The hydrocarbon group is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0232] The above R N The preferred method is as described above.

[0233] The above* 1 The meaning of * is the same as the meaning of * in equation (R1-1). 2 R represents the expression (R1-1) R1 The bonding sites.

[0234] Furthermore, in R R1 In the case of vinylphenyl, L R1 Preferably, it is an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group.

[0235] In R R1 In the case of (meth)acryloyloxy or (meth)acrylamide, L R1 Preferred* 1 -C(=O)NR N -L R2 -* 2 The group represented.

[0236] n is preferably an integer from 1 to 4, more preferably 1 or 2, and more preferably 1.

[0237] In formula (2-1), L is preferably a single bond, -C(CH3)2-, -C(CF3)2-, -S(=O)2-, or 9,9-fluorenyldiyl. Furthermore, L being a single bond, -C(CH3)2-, or -C(CF3)2- is also a preferred embodiment of the present invention.

[0238] Furthermore, in equation (1-1), Y 1 It can be a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-9).

[0239] The chemical resistance and flatness of the cured material are improved by using an organic group containing a structure formed by removing two or more hydrogen atoms from the structure represented by any of the formulas (V-1) to (V-9).

[0240] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), Y 1 Preferably, it is a group represented by the following formula (V-1-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms are denoted by n1, which is an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0241] [Chemical Formula 22]

[0242]

[0243] In Y 1 In the case where Y contains a group that forms a structure by removing two or more hydrogen atoms from the structure represented by formula (V-2), 1 Preferably, the group represented by formula (V-2-3) or formula (V-2-4) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-2-4) is preferred. In the following formula, L X1 Indicates a single bond or -O-, * indicates a Y in equation (1-1) 1 The bonding sites of the two nitrogen atoms. Furthermore, R X1 The preferred configuration is as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0244] [Chemical Formula 23]

[0245]

[0246] In Y 1In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), Y 1 Preferably, the group represented by formula (V-3-3) or formula (V-3-4) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-3) is preferred. In the following formulas, * represents Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0247] [Chemical Formula 24]

[0248]

[0249] In Y 1 In the case of a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), Y 1 Preferably, it is a group represented by the following formula (V-4-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms are represented by n1, which is an integer from 0 to 5. Furthermore, n1 being 0 is also one of the preferred embodiments of the present invention. Additionally, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0250] [Chemical Formula 25]

[0251]

[0252] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-5), Y 1 Preferably, it is a group represented by the following formula (V-5-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0253] [Chemical Formula 26]

[0254]

[0255] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-6), Y 1 Preferably, it is a group represented by the following formula (V-6-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0256] [Chemical Formula 27]

[0257]

[0258] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-7), Y 1 Preferably, it is a group represented by the following formula (V-7-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0259] [Chemical Formula 28]

[0260]

[0261] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-8), Y 1 Preferably, it is a group represented by the following formula (V-8-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0262] [Chemical Formula 29]

[0263]

[0264] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-9), Y 1 Preferably, it is a group represented by the following formula (V-9-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0265] [Chemical Formula 30]

[0266]

[0267] In addition, Y 1 It can be the group described in paragraphs 0042 to 0053 of Japanese Patent Application Publication No. 2023-003421.

[0268] Furthermore, Y 1 Preferably, the structure does not contain imide bonds.

[0269] Furthermore, Y 1 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0270] In addition, Y 1 Preferably, the structure does not contain ester bonds.

[0271] Among these, Y 1 Preferably, it is free of imide bonds, urethane bonds, urea bonds and amide bonds, and more preferably, it is free of imide bonds, urethane bonds, urea bonds, amide bonds and ester bonds.

[0272] [The repeating unit represented by equation (1-2)]

[0273] The first specific resin is preferably a repeating unit represented by the following formula (1-2) as the repeating unit represented by formula (1-1).

[0274] The third specific resin is preferably a repeating unit represented by formula (1-2). In this case, X in formula (1-2) 1 Y is derived from the structure of a specific carboxylic acid compound described later. 2 The structure of the diamine compound derived from this invention is shown.

[0275] [Chemical Formula 31]

[0276]

[0277] In equation (1-2), X 1 Y represents a tetravalent organic group. 2 A group that includes the group represented by formula (2-1).

[0278] In equation (1-2), X 1 The preferred method is the same as X in the above formula (1-1). 1 The preferred method is the same.

[0279] In equation (1-2), Y 2 The preferred manner of the group represented by the included formula (2-1) is the same as that of Y in the above formula (1-1). 1 The preferred mode of the group represented by the included formula (2-1) is the same.

[0280] [The repeating unit represented by equation (1-3)]

[0281] The second resin composition comprises repeating units represented by the following formulas (1-3).

[0282] [Chemical Formula 32]

[0283]

[0284] In equation (1-3), X 1 Y represents a tetravalent organic group. 3 This refers to a group that contains the group represented by the following formula (2-2).

[0285] [Chemical Formula 33]

[0286]

[0287] In equation (2-2), R 1 and R 2 Each group independently represents a group with an olefinic unsaturated bond, L represents a single bond, -C(CH3)2- or -C(CF3)2-, and * represents the bonding site with other structures.

[0288] In equation (1-3), X 1 The preferred method is the same as X in equation (1-1) 1 The preferred method is the same.

[0289] In equation (2-2), R 1 and R 2 The preferred method is the same as R in equation (2-1) 1 and R 2 The preferred method is the same.

[0290] [The structures represented by equations (3-1) to (3-3)]

[0291] The specific resin is preferably a structure represented by any of the following formulas (3-1) to (3-3).

[0292] [Chemical Formula 34]

[0293]

[0294] In equation (3-1), X 31 Y represents a tetravalent organic group. 31 R represents a divalent organic group. 31 The symbol indicates a group with an olefinic unsaturated bond, and * indicates a bonding site with other structures.

[0295] In equation (3-2), X 31 Y represents a tetravalent organic group. 31 R represents a divalent organic group. 31 The symbol indicates a group with an olefinic unsaturated bond, and * indicates a bonding site with other structures.

[0296] In equation (3-3), X 31Y represents a tetravalent organic group. 31 R represents a divalent organic group. 32 and R 33 R represents an organic group that is either -OH or monovalent, respectively. 32 and R 33 At least one of them is a group with an olefinic unsaturated bond, and * indicates a bonding site with other structures.

[0297] In equations (3-1) to (3-3), X 31 and Y 31 The preferred method is the same as X in the above formula (1-1). 1 and Y 1 The preferred method is the same.

[0298] In equations (3-1) to (3-3), R 31 ~R 33 Preferably, it contains a group having an olefinic unsaturated bond; more preferably, it contains a group having an aromatic ring directly bonded to a vinyl group; and even more preferably, it contains a group having a vinylphenyl group.

[0299] Furthermore, in equations (3-1) to (3-3), R 31 ~R 33 Preferably, it does not contain imide bonds.

[0300] In these, a particular resin preferably comprises the structure represented by formula (3-1), preferably formula (3-1) and R 31 It is the group represented by the following formula (R3-1).

[0301] [Chemical Formula 35]

[0302]

[0303] In equation (R3-1), R 34 The symbol represents a substituent, n represents an integer from 0 to 5, and * represents the bonding site with the nitrogen atom in formula (3-1).

[0304] R 34 Preferably, it is an alkyl, aryl, or group containing a group having an olefinic unsaturated bond, preferably alkyl or vinylphenylmethyl.

[0305] n is preferably 0 or 1, more preferably 1.

[0306] [Reaction products]

[0307] The third specific resin is the reaction product of the diamine compound of the present invention with a compound having a total of two or more carboxyl groups and carboxylic anhydride groups (also called "specific carboxylic acid compound") or its derivatives.

[0308] Here, when the reaction is carried out by chemical imidization for the purpose of obtaining the reaction product, the third specific resin is preferably the reaction product of the diamine compound and the specific carboxylic acid compound of the present invention.

[0309] The first specific resin and the second specific resin are preferably reaction products of the diamine compound of the present invention and a compound having two carboxylic anhydride groups or derivatives thereof.

[0310] The details of the diamine compounds of the present invention will be described later.

[0311] As described later, the diamine compounds of the present invention comprise groups having olefinically unsaturated bonds.

[0312] Here, for example, if it is desired to introduce the group represented by the above formula (2-1) into a specific resin, the following can also be considered: as shown in the following formula (2-1C), the structure having phenolic hydroxyl groups is taken as Y of formula (1-1). 1 After introduction, a compound containing an isocyanate compound having an olefinically unsaturated bond, or a compound containing an olefinically unsaturated bond and reacting with a phenolic hydroxyl group, is reacted with the aforementioned phenolic hydroxyl group to form R in formula (2-1). 1 R 2 .

[0313] [Chemical Formula 36]

[0314]

[0315] In equation (2-C), the meaning of L is the same as that of L in equation (2-1) above, and the preferred method is also the same.

[0316] However, this approach can sometimes leave residual phenolic hydroxyl groups in the resin, and can sometimes lead to deviations in the amount of groups with olefinic unsaturated bonds introduced.

[0317] Thus, if the amount introduced is off, deviations may occur in the elongation at break of the cured film, and the loss tangent of the cured film may increase due to the residue of phenolic hydroxyl groups.

[0318] The diamine of the present invention contains a group having an olefinically unsaturated bond, and therefore, by using it in a reaction with a specific carboxylic acid compound, the group represented by formula (2-1) can be easily introduced into the resin, suppressing the presence of residual phenolic hydroxyl groups in the resin. As a result, it is believed that effects such as suppression of elongation at break and reduction of loss tangent in the cured product can be obtained.

[0319] Examples of specific carboxylic acid compounds include compounds having two carboxyl groups, compounds having one carboxyl group and one carboxylic anhydride group, and compounds having two carboxylic anhydride groups, with compounds having two carboxylic anhydride groups being preferred (i.e., carboxylic dianhydrides).

[0320] Specific resins that function as polyimides can be obtained by using compounds having two carboxylic anhydride groups or their derivatives.

[0321] As derivatives of compounds having two carboxylic anhydride groups, examples include diesters of compounds having two carboxylic anhydride groups or diester dihalides obtained from compounds having two carboxylic anhydride groups.

[0322] The aforementioned diesters are obtained, for example, by reacting an alkylating agent or an alcohol with a compound having two carboxylic anhydride groups.

[0323] 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.

[0324] As an example of the above-mentioned alcohols, R can be listed. C1 Compounds represented by -OH. R C1 The meaning of R in the following formula (C1-2) C1 The meanings are the same, and the preferred methods are also the same.

[0325] The aforementioned diester dihalide compounds are obtained, for example, by reacting a halogenating agent with the aforementioned diester.

[0326] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0327] Compounds having two carboxylic anhydride groups or their derivatives may be listed as compounds represented by formulas (C1-1) to (C1-3) below, but are not limited thereto.

[0328] Here, in the case of a reaction carried out by chemical imidization for the purpose of obtaining the reaction product, the compound represented by formula (C1-1) is preferred.

[0329] [Chemical Formula 37]

[0330]

[0331] In equation (C1-1), X 1 This indicates a tetravalent organic group.

[0332] In equation (C1-2), X 1 R represents a tetravalent organic group. C1 Each of these represents a monovalent organic group independently.

[0333] In equation (C1-3), X 1 R represents a tetravalent organic group. C1Each of these represents a monovalent organic group independently.

[0334] In equations (C1-1) to (C1-3), X 1 The preferred method is the same as X in equation (1-1) 1 The preferred method is the same.

[0335] In equations (C1-2) to (C1-3), R C1 The preferred method is the same as that described in paragraphs 0058 to 0063 of Japanese Patent Application Publication No. 2023-003421. 113 and R 114 The preferred method is the same.

[0336] By using compounds having one carboxyl group and one carboxylic anhydride group, a specific resin that acts as a polyamide imide can be obtained.

[0337] By using compounds having two carboxylic anhydride groups, specific resins that function as polyamides can be obtained.

[0338] [Detailed information about the reactions that yield the products]

[0339] In reactions that yield reaction products, it is preferable to use an organic solvent during the reaction. The organic solvent can be one type or two or more types.

[0340] As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0341] In the reaction that yields the reaction products, it is preferable to add a basic compound during the reaction. The basic compound can be one type or two or more types.

[0342] Basic compounds can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0343] Furthermore, when the reaction product is a compound with an imide bond, imidization (chemical imidization) can be promoted in the reaction to obtain the reaction product by using a dehydration cyclizing agent such as a combination of carboxylic anhydride and amine. As a dehydration cyclizing agent, for example, a combination of acetic anhydride and pyridine, a reagent known in the field of chemical imidization, can be used.

[0344] Chemical imidization allows for imidization reactions to occur at low temperatures, and the open-ring portion is less likely to remain. Therefore, it offers advantages such as suppressing amine oxidation and discoloration, minimizing the retention of open-ring portions and carboxyl or amide groups, improving the reliability of the cured product, and reducing loss tangent.

[0345] Furthermore, since the diamine compound of the present invention contains a group having an olefinically unsaturated bond, it is preferable to add a polymerization inhibitor in the reaction to obtain the reaction product. Examples of polymerization inhibitors include those contained in the resin compositions of the present invention, which will be described later.

[0346] In reactions that yield reaction products, end-capping materials are also preferred. Other end-capping agents include monools, phenols, thiols, thiophenols, and monoamines. Considering reactivity and film stability, monools, phenols, or monoamines are preferred. Preferred monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tert-butanol, adamantanol, etc. Preferred phenols include phenol, methoxyphenol, methylphenol, naphthol-1-ol, naphthol-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds as monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-5-aminonaphthalene. Examples of amino acids include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, and 4-aminobenzenethiophenol. More than two of these can be used, and multiple different end groups can be introduced by reacting various end-capping agents.

[0347] Furthermore, when sealing the amino group at the end of the resin, compounds having functional groups capable of reacting with the amino group can be used for sealing. Preferred sealants for the amino group include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Examples of preferred carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of preferred carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, neopentanoyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0348] Furthermore, the structure represented by any of the above formulas (3-1) to (3-3) can also be introduced into a specific resin by using a capping agent containing a group having an olefinic unsaturated bond.

[0349] For example, by using a monoamine represented by the following formula (AM-1), it is possible to introduce the structure represented by formula (3-1) at the end and R 31 The structure of the group represented by (R3-1).

[0350] [Chemical Formula 38]

[0351]

[0352] Regarding the reaction temperature in the reaction to obtain the reaction products, in the case of thermal imidization, it is preferably set to 150 to 350°C, and more preferably to 160 to 250°C.

[0353] However, as described above, in this invention, it is also preferable to carry out the reaction at a low temperature by chemical imidization, wherein the reaction temperature is preferably room temperature (23°C) to 100°C, and more preferably 50 to 90°C.

[0354] The reaction temperature can be determined by referring to known conditions or by considering the rate of change of imide group values, as described later.

[0355] The reaction time (i.e., the time exposed to the above-mentioned reaction temperature) in the reaction to obtain the reaction product is not particularly limited, and can be determined by referring to known conditions or taking into account the rate of change of the imide group value described later. For example, it can be set to 30 minutes to 24 hours, preferably 1 to 15 hours, more preferably 2 to 10 hours, and even more preferably 3 to 8 hours.

[0356] Following the reaction to obtain the reaction products, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, thereby precipitating it as a solid and drying it to obtain a specific resin such as polyimide. To improve the purity, the specific resin such as polyimide may be repeatedly subjected to operations such as redissolution, reprecipitation, and drying. In addition, a step of removing ionic impurities using an ion exchange resin may also be included.

[0357] The preferred resin is one in which the change rate of the imide group value calculated by the following formula is less than 25% before and after heating at 350°C and 1 atm for 1 hour.

[0358] Change rate (%) = (Im2 - Im1) × 100 / Im1

[0359] Im1: Imine group value before heating (mmol / g)

[0360] Im2: Imine group value (mmol / g) after heating at 350℃ and 1 atm for 1 hour.

[0361] The aforementioned rate of change is preferably 15% or less, more preferably 10% or less. Furthermore, there is no particular limitation on the lower limit of the aforementioned rate of change; 0% or more is acceptable.

[0362] The aforementioned rate of change can be determined, for example, by the following method.

[0363] The infrared absorption spectrum of a specific resin was measured, and the absorption peak at 1377 cm⁻¹, which is the origin of the imide bond, was determined. -1 The peak intensity P1 is located nearby. Next, after heat-treating the specific resin at 350°C and 1 atm for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity at 1377 cm⁻¹ was determined. -1 The nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the rate of change of the imide group value can be calculated according to the following formula. Peak intensity P1 represents the imide group value before heating, i.e., Im1, and peak intensity P2 represents the imide group value Im2 after heating.

[0364] The rate of change of imide group value (%) = (peak intensity P2 - peak intensity P1) × 100 / peak intensity P1

[0365] The content of the repeating unit represented by formula (1-1) relative to the total mass of a specific resin 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. The upper limit of the above content is not particularly limited, and may also be 100% by mass.

[0366] Furthermore, a particular resin may contain two or more repeating units represented by formula (1-1). In this case, it is preferable that the total amount is within the above-mentioned range.

[0367] The content of the repeating unit represented by formula (1-2) relative to the total mass of the specific resin is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. There is no particular limitation on the upper limit of the above content, and it may also be 100% by mass.

[0368] Furthermore, a particular resin may contain two or more repeating units represented by formulas (1-2). In this case, it is preferable that the total amount is within the above-mentioned range.

[0369] The content of the repeating unit represented by formula (1-3) relative to the total mass of the specific resin is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. There is no particular limitation on the upper limit of the above content, and it may also be 100% by mass.

[0370] Furthermore, a particular resin may contain two or more repeating units represented by formula (1-1). In this case, it is preferable that the total amount is within the above-mentioned range.

[0371] The weight-average molecular weight (Mw) of a particular resin is preferably 3,000 to 100,000.

[0372] The lower limit of Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more.

[0373] The upper limit of Mw is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 25,000 or less.

[0374] By setting the weight-average molecular weight to 3,000 or higher, the folding resistance of the cured film can be improved. For organic films with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 5,000 or higher is particularly preferred.

[0375] The number average molecular weight (Mn) of the specific resin is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, even more preferably 5,000 to 20,000, and particularly preferably 6,000 to 12,000.

[0376] The molecular weight dispersion of a particular resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. In this specification, the molecular weight dispersion is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. There is no particular limitation on the upper limit of the molecular weight dispersion of a particular resin; for example, it is preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, even more preferably 4.5 or less, and particularly preferably 3.0 or less.

[0377] When the resin composition comprises multiple specific resins as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one specific resin 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 multiple specific resins are considered as one resin are each within the above-mentioned ranges.

[0378] [Specific example]

[0379] Specific examples of a particular resin include polyimide (A-1) to (A-20) in the examples described later, but the present invention is not limited thereto.

[0380] 〔content〕

[0381] 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, even more preferably 50% by mass or more, and most preferably 60% by mass or more, relative to the total solids content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the resin composition.

[0382] The resin composition of the present invention may contain only one specific resin or may contain two or more resins. When containing two or more resins, it is preferable that the total amount is within the above-mentioned range.

[0383] <Other Resins>

[0384] The resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins").

[0385] As other resins, to distinguish them from specific resins, examples include resins belonging to the categories of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, polyamide-imide precursors, polyamide-imides, aromatic polyethers, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.

[0386] As other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamide-imide precursors, and polyamide-imides, examples include compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355. The above descriptions are incorporated herein by reference.

[0387] There are no particular limitations on aromatic polyethers, but polyphenylene ether is preferred.

[0388] Polyphenylene ether is preferably composed of repeating units represented by the following formula (PE).

[0389] [Chemical Formula 39]

[0390]

[0391] In formula (PE), R E1 This represents a hydrogen atom or a substituent. Examples of substituents include halogen atoms, alkyl groups that may have substituents, alkoxy groups that may have substituents, amino groups, nitro groups, carboxyl groups, etc.

[0392] Furthermore, polyphenylene ether is preferably a compound having polymerizable groups.

[0393] The polymerizable groups described above are preferably epoxy groups, oxazolyl groups, oxazolyl groups, hydroxymethyl groups, alkoxymethyl groups, acyloxymethyl groups, terminal isocyanate groups, or groups having olefinic unsaturated bonds, and more preferably groups having olefinic unsaturated bonds.

[0394] Examples of groups having an olefinic unsaturated bond include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, etc., preferably vinylphenyl, (meth)acrylamido, or (meth)acryloyloxy, more preferably vinylphenyl or (meth)acryloyloxy, and even more preferably (meth)acryloyloxy.

[0395] When polyphenylene ether is a compound having polymerizable groups, the position of the polymerizable groups is not particularly limited. For example, a structure in which polymerizable groups are introduced at the end of the main chain is preferred.

[0396] Polyphenylene ether may contain other repeating units. The content of these other repeating units relative to the total mass of the polyphenylene ether is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0397] The number average molecular weight of polyphenylene ether is not particularly limited, but is preferably 500 to 50,000.

[0398] The lower limit of the number-average molecular weight is preferably 800 or more, more preferably 1000 or more, and even more preferably 1500 or more.

[0399] The upper limit of the number-average molecular weight is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 10,000 or less.

[0400] Specific examples of polyphenylene ether (PPE) include, for example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), copolymers of 2,6-dimethylphenol with other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.), polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols, and polyphenylene ethers with linear or branched structures obtained by heating poly(2,6-dimethyl-1,4-phenylene ether) in toluene solvent in the presence of an organic peroxide to cause a redistribution reaction with phenolic compounds such as bisphenols or triphenols, but are not limited to these examples.

[0401] When the resin composition of the present invention contains other resins, the content of the other resins relative to the total solids 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.

[0402] The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0403] As a preferred embodiment of the resin composition of the present invention, it is also possible to set 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.

[0404] Furthermore, when the resin composition of the present invention contains other resins, the content of the specific resin relative to the total content of the specific resin and other resins is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and even more preferably 55 to 70% by mass.

[0405] The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When containing two or more other resins, it is preferable that the total amount is within the above-mentioned range.

[0406] <polymeric compounds with olefinic unsaturated bonds>

[0407] The resin composition of the present invention contains a polymeric compound having olefinic unsaturated bonds.

[0408] Polymerizable compounds having olefinic unsaturated bonds have groups containing olefinic unsaturated bonds. Examples of such groups containing olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0409] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl groups are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0410] Polymerizable compounds having olefinic unsaturated bonds are preferably compounds having one or more groups containing olefinic unsaturated bonds, more preferably compounds having two or more groups. Polymerizable compounds having olefinic unsaturated bonds may have three or more groups containing olefinic unsaturated bonds.

[0411] The compounds having two or more groups containing olefinic unsaturated bonds are preferably compounds having 2 to 15 groups containing olefinic unsaturated bonds, more preferably compounds having 2 to 10 groups, and even more preferably compounds having 2 to 6 groups.

[0412] From the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains compounds having two groups comprising olefinic unsaturated bonds and compounds having three or more groups comprising the aforementioned olefinic unsaturated bonds.

[0413] The molecular weight of the polymeric compound having olefinic unsaturated bonds 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 polymeric compound having olefinic unsaturated bonds is preferably 100 or more.

[0414] Specific examples of polymerizable compounds having olefinically unsaturated groups 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 polyols, and amides of unsaturated carboxylic acids and polyamines. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl, amino, or thioalkyl groups with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids, are also preferred. Furthermore, preferred reaction products are addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups to monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups to monofunctional or polyfunctional alcohols, amines, or thiols. As another example, compounds that replace the aforementioned unsaturated carboxylic acids with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, 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.

[0415] Polymerizable compounds having olefinic unsaturated bonds are preferably compounds having a boiling point of 100°C or higher at atmospheric pressure. Examples of compounds having a boiling point of 100°C or higher at atmospheric pressure include compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0416] Preferred polymerizable compounds with olefinic unsaturated bonds, 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 herein by reference.

[0417] Preferred polymeric compounds having olefinically unsaturated bonds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) 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.

[0418] Commercially available examples of polymerizable compounds containing olefinic unsaturated bonds include, for instance, tetrafunctional acrylates SR-494 (with four vinyl groups), difunctional methacrylates SR-209, 231, and 239 (all manufactured by Sartomer Company, Inc.) with four vinyl groups, hexafunctional acrylates DPCA-60 (with six pentenyl groups), trifunctional acrylates TPA-330 (with three isobutylenyl groups) (all manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (all manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical). (Manufactured by Kyoeisha Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

[0419] As polymerizable compounds having olefinic unsaturated bonds, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. As polymeric compounds with olefinic unsaturated bonds, compounds having an amino structure or a thioether structure within the molecule, as described in Japanese Patent Application Publication Nos. 63-277653, 63-260909, and 01-105238, can also be used.

[0420] Polymerizable compounds having olefinic unsaturated bonds can be compounds having acid groups such as carboxyl groups or phosphate groups. Polymerizable compounds having both acid groups and olefinic unsaturated bonds are preferably esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, more preferably polymerizable compounds having olefinic unsaturated bonds in which a non-aromatic carboxylic anhydride is reacted with the unreacted hydroxyl groups of an aliphatic polyhydroxy compound to form an acid group. Particularly preferred are polymerizable compounds having olefinic unsaturated bonds in which aliphatic polyhydroxy compounds are reacted with the unreacted hydroxyl groups of a non-aromatic carboxylic anhydride to form an acid group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Commercially available examples include, for instance, polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD.

[0421] The acid value of a polymerizable compound having an acid group and an olefinically unsaturated bond is preferably 0.1 to 300 mg KOH / g, more preferably 1 to 100 mg KOH / g. If the acid value of the polymerizable compound having the olefinically unsaturated bond is within the above range, it exhibits excellent manufacturability, excellent developability, and good polymerizability. The acid value is determined according to the description in JIS K 0070:1992.

[0422] As a polymeric compound having an olefinic unsaturated bond, it is also preferred to include a polymeric compound having at least one of the groups selected from urea bonds and urethane bonds (hereinafter also referred to as "polymeric compound U").

[0423] In this invention, the urea bond is *-NR. N -C(=O)-NR N -* represents the key, R NEach symbol represents a hydrogen atom or a monovalent organic group, and * represents the bonding site with a carbon atom.

[0424] In this invention, the carbamate bond is *-OC(=O)-NR. N -* represents the key, R N The symbol represents a hydrogen atom or a monovalent organic group, and * indicates the bonding site with a carbon atom.

[0425] By including polymerizable compound U in the resin composition, chemical resistance, resolution, and other properties are sometimes improved.

[0426] The mechanism by which the above effects are achieved is not yet clear, but it is believed that, for example, during curing based on heating, a portion of the polymeric compound U undergoes thermal decomposition, thereby producing amines, which in turn promote the cyclization of cyclized resin precursors such as polyimide precursors.

[0427] The polymeric compound 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.

[0428] The total number of urea bonds and urethane bonds in the polymeric compound U is preferably 1 or more, 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0429] When the polymeric compound U does not have urethane bonds, the number of urea bonds in the polymeric compound U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0430] When the polymeric compound U does not have urea bonds, the number of urethane bonds in the polymeric compound U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0431] The free radical polymerizable group in the polymerizable compound U is not particularly limited, and examples include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0432] When a polymeric compound U has two or more free radical polymeric groups, the structures of each free radical polymeric group can be the same or different.

[0433] The number of free radical polymerizable groups in the polymerizable compound U can be only one or more, preferably 1 to 10, more preferably 1 to 6, and especially preferably 1 to 4.

[0434] The free radical polymerizable group value (mass of 1 mole of compound with free radical polymerizable groups) in polymerizable compound U is preferably 150-400 g / mol.

[0435] 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.

[0436] From the viewpoint of reproducibility, 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.

[0437] The polymeric group value of polymeric compound U is preferably 210–400 g / mol, more preferably 220–400 g / mol.

[0438] The polymeric compound U is preferably represented by the structure of the following formula (U-1).

[0439] [Chemical Formula 40]

[0440]

[0441] In equation (U-1), R U1 A is a hydrogen atom or a monovalent organic group, and A is -O- or -NR. N -, R N Z is a hydrogen atom or a monovalent organic group. U1 For an organic group with an m valence, Z U2 X is an organic group with a valence of n+1, X is a free radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 1.

[0442] R U1 Preferably, it is a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0443] R N Preferably, it is a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0444] Z U1 Preferably, the radicals are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, or -NR.N -Or these groups bonded together in two or more, more preferably hydrocarbon groups or hydrocarbon groups combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - A group formed by bonding at least one of the groups in the group.

[0445] The aforementioned hydrocarbon group is preferably a hydrocarbon group with 20 or fewer carbon atoms, more preferably a hydrocarbon group with 18 or fewer carbon atoms, and even more preferably a hydrocarbon group with 16 or fewer carbon atoms. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by bonds of these. N The organic group representing a hydrogen atom or a monovalent group is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.

[0446] Z U2 Preferably, the radicals are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, or -NR. N -Or these groups bonded together in two or more, more preferably hydrocarbon groups or hydrocarbon groups combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - A group formed by bonding at least one of the groups in the group.

[0447] As the aforementioned hydrocarbon group, examples can be cited that are similar to those in Z. U1 The same hydrocarbon groups mentioned above are preferred in the same way.

[0448] X is not particularly limited, but examples include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0449] n is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, even more preferably 1 or 2, and especially preferably 1.

[0450] m is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0451] The polymeric compound U preferably has at least one of hydroxyl, alkeneoxy, amide and cyano groups.

[0452] From the viewpoint of the chemical resistance of the obtained cured film, the hydroxyl group can be an alcoholic hydroxyl group or a phenolic hydroxyl group, preferably an alcoholic hydroxyl group.

[0453] From the viewpoint of the chemical resistance of the obtained cured film, the alkene group is preferably an alkene group with 2 to 20 carbon atoms, more preferably an alkene group with 2 to 10 carbon atoms, even more preferably an alkene group with 2 to 4 carbon atoms, and even more preferably ethylene or propylene, especially ethylene.

[0454] The alkene oxide can be included as a polyalkene oxide in the polymerizable compound U. The number of repetitions of the alkene oxide is preferably 2 to 10, more preferably 2 to 6.

[0455] The amide group refers to -C(=O)-NR N - The key it represents. R N As described above. When the polymerizable compound U has an amide group, the polymerizable compound U can, for example, act as RC(=O)-NR. N -* indicates the group or *-C(=O)-NR N -R represents a group containing an amide group. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0456] The polymeric compound U may have two or more structures selected from the group consisting of hydroxyl, alkene (wherein, when constituting polyalkene, it is polyalkene), amide, and cyano groups within the molecule, but is also preferred to have only one within the molecule.

[0457] The aforementioned hydroxyl, alkeneoxy, amide, and cyano groups can be present at any position in the polymerizable compound U. However, from the viewpoint of chemical resistance, the polymerizable compound U is preferably connected to at least one of the groups selected from the group consisting of the aforementioned hydroxyl, alkeneoxy, amide, and cyano groups through a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1").

[0458] In particular, when the polymerizable compound U contains only one free radical polymerizable group, it is preferable to connect the free radical polymerizable group contained in the polymerizable compound U to at least one of the following groups selected from hydroxyl, alkene, amide, and cyano groups via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").

[0459] When the polymerizable compound U contains an alkene group (wherein, in the case of constituting a polyalkene group, it is a polyalkene group) and has the aforementioned linking group L2-1 or the aforementioned linking group L2-2, the structure of the alkene group (wherein, in the case of constituting a polyalkene group, it is a polyalkene group) bonded to the side opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by these combinations. As the aforementioned hydrocarbon group, it is preferably a hydrocarbon group with 20 or fewer carbon atoms, more preferably a hydrocarbon group with 18 or fewer carbon atoms, and even more preferably a hydrocarbon group with 16 or fewer carbon atoms. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by these bonds. Furthermore, the preferred manner for the free radical polymerizable group is the same as the preferred manner for the free radical polymerizable group in the aforementioned polymerizable compound U.

[0460] When the polymerizable compound U contains an amide group and has the aforementioned linking group L2-1 or L2-2, the structure of the amide group bonded to the side opposite to the linking group L2-1 or L2-2 is not particularly limited, but is preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by these combinations. As the aforementioned hydrocarbon group, it is preferably a hydrocarbon group with 20 or fewer carbon atoms, more preferably a hydrocarbon group with 18 or fewer carbon atoms, and even more preferably a hydrocarbon group with 16 or fewer carbon atoms. Furthermore, examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by these bonds. The preferred manner for the free radical polymerizable group is the same as the preferred manner for the free radical polymerizable group in the aforementioned polymerizable compound U. Furthermore, in the above manner, the amide group can be bonded to the linking group L2-1 or L2-2 on the carbon atom side, or it can be bonded to the linking group L2-1 or L2-2 on the nitrogen atom side of the amide group.

[0461] Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, the polymeric compound U is preferably one with hydroxyl groups.

[0462] From the viewpoint of compatibility with specific resins, the polymerizable compound U is preferably containing aromatic groups.

[0463] The aromatic group is preferably directly bonded to the urea bond or urethane bond contained in the polymerizable compound U. When the polymerizable compound U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.

[0464] The aromatic group can be an aromatic hydrocarbon group or an aromatic heterocyclic group, or it can be one of these structures that form a fused ring, preferably an aromatic hydrocarbon group.

[0465] The aromatic hydrocarbon group described above is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, and even more preferably a group formed by removing 2 or more hydrogen atoms from a benzene ring structure.

[0466] The aromatic heterocyclic group described above is preferably a 5-membered or 6-membered aromatic heterocyclic group. Examples of aromatic heterocycles in such aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetraazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings can be further condensed with other rings, such as indole and benzimidazole.

[0467] The heteroatom contained in the above-mentioned aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.

[0468] The aromatic group is preferably a linking group that connects two or more free radical polymerizable groups and contains a urea bond or a carbamate bond, or a linking group that connects at least one of the groups selected from the group consisting of hydroxyl, alkoxy, amide and cyano groups to at least one free radical polymerizable group contained in the polymerizable compound U.

[0469] The number of atoms (linkage chain length) between the urea bond or urethane bond in the polymerizable compound U and the free radical polymerizable group is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.

[0470] In the case where the polymeric compound U contains a total of two or more urea bonds or urethane bonds, contains two or more free radical polymerizable groups, or contains two or more urea bonds or urethane bonds and contains two or more free radical polymerizable groups, the minimum number of atoms (linking chain length) of the urea bonds or urethane bonds and the free radical polymerizable groups shall be within the above-mentioned range.

[0471] In this specification, "the number of atoms (linkage chain length) between the urea bond or urethane bond and the polymerizable group" refers to the shortest (minimum number of atoms) atomic chain connecting the two atoms or groups of atoms in the path that links them. For example, in the structure represented by the following formula, the number of atoms (linkage chain length) between the urea bond and the free radical polymerizable group (methacryloyloxy) is 2.

[0472] [Chemical Formula 41]

[0473]

[0474] [Axis of symmetry]

[0475] The polymerizable compound U is also preferably a compound without a symmetry axis.

[0476] The absence of a symmetry axis in polymeric compound U refers to a compound that is asymmetrical to the left and right by rotating the compound as a whole, without producing molecules identical to the original molecule. Furthermore, when the structural formula of polymeric compound U is written on paper, the absence of a symmetry axis means that the structural formula of polymeric compound U cannot be written in a form that exhibits a symmetry axis.

[0477] It is believed that the lack of a symmetry axis in the polymeric compound U inhibits the aggregation of polymeric compounds U in the composite film.

[0478] [Molecular weight]

[0479] The molecular weight of the polymeric compound U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0480] There is no particular limitation on the method of manufacturing polymeric compound U, but it can be obtained, for example, by reacting a compound having a free radical polymeric compound and an isocyanate group with a compound having at least one of a hydroxyl or an amino group.

[0481] Specific examples of polymeric compound U are shown below, but polymeric compound U is not limited thereto.

[0482] [Chemical Formula 42]

[0483]

[0484] [Chemical Formula 43]

[0485]

[0486] [Chemical Formula 44]

[0487]

[0488] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses difunctional methacrylate or acrylate.

[0489] 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, 1,6-hexanediol diacrylate, etc. 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, EO-modified dimethacrylate of isocyanuric acid, EO-modified dimethacrylate of isocyanuric acid, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be used in combination as needed.

[0490] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of about 200 for the polyethylene glycol chain.

[0491] From the viewpoint of suppressing warping of the pattern (cured product), the resin composition of the present invention preferably uses a polymeric compound having only one olefinic unsaturated bond (a monofunctional polymeric compound). As a monofunctional polymeric compound, preferably used are n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, butoxyethyl methacrylate, carbitol methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, N-hydroxymethyl methacrylamide, glycidyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, and other methacrylic acid derivatives, N-vinylpyrrolidone, N-vinylcaprolactam, and other N-vinyl compounds, allyl glycidyl ether, etc. As a monofunctional polymeric compound, in order to suppress volatilization before exposure, compounds having a boiling point of 100°C or higher at ambient pressure are also preferred.

[0492] In addition, as polymeric compounds with two or more olefinic unsaturated bonds, examples include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0493] The content of the polymerizable compound having olefinic unsaturated bonds 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.

[0494] Polymerizable compounds having olefinic unsaturated bonds can be used alone or in combination of two or more. When using two or more, it is preferable that their total amount is within the range described above.

[0495] [Other polymeric compounds]

[0496] The resin composition of the present invention preferably further contains other polymeric compounds that are different from the polymeric compounds having olefinic unsaturated bonds described above.

[0497] Other polymeric compounds refer to polymeric compounds other than those with olefinic unsaturated bonds as described above. Preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by photosensitization by the aforementioned photoacid generators or photoalkali generators. More preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of acids or bases.

[0498] Other polymerizable compounds may be listed in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0499] [Polymerization initiator]

[0500] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator can be a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is particularly preferred.

[0501] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible regions is preferred. Furthermore, it can also be an active agent that reacts with a photoexcited sensitizer to generate active free radicals.

[0502] The photoradical polymerization initiator preferably contains at least one initiator 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 -1The molar absorptivity of a compound. The molar absorptivity of a compound can be determined using known methods. For example, it is preferably determined using a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0503] As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl biimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azido compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For detailed information on these compounds, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are incorporated herein by reference.

[0504] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference, can be cited. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0505] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, as these are incorporated herein by reference.

[0506] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE127 (all manufactured by BASF) can be used.

[0507] 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.

[0508] As an aminoacetophenone-based initiator, an acylphosphine oxide-based initiator, or a metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 may also be used. This content is incorporated herein by reference.

[0509] Oxime compounds are more preferably used as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be improved more effectively. Oxime compounds have a wide exposure latitude (exposure margin) and also act as photocuring accelerators, making them particularly preferred.

[0510] 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 and... The compounds described in Technology (1995, pp. 202-232), Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2017-019766, Japanese Patent No. 6065596, International Publication No. 2015 / 152153, International Publication No. 2017 / 051680, Japanese Patent Application Publication No. 2017-198865, International Publication No. 2017 / 164127 (paragraphs 0025-0038), and International Publication No. 2013 / 167515 are included in this specification.

[0511] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In resin compositions, the use of oxime compounds as photoradical polymerization initiators is particularly preferred. Oxime compounds used as photoradical polymerization initiators have an intramolecular linking group >C=NOC(=O)-.

[0512] [Chemical Formula 45]

[0513]

[0514] 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 Electronic Materials CO., LTD.), ADEKAARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Furthermore, oxime compounds with the following structures can also be used.

[0515] [Chemical Formula 46]

[0516]

[0517] As photoradical polymerization initiators, for example, oxime compounds with fluorene rings, oxime compounds with at least one benzene ring forming a naphthalene ring skeleton, and oxime compounds with fluorine atoms, as described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189, can also be used.

[0518] Furthermore, it is also possible to use oxime compounds with nitro groups, oxime compounds with benzofuran skeletons, and oxime compounds with hydroxyl substituents bonded to a carbazole skeleton as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359. These contents are incorporated in this specification.

[0519] As a photopolymerization initiator, Ar aromatic cyclic groups with electron-withdrawing groups introduced onto the aromatic ring can also be used. OX1 Oxime compounds (hereinafter also referred to as oxime compounds OX). As the above aromatic cyclic group Ar... OX1Examples of electron-withdrawing groups include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano, with acyl and nitro being preferred. Acyl is more preferred due to its ease of forming a film with excellent lightfastness, and benzoyl is even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthioalkyl, arylthioalkyl, acyl, or amino, with alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthioalkyl, or amino being even more preferred, and alkoxy, alkylthioalkyl, or amino being even more preferred.

[0520] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2).

[0521] [Chemical Formula 47]

[0522]

[0523] In the formula, R X1 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphinyl, carbamoyl, or aminosulfonyl.

[0524] R X2 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy, or amino.

[0525] R X3 ~R X14 Each can be used to represent a hydrogen atom or a substituent independently.

[0526] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0527] In the above formula, R is preferred. X12 It is an electron-withdrawing group and R X10 R X11 R X13 R X14 It is a hydrogen atom.

[0528] As a specific example of the oxime compound OX, the compound described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 is cited, which is incorporated in this specification.

[0529] Examples of particularly preferred oxime compounds include oxime compounds with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and oxime compounds with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061, the contents of which are incorporated herein by reference.

[0530] From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0531] Furthermore, the photoradical polymerization initiator is a trihalomethane triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. More preferably, it is at least one compound selected from the group consisting of trihalomethane triazine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. More preferably, it is a metallocene compound or an oxime compound.

[0532] As a photoradical polymerization initiator, compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359 and paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, as these are incorporated herein by reference.

[0533] As photoradical polymerization initiators, difunctional or trifunctional or higher photoradical polymerization initiators can be used. By using such initiators, good sensitivity can be obtained because one molecule of the initiator generates two or more free radicals. Furthermore, when using compounds with asymmetric structures, crystallinity decreases while solubility in solvents and the like is improved, making it difficult for the resin composition to precipitate over time, thereby improving its long-term stability. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and compounds described in Japanese Patent Application Publication No. 2013-522445. The following are included in this specification: oxime ester photoinitiators as described in International Publication No. 2016 / 034963 (G), Cmpdl-7, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators as described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342 (A), and oxime ester photoinitiators as described in Japanese Patent Publication No. 6469669.

[0534] 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 contain only one type or two or more types. When two or more photopolymerization initiators are contained, their total amount is preferably within the above-mentioned range.

[0535] In addition, since photopolymerization initiators sometimes also function as thermal polymerization initiators, crosslinking using photopolymerization initiators is sometimes further carried out by heating in ovens, heating plates, etc.

[0536] [Sensitizer]

[0537] The resin composition may contain a sensitizer. The sensitizer absorbs specific active light and becomes electronically excited. The electronically excited sensitizer comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or bases.

[0538] As usable sensitizers, compounds of the following series can be used: benzophenone series, milchone series, coumarin series, pyrazole azo series, aniline azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, anthocyanin series, phenothiazine series, pyrrolopyrazole methylene azo series, guttan series, phthalocyanine series, benzopyran series, indigo series, etc.

[0539] Examples of sensitizers include milchone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylindanone, and p-dimethylaminocinnamylindanone. Benzylindanone, 2-(p-dimethylaminophenylbenzylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylamino Isoamyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0540] Furthermore, other sensitizing pigments can be used.

[0541] For details regarding the sensitizing pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0542] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used in combination.

[0543] [Chain transfer agent]

[0544] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds with thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferably used.

[0545] Furthermore, the chain transfer agent can also be the compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0546] When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solids content of the resin composition. There may be only one type of chain transfer agent, or there may be two or more types. When there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0547] Furthermore, a photoacid generator can be used as a photopolymerization initiator. Preferably, a photoacid generator that generates free radicals is preferred.

[0548] Specifically, the preferred compound is one that absorbs light to decompose and generate free radicals, and extracts hydrogen from the solvent or the acid-generating agent itself to generate an acid.

[0549] Examples of photoacid-generating agents include quinone diazide compounds, oxime sulfonate compounds, organohalides, organoborates, disulfones, and onium salts, with onium salts being preferred.

[0550] Examples of onium salts include diazonium salts, phosphonium salts, sulfonium salts, and iodized salts.

[0551] Furthermore, onium salts are salts of cations and anions with onium structures, and these cations and anions may or may not be bonded by covalent bonds.

[0552] That is, the onium salt can be an intramolecular salt having a cationic and anionic portion within the same molecular structure, or it can be an intermolecular salt formed by ionic bonding of cationic and anionic molecules that are different molecules, but it is preferably an intermolecular salt. Furthermore, in the composition of the present invention, the above-mentioned cationic portion or cationic molecule can be bonded to or dissociated from the above-mentioned anionic portion or anionic molecule by ionic bonds.

[0553] [Sulfur]

[0554] In this invention, sulfonium salt refers to a salt of sulfonium cation and anion.

[0555] -sulfonium cation-

[0556] As a sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.

[0557] Furthermore, the preferred cation as a sulfonium cation is the cation represented by the following formula (103).

[0558] [Chemical Formula 48]

[0559]

[0560] In equation (103), R 8 ~R 10 Each hydrocarbon group can be represented independently.

[0561] R 8 ~R 10 Each is preferably alkyl or aryl, more preferably alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, even more preferably aryl with 6 to 12 carbon atoms, and even more preferably phenyl.

[0562] R 8 ~R 10 It may also have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, etc. Among these, it is preferable to have alkyl or alkoxy groups as substituents, more preferably to have branched alkyl or alkoxy groups, and even more preferably to have branched alkyl groups with 3 to 10 carbon atoms or alkoxy groups with 1 to 10 carbon atoms.

[0563] R 8 ~R 10The groups can be the same or different groups; from the point of view of synthetic suitability, the same groups are preferred.

[0564] -Anion-

[0565] There are no specific restrictions on the anion; the choice should be based on the acid produced. However, B(C6F5)4 can be cited as an example. - BF4 - Boron-based anions, (Rf) n PF 6-n - PF3(C2F5) 3- PF6 - Phosphine anions, SbF6 - Antimony anions, other carboxylic acid anions, sulfonic acid anions, etc.

[0566] Iodized salt

[0567] In this invention, iodine salt refers to a salt of iodine cation and anion. Examples of anions include those identical to those in the above-described matte salts, and the preferred embodiments are also the same.

[0568] -iodocation-

[0569] As an iodine cation, a diaryliodocation is preferred.

[0570] Furthermore, the iodine cation is preferably the cation represented by the following formula (104).

[0571] [Chemical Formula 49]

[0572]

[0573] In equation (104), R 11 and R 12 Each hydrocarbon group can be represented independently.

[0574] R 11 and R 12 Each is preferably alkyl or aryl, more preferably alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, even more preferably aryl with 6 to 12 carbon atoms, and even more preferably phenyl.

[0575] R 11 and R 12It may also have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, etc. Among these, it is preferable to have alkyl or alkoxy groups as substituents, more preferably to have branched alkyl or alkoxy groups, and even more preferably to have branched alkyl groups with 3 to 10 carbon atoms or alkoxy groups with 1 to 10 carbon atoms.

[0576] R 11 and R 12 The groups can be the same or different groups; from the point of view of synthetic suitability, the same groups are preferred.

[0577] [phosphorus salt]

[0578] In this invention, phosphonium salt refers to a salt of phosphonium cation and anion. Examples of anions include those identical to the anions in the sulfonium salts described above, and the preferred embodiments are also the same.

[0579] -phosphocation-

[0580] As a phosphonium cation, a quaternary phosphonium cation is preferred, and examples include tetraalkylphosphonium cations and triarylmonylphosphonium cations.

[0581] Furthermore, the preferred cation is the one represented by the following formula (105).

[0582] [Chemical Formula 50]

[0583]

[0584] In equation (105), R 13 ~R 16 Each can be used to represent a hydrogen atom or a hydrocarbon group independently.

[0585] R 13 ~R 16 Each is preferably alkyl or aryl, more preferably alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, even more preferably aryl with 6 to 12 carbon atoms, and even more preferably phenyl.

[0586] R 13 ~R 16 It may also have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, etc. Among these, it is preferable to have alkyl or alkoxy groups as substituents, more preferably to have branched alkyl or alkoxy groups, and even more preferably to have branched alkyl groups with 3 to 10 carbon atoms or alkoxy groups with 1 to 10 carbon atoms.

[0587] R 13 ~R16 The groups can be the same or different groups; from the point of view of synthetic suitability, the same groups are preferred.

[0588] The content of photoacid generator relative to the total solids content of the resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.

[0589] A single photoacid-generating agent can be used alone, or multiple agents can be used in combination. In the case of multiple combinations, it is preferable that the total amount of these agents is within the range described above.

[0590] Furthermore, in order to impart photosensitivity to the desired light source, it is preferable to use it in combination with a sensitizer.

[0591] Furthermore, the resin composition of the present invention containing two or more polymerization initiators is also one of the preferred embodiments of the present invention.

[0592] Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0593] By including a photopolymerization initiator and a thermal polymerization initiator (described later), it has properties such as the ability to perform exposure-based pattern formation, ease of free radical polymerization during curing based on the heating process (described later), and improved chemical resistance.

[0594] As for the ratio of the photopolymerization initiator and the thermal polymerization initiator (described later), the content of the thermal polymerization initiator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0595] By including photoradical polymerization initiators and photoacid-producing agents, it has properties such as improved resolution.

[0596] As for the ratio of photopolymerization initiator and photoacid generator, the content of photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of photopolymerization initiator and photoacid generator.

[0597] [Thermal polymerization initiator]

[0598] 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 and initiate or promote the polymerization reaction of polymerizable compounds. By adding thermal free radical polymerization initiators, polymerization reactions of resins and polymerizable compounds can also be carried out, thus further improving solvent resistance.

[0599] As thermal free radical polymerization initiators, specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the contents of which are incorporated in this specification, can be cited.

[0600] When the resin composition contains a thermal polymerization 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, and even more preferably 0.5 to 15% by mass. The resin composition may contain only one thermal polymerization initiator or may contain two or more thermal polymerization initiators. When containing two or more thermal polymerization initiators, the total amount is preferably within the above range.

[0601] <Alkali-generating agents>

[0602] 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. Preferred alkali-generating agents include thermal alkali-generating agents and photo-alkali-generating agents.

[0603] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains an alkali-generating agent. By containing a thermally alkali-generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, thereby resulting in good mechanical properties or chemical resistance of the cured product, and its performance as an interlayer insulating film for rewiring layers included in semiconductor packages becomes excellent.

[0604] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from the base-generating agent include, for example, secondary and tertiary amines.

[0605] There are no particular limitations on the alkali-generating agent; any known alkali-generating agent may be used. Examples of known alkali-generating agents include, for instance, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imine salts, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimide compounds.

[0606] Specific examples of nonionic base generating agents include compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0607] The following compounds can be cited as base-generating agents, but are not limited to these.

[0608] [Chemical Formula 51]

[0609]

[0610] [Chemical Formula 52]

[0611]

[0612] The molecular weight of the nonionic alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0613] Specific preferred compounds for generating ionic bases include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0614] Specific examples of ammonium salts include the following compounds, but are not limited to these.

[0615] [Chemical Formula 53]

[0616]

[0617] The following compounds can be cited as specific examples of imine salts, but are not limited to these.

[0618] [Chemical Formula 54]

[0619]

[0620] Furthermore, from the viewpoint of storage stability and the deprotection and generation of bases during curing, an amine with an amino group protected by a tert-butoxycarbonyl group is preferred as an alkali generating agent.

[0621] Examples of amine compounds protected by the tert-butoxycarbonyl group include, for example, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, and α-[2-(methylamino)ethyl]benzylethanolamine. Compounds containing alcohols, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxobis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxotetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxoundecane, or amino acids and their derivatives, wherein the amino group is protected by a tert-butoxycarbonyl group, but not limited to these.

[0622] 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.

[0623] One or more alkali-generating agents can be used. When using two or more, it is preferable that the total amount is within the above range.

[0624] Solvent

[0625] The resin composition of the present invention preferably contains a solvent.

[0626] 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.

[0627] 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, γ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetic acid, ethyl alkoxyacetic acid, butyl alkoxyacetic acid (e.g., methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, etc.)), and alkyl 3-alkoxypropionate esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.). Ethyl propionate, 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 examples.

[0628] Examples of preferred ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether 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.

[0629] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0630] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred examples.

[0631] As a sulfoxide, dimethyl sulfoxide is a preferred example.

[0632] Preferred examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0633] Examples of preferred urea compounds include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0634] 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.

[0635] Regarding solvents, from the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvents.

[0636] In this invention, the solvent is preferably selected from one of the following: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic 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 and propylene glycol methyl ether acetate, L-glucosamine, dihydroL-glucosamine, or a mixed solvent consisting of two or more of these solvents. Particularly preferred methods include the use of dimethyl sulfoxide and γ-butyrolactone, dimethyl sulfoxide and γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone and ethyl lactate. Further addition of approximately 1 to 10% by weight of toluene relative to the total mass of the solvent in these solvents is also a preferred method of the invention.

[0637] In particular, from the viewpoint of the storage stability of the resin composition, including γ-valerol as a solvent is one of the preferred embodiments of the present invention. In this embodiment, the content of γ-valerol 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 taking into account the solubility of the specific resin or other components contained in the resin composition.

[0638] Furthermore, when using dimethyl sulfoxide and γ-valerolactone together, the total mass relative to 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.

[0639] From the viewpoint of coatability, the solvent content is preferably set to an amount where the total solids concentration of the resin composition of the present invention reaches 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. Regarding the solvent content, it can be adjusted according to the desired thickness of the coating and the coating method. When two or more solvents are contained, it is preferable that their total content is within the above range.

[0640] <Metal Adhesion Improver>

[0641] 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 improver. Examples of metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0642] [Silane coupling agent]

[0643] 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, it is preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. The silane coupling agent is also preferably a compound as follows: In the following formula, Me represents methyl and Et represents ethyl. Furthermore, the following R can be a structure derived from a capping agent with a capping isocyanate group. As a capping agent, it can be selected based on the deactivation temperature; examples include alcohol compounds, phenolic compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the deactivation temperature to 160–180°C, caprolactam is preferred. Commercially available examples of this compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0644] [Chemical Formula 55]

[0645]

[0646] [Chemical Formula 56]

[0647]

[0648] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimeth ... Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0649] Furthermore, as a silane coupling agent, compounds of oligomer type having multiple alkoxysilyl groups can also be used.

[0650] Examples of this type of oligomer include compounds containing repeating units represented by the formula (S-1) below.

[0651] [Chemical Formula 57]

[0652]

[0653] In equation (S-1), R S1 R represents a monovalent organic group. S2 It represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer from 0 to 2.

[0654] R S1The preferred structure includes a polymerizable group. Examples of polymerizable groups include groups having an olefinic unsaturated bond, epoxy groups, oxobutyl groups, benzoxazolyl groups, terminal isocyanate groups, and amino groups. Examples of groups having an olefinic unsaturated bond include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, etc., preferably vinylphenyl, (meth)acrylamido, or (meth)acryloyloxy, more preferably vinylphenyl or (meth)acryloyloxy, and even more preferably (meth)acryloyloxy.

[0655] R S2 Preferably, it is alkoxy, more preferably methoxy or ethoxy.

[0656] n represents an integer from 0 to 2, preferably 1.

[0657] Here, the repeating units represented by multiple formulas (S-1) contained in oligomer-type compounds may have the same structure.

[0658] Here, in the oligomer-type compound, among the multiple repeating units represented by formula (S-1), it is preferable that at least one has n of 1 or 2, more preferably that at least two have n of 1 or 2, and even more preferably that at least two have n of 1.

[0659] As for this type of oligomer compound, commercially available products can be used, such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0660] [Aluminum-based adhesive additives]

[0661] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[0662] As other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are incorporated in this specification.

[0663] The content of the metal adhesion improver relative to 100 parts by weight of a specific resin is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting the content to the lower limit or above, the adhesion between the pattern and the metal layer becomes good; by setting the content to the upper limit or below, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be only one type or may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0664] <Migration Inhibitors>

[0665] 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.

[0666] 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, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and thioalkyl 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.

[0667] Among these, the resin composition of the present invention preferably contains an azole compound.

[0668] Azole compounds are compounds containing an azole structure, which refers to a 5-membered ring structure containing a nitrogen atom as a cyclic atom, preferably a 5-membered ring structure containing two or more nitrogen atoms as cyclic atoms. Specifically, examples of azole structures include imidazole, triazole, and tetraazole structures. Examples include benzimidazole and benzotriazole. These structures can form polycyclic rings with other ring structures through condensation or other processes.

[0669] Furthermore, as a compound having an azole structure, it is preferred to be a compound in which the group represented by the following formula (R-1) or the following formula (R-2) is directly bonded to the azole structure.

[0670] [Chemical Formula 58]

[0671]

[0672] In equation (R-1), R1 The symbol represents a monovalent organic group, and * indicates the bonding site with the azole structure.

[0673] In equation (R-2), R 2 R represents a hydrogen atom or a monovalent organic group. 3 The symbol represents a monovalent organic group, and * indicates the bonding site with the azole structure.

[0674] In equation (R-1), R 1 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by the bond of at least one group in the group. R N As described above.

[0675] The preferred hydrocarbon group is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these.

[0676] Furthermore, R 1 The total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.

[0677] R 1 The bonding site between the carbonyl group in formula (R-1) and the carbonyl group is preferably a hydrocarbon group or -NR. N -

[0678] In formula (R-1), * represents the bonding site with the azole structure, preferably the bonding site with the carbon atom that is the cyclic atom of the azole structure.

[0679] In equation (R-2), R 2 Hydrogen atoms are preferred.

[0680] In R 2 When R is a monovalent organic group, 2 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by the bond of at least one group in the group. R N As described above.

[0681] The preferred hydrocarbon group is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these.

[0682] Furthermore, in R 2 When the organic group is monovalent, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.

[0683] In R 2 When R is a monovalent organic group, 2The bonding sites between the nitrogen atom in formula (R-2) and the nitrogen atom in formula (R-2) are preferably hydrocarbon groups or -C(=O)-.

[0684] In equation (R-2), R 3 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by the bond of at least one group in the group. R N As described above.

[0685] The preferred hydrocarbon group is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these.

[0686] Furthermore, in R 3 When the organic group is monovalent, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.

[0687] R 3 The bonding sites between the nitrogen atom in formula (R-2) and the nitrogen atom in formula (R-2) are preferably hydrocarbon groups or -C(=O)-.

[0688] In formula (R-2), * represents the bonding site with the azole structure, preferably the bonding site with the carbon atom that is the cyclic atom of the azole structure.

[0689] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[0690] Other migration inhibitors include rust inhibitors described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are included in this specification.

[0691] The following compounds can be cited as specific examples of migration inhibitors.

[0692] [Chemical Formula 59]

[0693]

[0694] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor relative to the total solids content of the resin composition 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.

[0695] There may be only one migration inhibitor or two or more. If there are two or more migration inhibitors, it is preferable that their total number is within the range mentioned above.

[0696] <Light absorber>

[0697] The resin composition of the present invention is also preferably a compound (light absorber) that reduces the absorbance of its exposure wavelength due to exposure.

[0698] Examples of light absorbers include compounds described in paragraphs 0159 to 0183 of International Patent Publication No. 2022 / 202647 and compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These contents are included in this specification.

[0699] The content of light absorber relative to the total solids content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0700] <Polymerization Inhibitor>

[0701] 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.

[0702] Specific compounds that can be cited 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, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. This content is incorporated herein by reference.

[0703] 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.

[0704] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the range mentioned above.

[0705] <Other Additives>

[0706] 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, organotitanium compounds, antioxidants, photoacid generators, anticoagulants, phenolic 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. Regarding these components, for example, reference can be made to paragraphs 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are incorporated, their total content is preferably set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0707] [Inorganic particles]

[0708] 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.

[0709] 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.

[0710] 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.).

[0711] In cases where the above measurements are difficult to perform, measurements can also be taken using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0712] [Organotitanium compounds]

[0713] By incorporating organic titanium compounds into the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0714] As usable organotitanium compounds, examples include compounds in which organic groups are bonded to titanium atoms via covalent or ionic bonds.

[0715] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0716] I) Titanium chelate compounds: From the viewpoint of good storage stability of the resin composition and obtaining a good cured pattern, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples are bis(triethanolamine)diisopropoxide titanium, bis(n-butanol)bis(2,4-pentanedione) titanium, bis(2,4-pentanedione)diisopropoxide titanium, bis(tetramethylheptanedione)diisopropoxide titanium, bis(ethyl acetoacetate)diisopropoxide titanium, etc.

[0717] 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, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc.

[0718] III) Dioctenotin compounds: such as pentamethylcyclopentadienyltrimethoxytitanium, 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.

[0719] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecylbenzenesulfonate) isopropoxy titanium, etc.

[0720] V) Titanium oxide compounds: such as bis(pentanedione) titanium oxide, bis(tetramethylheptanedione) titanium oxide, phthalocyanine titanium oxide, etc.

[0721] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0722] VII) Titanate coupling agents: such as isopropyltridodecylbenzenesulfonyl titanate, etc.

[0723] From the viewpoint of better chemical resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dicarboxylated titanium compounds is preferred as the organotitanium compound. In particular, bis(ethyl acetoacetate)diisopropoxide titanium, tetra(n-butoxy) titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium are preferred.

[0724] Furthermore, as an organotitanium compound or a substitute for an organotitanium compound, it is also preferable to include a compound represented by the following formula (T-1).

[0725] [Chemical Formula 60]

[0726]

[0727] In equation (T-1), M represents titanium, zirconium, or hafnium; 11 is an integer from 0 to 2; 12 is 0 or 1; 11 + 12 × 2 is an integer from 0 to 2; m is an integer from 0 to 4; n is an integer from 0 to 2; 11 + 12 + m + n × 2 = 4; R 11 R is independently substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted phenoxy. 12 For substituted or unsubstituted hydrocarbon groups, R 2 Each is an independent group comprising the structure represented by the following formula (T-2), R 3 Each is an independent group comprising the structure represented by the following formula (T-2), X A Each can be an oxygen atom or a sulfur atom, independently.

[0728] [Chemical Formula 61]

[0729]

[0730] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= are represented independently, with * indicating the bonding site with other structures and # indicating the bonding site with metal atoms, respectively.

[0731] In formula (T-1), from the viewpoint of the storage stability of the composition, M is preferably titanium.

[0732] In formula (T-1), the method in which l1 and l2 are 0 is also one of the preferred methods of the present invention.

[0733] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0734] In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1.

[0735] In this case, in equation (T-1), it is also preferable that 11 and 12 are 0 and m is 0, 2 or 4.

[0736] In equation (T-1), considering the stability of a specific metal complex, R 11 Preferably, it is a substituted or unsubstituted cyclopentadiene ligand.

[0737] Furthermore, R 11 The cyclopentadienyl, alkoxy, and phenoxy groups in the compound can be substituted, but the unsubstituted form is also one of the preferred forms of the present invention.

[0738] In equation (T-1), R 12 Preferably, it is a hydrocarbon group with 1 to 20 carbon atoms, and more preferably a hydrocarbon group with 2 to 10 carbon atoms.

[0739] As R 12 The hydrocarbon group in the hydrocarbon group can be any one of aliphatic hydrocarbon group or aromatic hydrocarbon group, preferably an aromatic hydrocarbon group.

[0740] As an aliphatic hydrocarbon group, it can be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.

[0741] As an aromatic hydrocarbon group, it is preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 10 carbon atoms, and even more preferably a phenylene group.

[0742] As R 12 The substituents in R are preferably monovalent substituents, such as halogen atoms. Furthermore, R... 12 In the case of aromatic hydrocarbon groups, alkyl groups can be used as substituents.

[0743] In these, in equation (T-1), R 12 Preferably, it is an unsubstituted phenylene oxide. Furthermore, R 12 The phenylene oxide in the sample is preferably 1,2-phenylene oxide.

[0744] In equation (T-1), m is 2 or more, containing more than 2 R. 2 In the case of two or more R 2 The structures can be the same or different.

[0745] In equation (T-1), n ​​is 2 or more, and contains more than 2 R. 3 In the case of two or more R 3 The structures can be the same or different.

[0746] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= can be represented independently, preferably at least one representation of -C(-*)=, more preferably at least two representations of -C(-*)=.

[0747] As specific examples of compounds represented by formula (T-1), compounds corresponding to I-5 to I-8 in the examples can be cited, but are not limited to these.

[0748] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 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.

[0749] 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.

[0750] Other additives may include compounds described in paragraphs 0316 to 0358 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0751] <Characteristics of Resin Compositions>

[0752] 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 1,000 mm... 2 If the thickness is above / s, it is easy to coat with the film thickness required for reinsertion insulation, for example, if it is 12,000 mm. 2 When the speed is below / s, a coating film with excellent surface finish can be obtained.

[0753] <Restrictions on the substances contained in the resin composition>

[0754] 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.

[0755] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container.

[0756] 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 contained, it is preferable that the total amount of these metals is within the above-described range.

[0757] Furthermore, as a method to reduce metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0758] Regarding 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. The amount present as halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. Preferably, the total amount of chlorine atoms and bromine atoms, or the total amount of chloride ions and bromide ions, is within the above-mentioned ranges.

[0759] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[0760] 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-layer bottles with an inner wall formed of six layers of six different resins, or bottles with a seven-layer structure formed of six different resins, are also preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0761] <Cure of the resin composition>

[0762] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0763] The cured product of the present invention is a cured product obtained by curing a resin composition.

[0764] 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 cured form of the 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 form is preferably film-shaped. Through patterning of the resin composition, the shape of the cured form can also be selected according to applications such as forming a protective film on a wall surface, forming conductive through-holes, adjusting impedance, electrostatic capacitance or internal stress, or imparting heat dissipation. The film thickness of the cured form (the film formed by the cured form) is preferably 0.5 μm or more and 150 μm or less.

[0765] 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, 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.

[0766] Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0767] <Characteristics of cured resin compositions>

[0768] 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 sometimes results in a cured product with excellent mechanical properties.

[0769] 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.

[0770] 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.

[0771] <Preparation of Resin Compositions>

[0772] 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.

[0773] Examples of mixing methods include mixing using stirring blades, mixing using a ball mill, and mixing by rotating a tank.

[0774] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0775] 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. Regarding the filter pore size, it is preferably 5 μm or less, more preferably 1 μm or less, further preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. Filters that have been pre-cleaned with an organic solvent can be used. In the filtration process, multiple filters can be connected in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, an HDPE filter with a 1 μm pore size can be used as the first stage, and an HDPE filter with a 0.2 μm pore size can be used as the second stage, and the two can be connected in series. Furthermore, various materials can be filtered multiple times. In the case of multiple filtrations, it can be a circulating filtration. Furthermore, pressure filtration can be performed. When pressure filtration is performed, the pressure applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[0776] In addition to filtration using filters, impurities can also be removed using adsorption materials. A combination of filtration and impurity removal using adsorption materials can also be used. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0777] After filtration, the resin composition filled in the bottle can be degassed under reduced pressure.

[0778] (Method for manufacturing solidified products)

[0779] 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.

[0780] A more preferred method for manufacturing a cured material is to include the above-described film forming step, an exposure step for selectively exposing the film formed by the film forming step, and a developing step for developing the film exposed by the exposure step using a developing solution to form a pattern.

[0781] 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.

[0782] Furthermore, the method for manufacturing the cured material is preferably to include the above-described film formation process and the process of heating the film.

[0783] The following is a detailed explanation of each process.

[0784] <Membrane Formation Process>

[0785] The resin composition of the present invention can be used in a film forming process in which it is applied to a substrate to form a film.

[0786] 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.

[0787] [Substrate]

[0788] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any substrate formed of metal or substrates with a metal layer formed by electroplating or vapor deposition); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In particular, semiconductor substrates are preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[0789] Layers such as a sealing layer or an oxide layer formed of hexamethyldisilazane (HMDS) can be provided on the surface of these substrates.

[0790] The shape of the substrate is not particularly limited; it can be circular or rectangular.

[0791] Regarding the dimensions of the substrate, if it is circular, the diameter is preferably 100–450 mm, more preferably 200–450 mm. If it is rectangular, the length of the shorter side is preferably 100–1000 mm, more preferably 200–700 mm.

[0792] As a substrate, a plate-like material can be used, and a panel-like substrate (substrate) is preferred.

[0793] When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer formed by curing) or a metal layer, the resin layer or the metal layer becomes the substrate.

[0794] As a method for applying the resin composition to a substrate, coating is preferred.

[0795] 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 viewpoints 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 is preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating is preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[0796] Furthermore, it is also possible to apply a method for transferring a coating that has been applied and formed on a temporary support in advance by the above-described application method onto a substrate.

[0797] 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 may preferably be used.

[0798] Furthermore, a process can be performed to remove excess film from the ends of the substrate. Examples of such processes include edge bead rinse (EBR) and back-side rinse.

[0799] 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 the wettability of the substrate, and then the resin composition is applied.

[0800] <Drying Process>

[0801] 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).

[0802] 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.

[0803] The drying process described above is preferably performed after the film formation process and before the exposure process.

[0804] The drying temperature of the membrane in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Furthermore, drying can be carried out under reduced pressure. The drying time can be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0805] <Exposure Process>

[0806] The above-mentioned film can be used in an exposure process that selectively exposes the film.

[0807] The method for manufacturing a cured material may include an exposure process that selectively exposes a film formed by a film forming process.

[0808] Selective exposure refers to exposing only a portion of the film. Furthermore, by selectively exposing the film, exposed areas (exposed portions) and unexposed areas (non-exposed portions) are formed on the film.

[0809] The exposure amount 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 10,000 mJ / cm based on the exposure energy at a wavelength of 365 nm. 2 More preferably 200–8,000 mJ / cm 2 .

[0810] The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0811] 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), and wide wavelengths (gamma, h, i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet (EUV) (wavelength 13.6nm), (6) electron beams, and (7) second harmonic 532nm and third harmonic 355nm of YAG lasers. Regarding the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and from the viewpoint of exposure sensitivity, exposure using i-rays is more preferred.

[0812] There is no particular limitation on the exposure method, as long as at least a portion of the film formed by the resin composition of the present invention is exposed, but examples include exposure using a photomask, exposure using direct laser imaging, etc.

[0813] <Post-exposure heating process>

[0814] The above-mentioned film can be used in a process of heating after exposure (post-exposure heating process).

[0815] 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.

[0816] The post-exposure heating process can be performed after the exposure process and before the development process.

[0817] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0818] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0819] 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.

[0820] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0821] There are no particular limitations on the heating method used in the post-exposure heating process; known heating plates, ovens, infrared heaters, etc., can be used.

[0822] Furthermore, during heating, it is preferable to conduct the process in a low-oxygen environment by circulating inactive gases such as nitrogen, helium, or argon.

[0823] <Developing Process>

[0824] The exposed film can be used in the developing process to form a pattern by developing it with a developing solution.

[0825] 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.

[0826] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[0827] 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.

[0828] [Developing solution]

[0829] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0830] 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 alkaline 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.

[0831] 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., are preferably examples of alcohols, and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., are preferably examples of amides.

[0832] When the developer contains an organic solvent, one or more organic solvents may 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.

[0833] 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.

[0834] The developer may further contain other ingredients.

[0835] Other components include, for example, well-known surfactants or well-known defoamers.

[0836] [Method for supplying developer]

[0837] 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.

[0838] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, the method of supplying developer with a straight nozzle or the method of continuous supply with a spray nozzle is preferred. From the viewpoint of developer penetration into the image area, the method of supplying with a spray nozzle is more preferred.

[0839] Furthermore, the following steps can be adopted: after continuously supplying developer with a straight nozzle, rotating the substrate to remove developer from the substrate, rotating and drying, and then continuously supplying developer with a straight nozzle again, rotating the substrate to remove developer from the substrate, or repeating this step multiple times.

[0840] Methods for supplying developer in the developing process include: a process of continuously supplying developer to a substrate; a process of keeping the developer in a substantially static state on the substrate; a process of vibrating the developer on the substrate using ultrasound or the like; and processes that combine these methods.

[0841] 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 limited, but is preferably 10 to 45°C, more preferably 18°C ​​to 30°C.

[0842] In the developing process, the pattern can be further cleaned (rinsed) using a rinsing solution after treatment with the developing solution. Alternatively, the rinsing solution can be supplied before the developing solution in contact with the pattern has completely dried.

[0843] [Rinse solution]

[0844] 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.

[0845] As an organic solvent in the rinsing solution, examples of organic solvents can be the same as those exemplified in the developing solution described above.

[0846] The organic solvent contained in the rinsing solution is preferably an organic solvent that is different from the organic solvent contained in the developing solution, and more preferably an organic solvent with low solubility in the pattern compared to the organic solvent contained in the developing solution.

[0847] When the rinsing solution contains an organic solvent, one or more organic solvents may be used. Preferably, the organic solvent is cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME; more preferably, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME; and even more preferably, cyclohexanone or PGMEA.

[0848] When the rinsing solution contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Furthermore, the organic solvent can be 100% by mass, relative to the total mass of the rinsing solution.

[0849] The rinsing solution may further contain other ingredients.

[0850] Other components include, for example, well-known surfactants or well-known defoamers.

[0851] [Method for supplying flushing fluid]

[0852] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the rinsing liquid. Methods include immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by filling the container, supplying the rinsing liquid to the substrate by spraying, and continuously supplying the rinsing liquid to the substrate using a straight nozzle.

[0853] From the perspectives of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, methods for supplying rinsing fluid include spray nozzles, straight nozzles, and mist nozzles. A continuous supply method using a mist nozzle is preferred. From the perspective of the penetrability of the rinsing fluid to the image area, a supply method using a mist nozzle is even more preferred. There are no particular limitations on the type of nozzle; examples include straight nozzles, spray nozzles, and mist nozzles.

[0854] That is, the rinsing process is preferably a process of supplying or continuously supplying rinsing liquid to the exposed film using a straight nozzle, and more preferably a process of supplying rinsing liquid through a spray nozzle.

[0855] As a method for supplying rinsing fluid in the rinsing process, it is possible to employ a process of continuously supplying rinsing fluid to the substrate, a process of maintaining the rinsing fluid on the substrate in a substantially static state, a process of vibrating the rinsing fluid on the substrate using ultrasound or the like, and a process that combines these methods.

[0856] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution is not particularly limited, but is preferably 10 to 45°C, more preferably 18°C ​​to 30°C.

[0857] <Heating Process>

[0858] The pattern obtained through the developing process (the pattern after rinsing during the washing process) can be used in a heating process for heating the pattern obtained through the developing process.

[0859] 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.

[0860] 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.

[0861] During the heating process, resins such as polyimide precursors are cyclized to form resins such as polyimide.

[0862] Furthermore, crosslinking of unreacted crosslinking groups in specific resins or polymeric compounds other than specific resins is also performed.

[0863] The heating temperature (maximum heating temperature) in the heating process is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, and even more preferably 160 to 250°C, especially preferably 160 to 230°C.

[0864] The heating process is preferably a process in which the cyclization reaction of the polyimide precursor is promoted within the pattern by heating and utilizing the action of the alkali or the like generated by the alkali generating agent.

[0865] In the heating process, heating is preferably carried out from the initial temperature to the maximum heating temperature at a heating rate of 1 to 12°C / min. More preferably, the heating rate is 2 to 10°C / min, and even more preferably 3 to 10°C / min. Setting the heating rate to 1°C / min or more ensures productivity while preventing excessive evaporation of acid or solvent; setting the heating rate to 12°C / min or less reduces residual stress in the cured product.

[0866] 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.

[0867] The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the process of heating to the maximum heating temperature begins. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the dried film (layer) is preferred; for example, it is preferably started at a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0868] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0869] In particular, when forming a multilayered laminate, from the viewpoint of interlayer tightness, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher.

[0870] The upper limit of the above heating temperature is preferably below 350°C, more preferably below 250°C, and even more preferably below 240°C.

[0871] Heating can be performed in stages. For example, the following steps can be performed: increasing the temperature from 25°C to 120°C at a rate of 3°C / minute, holding at 120°C for 60 minutes, and increasing the temperature from 120°C to 180°C at a rate of 2°C / minute, holding at 180°C for 120 minutes. Furthermore, as described in U.S. Patent No. 9,159,547, it is also preferable to perform the treatment while irradiating with ultraviolet light. This pretreatment process can improve the properties of the membrane. The pretreatment process can be performed in a short time, approximately 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process can be a two-stage or more process; for example, the first stage of the pretreatment process can be performed in the range of 100–150°C, followed by the second stage of the pretreatment process in the range of 150–200°C.

[0872] In addition, cooling can be performed after heating, and the preferred cooling rate at this time is 1 to 5°C / minute.

[0873] From the viewpoint of preventing the decomposition of specific resins, the heating process is preferably carried out in a low-oxygen environment by circulating inactive gases such as nitrogen, helium, or argon and by conducting the process under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[0874] There are no particular limitations on the heating method used in the heating process. Examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0875] <Post-development exposure process>

[0876] The pattern obtained through the developing process (the pattern after rinsing during the washing process) can also replace the heating process described above, or, in addition to the heating process described above, can be used in a post-developing exposure process to expose the pattern after the developing process.

[0877] 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 either a heating step or a post-development exposure step.

[0878] In the post-development exposure process, for example, it can promote the cyclization reaction of polyimide precursors, etc., by photosensitive alkali-generating agents, and the removal of acid-degrading groups by photosensitive acid-generating agents.

[0879] 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.

[0880] Based on the exposure energy conversion at the wavelength where the photosensitive compound has sensitivity, the exposure amount in the post-development exposure process is preferably 50–20,000 mJ / cm². 2 More preferably 100–15,000 mJ / cm 2 .

[0881] Regarding the post-development exposure process, for example, the light source used in the above-described exposure process can be used, and broadband light is preferred.

[0882] <Metal Layer Formation Process>

[0883] 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 also be used in the metal layer forming process for forming a metal layer on the pattern.

[0884] That is, the method for manufacturing the cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably a pattern for at least one of a heating step and a post-developing exposure step).

[0885] 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.

[0886] 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, methods such as photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electrolytic plating can be cited. As a preferred method of electroplating, electrolytic plating using copper sulfate plating solution or copper cyanide plating solution can be cited.

[0887] The thickness of the metal layer, measured in the thickest part, is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

[0888] <Application>

[0889] Examples of applications in the manufacture of cured products to which the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress-relief films. Other applications include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), or patterns formed on insulating films used for mounting purposes, such as those described above, through etching. For these applications, references can be made to Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimides,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and the Japan Polyimide & Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[0890] The method for manufacturing the cured product of the present invention or the cured product of the present invention can also be used for manufacturing offset printing plates or screen printing plates, etching of shaped parts, manufacturing of protective coatings and dielectric layers in the electronic field, especially in the microelectronic field.

[0891] (Laminated bodies and methods for manufacturing laminated bodies)

[0892] The laminate of the present invention refers to a structure having multiple layers formed by the cured product of the present invention.

[0893] A laminate is a laminate containing two or more layers formed by a solidified material, or it can be a laminate consisting of three or more layers.

[0894] Of the two or more layers formed by the cured material contained in the above-described laminate, at least one layer is formed by 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 formed by the cured material contained in the above-described laminate are formed by the cured material of the present invention.

[0895] 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 repeated multiple times.

[0896] The laminate of the present invention preferably comprises two or more layers formed of a cured material, and a metal layer is included between any of the layers formed of the cured material. The metal layer is preferably formed by the aforementioned metal layer forming process.

[0897] That is, the method for manufacturing the laminate of the present invention preferably includes a metal layer forming step between the methods for manufacturing multiple cured products, wherein a metal layer is formed on the layer formed by the cured product. The preferred embodiment of the metal layer forming step is as described above.

[0898] As a preferred example of the aforementioned laminate, a laminate containing at least three layers stacked sequentially: a layer formed of a first cured material, a metal layer, and a layer formed of a second cured material is a preferred example.

[0899] 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 different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0900] <Layering Process>

[0901] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0902] The lamination process includes a series of steps on the surface of a pattern (resin layer) or metal layer, sequentially performing at least one of the following steps: (a) film formation (layer formation step), (b) exposure step, (c) development step, (d) heating step, and post-development exposure step. This can be done by repeating at least one of (a) film formation step, (d) heating step, and post-development exposure step. Furthermore, (e) metal layer formation step can be included after at least one of (d) heating step and post-development exposure step. The lamination process can, of course, further appropriately include the aforementioned drying step, etc.

[0903] 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 is an example of a surface activation treatment. Details regarding surface activation treatment will be described later.

[0904] The above-mentioned lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0905] For example, in a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer structure, 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.

[0906] The composition, shape, and film thickness of each of the above layers can be the same or different.

[0907] In this invention, it is particularly preferred that, after the metal layer is formed, a cured product (resin layer) of the resin composition of the present invention is further formed to cover 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.

[0908] (Surface activation treatment process)

[0909] The preferred method for manufacturing the laminate of the present invention includes a surface activation treatment step that involves surface activation treatment of at least a portion of the metal layer and the resin composition layer.

[0910] The surface activation treatment process is usually performed after the metal layer formation process, but it can also be performed after the above-mentioned 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.

[0911] 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 its surface can be improved.

[0912] The surface activation treatment is preferably performed on part or all of the exposed resin composition layer (resin layer). In this way, by performing a surface activation treatment on 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 cured, such as during negative development, it is less likely to be damaged by the surface treatment, and adhesion is easily improved.

[0913] Surface activation treatment 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.

[0914] (Semiconductor devices and their manufacturing methods)

[0915] The present invention also discloses semiconductor devices comprising the cured or laminated material of the present invention.

[0916] 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.

[0917] 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.

[0918] (Diamine compounds)

[0919] The diamine compound of the present invention is the compound represented by the following formula (4-1).

[0920] [Chemical Formula 62]

[0921]

[0922] In equation (4-1), R 3 and R 4 Each group independently represents a group having an olefinic unsaturated bond, R 3 and R 4At least one of them has an aromatic hydrocarbon group, where L represents a single bond, -C(CH3)2- or -C(CF3)2-.

[0923] In equation (4-1), R 3 and R 4 The preferred method is the same as R in the above formula (2-1). 1 and R 2 The preferred method is the same.

[0924] In these, in equation (4-1), R 3 and R 4 Each is preferably independently of having a vinylphenyl group.

[0925] The diamine of the present invention can be obtained, for example, by reacting a diamine having a phenolic hydroxyl group as represented by the following formula (4-C) with a benzyl halide substituted with a group having an olefinic unsaturated bond, an isocyanate compound containing a group having an olefinic unsaturated bond, or a compound containing a group having an olefinic unsaturated bond and reacting with a phenolic hydroxyl group.

[0926] However, the synthetic method is not limited as long as the compound with the structure represented by the above formula (4-1) can be obtained.

[0927] [Chemical Formula 63]

[0928]

[0929] In equation (4-C), the meaning of L is the same as that of L in equation (4-1) above, and the preferred method is also the same.

[0930] Example

[0931] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing contents, processing order, etc., shown in the following examples can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass measurements.

[0932] (Synthesis of monomers)

[0933] <Synthesis example AA-1>

[0934] 48.65 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide were mixed in a 1 L flask. 98.21 g (450 mmol) of di-tert-butyl dicarbonate was added dropwise under ice-cooling. After the addition was complete, the mixture was stirred at 60 °C for 5 hours. After the reaction was complete and cooled to room temperature, 35 mg of 2,2,6,6-tetramethylpiperidine 1-oxy radical, 68.68 g (450 mmol) of p-chloromethylstyrene, 74.63 g (540 mmol) of potassium carbonate, and 8.96 g (54.0 mmol) of potassium iodide were added, and the mixture was stirred at 60 °C for 3 hours. After the reaction was complete, the mixture was filtered by vacuum filtration, and the filtrate was added dropwise to 500 mL of water. White crystals precipitated, and the precipitated solid was recovered by vacuum filtration. The obtained white solid was purified by recrystallization using 1000 mL of acetone at 60 °C. 125 g (yield 85.6%) of the following intermediate AA-1a was obtained.

[0935] The structure of AA-1a is shown below. 1 H-NMR spectroscopy confirmed the following structure.

[0936] 1 H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6) 8.04-7.94 (s, 2H), 7.75-7.64 (d, 2H), 7.56-7.42 (m, 8H), 7.27-7.20 (d , 2H), 7.19-7.12(d, 2H), 6.79-6.64(2H), 5.89-5.77(2H), 5.30-5.15(6H), 1.49-1.43(s.18H)

[0937] [Chemical Formula 64]

[0938]

[0939] 75.0 g (115.6 mmol) of (AA-1a) and 500 mL of dichloromethane were mixed in a 1 L flask. After adding 131.8 g (1156 mmol) of trifluoroacetic acid at room temperature, the mixture was stirred at 40 °C for 5 hours. After the reaction was complete, 250 mL of methanol was added dropwise under ice-cooling, followed by 117.0 g (1156 mmol) of triethylamine. Pale yellow crystals precipitated, and the precipitated solid was recovered by filtration. The solid was washed with 750 mL of methanol to obtain 40.5 g of (AA-1) (73% yield). The structure of AA-1 is shown below. 1 H-NMR spectroscopy confirmed the following structure.

[0940] 1H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6) 7.53-7.45 (s, 8H), 7.05-6.98 (d, 2H), 6.92-6.85 (d, 2H), 6.79 -6.63(4H), 5.89-5.78(d, 2H), 5.29-5.22(d, 2H), 5.20-5.13(s, 4H), 4.92-4.64(4H)

[0941] [Chemical Formula 65]

[0942]

[0943] <Synthesis examples AA-2, AA-3, AA-4, AA-6, AA-7>

[0944] In synthetic example AA-1, 3,3'-dihydroxybenzidine was appropriately substituted, and AA-2, AA-3, AA-4, AA-6, and AA-7 were otherwise obtained by the same method. The structures of each compound are shown below. 1 H-NMR spectroscopy confirmed the following structure.

[0945] <Synthesis example AA-5>

[0946] In synthetic example AA-1, p-chloromethylstyrene was replaced with KALENDS MOI (manufactured by SHOWA DENK0K.K.), and AA-5 was otherwise obtained by the same method. The structure of AA-5 is shown below. 1 H-NMR spectroscopy confirmed the following structure.

[0947] [Chemical Formula 66]

[0948]

[0949] <Synthetic Example AT-1>

[0950] In synthetic example AA-1, 3,3'-dihydroxybenzidine was replaced with p-methoxyphenol, and AT-1 was otherwise obtained by the same method.

[0951] The following shows the structure of the AT-1. (The structure is described below.) 1 H-NMR spectroscopy confirmed the following structure.

[0952] 1H-NMR (BRUKER, AVANCE NE0400): δ (ppm, DMSO-d6) 7.52-7.42 (d, 2H), 7.42-7.32 (d, 2H), 6.80-6.63 (3H), 6. 54-6.43(d,2H),5.92-5.77(1H),5.30-5.19(1H),4.95-4.89(s,2H),4.68-4.54(2H)

[0953] [Chemical Formula 67]

[0954]

[0955] (Polymer Synthesis)

[0956] <Synthetic Example A-1: ​​Synthesis of Polyimide (A-1)>

[0957] 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 9.93 g (24.2 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 10.86 g (24.2 mmol) of AA-1, and 1.30 g (5.76 mmol) of AT-1 were dissolved in 100 g of NMP. This solution was added dropwise to the above solution over 1 hour at 0–10 °C. After stirring at 25 °C for 60 minutes, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the reaction was carried out at 80 °C for 4 hours. After the reaction was complete, the solution was cooled to 25°C and diluted with 200g of tetrahydrofuran. Next, the reaction solution was added dropwise to a mixture of 2.0L methanol and 0.5L water, and after stirring for 15 minutes, the polyimide resin was filtered. Then, the resin was re-slurryed with 1L water, filtered, and then re-slurryed again with 1L methanol, filtered, and dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in 250g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (A-1). The obtained polyimide (A-1) has a weight-average molecular weight of 25,000 and a number-average molecular weight of 9,960. Polyimide (A-1) is a resin having repeating units represented by the following formula (A-1). 1H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit. The phenolic hydroxyl value (content of phenolic hydroxyl groups) of A-1 is 0.010 mmol / g, and ΔIm = 2.1%.

[0958] The phenolic hydroxyl value was calculated using the following determination conditions.

[0959] -Determination Conditions-

[0960] · 1 H-NMR (BRUKER, AVANCE NEO 400)

[0961] • Analysis software: TopSpin 4.0.7

[0962] Solvent: DMSO-d6

[0963] Internal standard: 1,3,5-trimethoxybenzene

[0964] exist 1 In H-NMR, the proton of the phenolic hydroxyl group was detected by a specific peak near δ(DMSO-d6) = 10 ppm. Furthermore, 1,3,5-trimethoxybenzene, serving as an internal standard, was detected by a specific peak at 6.1 ppm.

[0965] ΔIm is the rate of change of the imide group value before and after heating at 350°C and 1 atmosphere for 1 hour, calculated by the following formula.

[0966] Rate of change (ΔIm, %) = (Im2 - Im1) × 100 / Im1

[0967] Im1: Imine group value before heating (mmol / g)

[0968] Im2: Imine group value (mmol / g) after heating at 350℃ and 1 atm for 1 hour.

[0969] Specifically, by measuring the infrared absorption spectrum of a specific resin, the absorption peak at 1377 cm⁻¹, which originates from the imide bond, was determined. -1 The peak intensity P1 was observed nearby. Next, after heat-treating the specific resin at 350°C and 1 atm for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity at 1377 cm⁻¹ was determined. -1 The nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the rate of change of the imide group value was calculated according to the following formula. Peak intensity P1 represents the imide group value before heating, i.e., Im1, and peak intensity P2 represents the imide group value Im2 after heating.

[0970] The rate of change of imide group value (%) = (peak intensity P2 - peak intensity P1) × 100 / peak intensity P1

[0971] [Chemical Formula 68]

[0972]

[0973] <Synthetic Example A-2: Synthesis of Polyimide (A-2~15)>

[0974] With appropriate changes to the raw materials used, polyimides (A-2) to (A-15) were synthesized using the same method as polyimide (A-1).

[0975] Polyimide (A-2) to (A-15) are resins having repeating units represented by the formulas (A-2) to (A-15). 1 H-NMR spectroscopy determined the structure of each repeating unit. In the following structures, the ratios indicate the molar ratio of each structure. Furthermore, the weight-average molecular weight and number-average molecular weight of these resins are listed in the table below.

[0976] [Chemical Formula 69]

[0977]

[0978] [Chemical Formula 70]

[0979]

[0980] [Chemical Formula 71]

[0981]

[0982] [Chemical Formula 72]

[0983]

[0984] [Chemical Formula 73]

[0985]

[0986] [Chemical Formula 74]

[0987]

[0988] [Table 1]

[0989] resin weight average molecular weight Number average molecular weight Phenolic hydroxyl value (mmol / g) AIm(%) A-2 20,000 8,060 0.015 1.0 A-3 22,000 9,130 0.030 1.7 A-4 21,000 8,800 0.040 1.5 A-5 23,000 9,020 0.020 2.0 A-6 21,000 8,940 0.075 2.0 A-7 19,000 8,150 0.010 1.0 A-8 22,500 9,180 0.015 1.5 A-9 21,000 8,400 0.033 2.5 A-10 28,500 10,900 0.080 2.8 A-11 22,000 9,160 0.025 1.0 A-12 19,500 8,230 0.015 1.5 A-13 51,000 17,250 0.055 5.2 A-14 19,000 7,450 0.105 1.3 A-15 21,000 9,250 0.035 1.5 A-19 24,500 10,100 0.040 1.5 A-20 20,300 8,500 0.050 1.3

[0990] <Synthetic Example A-16: Synthesis of Polyimide (A-16)>

[0991] In Synthesis Example 1, 10.86 g (24.2 mmol) of AA-1 was replaced with a mixture of 10.32 g (23.0 mmol) of AA-1 and 0.26 g (1.2 mmol) of 3,3'-dihydroxybenzidine. Otherwise, polyimide (A-16) was synthesized by the same method as polyimide (A-1). The obtained polyimide (A-16) had a weight-average molecular weight of 23,000 and a number-average molecular weight of 9,150.

[0992] The phenolic hydroxyl value is 0.230 mmol / g, and ΔIm = 2.0%.

[0993] <Synthetic Examples A-17, A-18: Synthesis of Polyimide (A-17, A-18)>

[0994] In Synthesis Example 1, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the reaction time of 4 hours at 80°C was changed to 1 hour (A-17) or 2 hours (A-18). Otherwise, polyimides (A-17) and (A-18) were synthesized by the same method as polyimide (A-1). The obtained polyimide (A-17) had a weight-average molecular weight of 23,300, a number-average molecular weight of 9,250, a phenolic hydroxyl value of 0.015 mmol / g, and ΔIm = 25.5%. The polyimide (A-18) had a weight-average molecular weight of 24,700, a number-average molecular weight of 9,850, a phenolic hydroxyl value of 0.010 mmol / g, and ΔIm = 20.7%.

[0995] <Comparative Synthesis Example AC-1: Synthesis of Polyimide (AC-1)>

[0996] 24.74 g (40 mmol) of 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl-1,3-dioxoisobenzofuran-5-carboxylic acid ester was dissolved in 70 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 6.45 g (17.6 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 5.64 g (17.6 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl were dissolved in 50 g of NMP and added dropwise to the above solution over 1 hour at a temperature of 10°C–25°C. After stirring at 25°C for 30 minutes, 10 g of toluene was added, and the reaction was carried out at 200°C for 4 hours under nitrogen gas. The mixture was then cooled to 25°C. Next, 4.97 g (35.2 mmol) of 2-isocyanatoethyl acrylate and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were added. The mixture was reacted at 95°C for 15 hours, then cooled to 25°C and diluted with 120 g of tetrahydrofuran. The reaction mixture was then added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered. The resin was then re-slurried with 1 L of water and filtered, followed by re-slurrying again with 1 L of methanol and filtering. The resin was dried under reduced pressure at 40°C for 8 hours. The dried resin was then dissolved in 250 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, filtered to remove the ion exchange resin, and the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried at 45°C under reduced pressure for 1 day to obtain polyimide (AC-1). Polyimide (AC-1) is a resin having repeating units represented by the following formula (AC-1). 1 H-NMR spectroscopy determined the structure of the repeating unit. The obtained polyimide (AC-1) had a weight-average molecular weight of 19,500 and a number-average molecular weight of 7,450.

[0997] The phenolic hydroxyl value is 0.370 mmol / g, and ΔIm = 3.1%.

[0998] [Chemical Formula 75]

[0999]

[1000] <Examples and Comparative Examples>

[1001] In each embodiment, the components listed in the table were mixed to obtain each resin composition. Furthermore, in each comparative example, the components listed in the table were mixed to obtain each comparative composition.

[1002] Specifically, the content of each component listed in the table, excluding the solvent, is set as the amount (parts by mass) recorded in the "parts by mass" column of each column in the table.

[1003] The solvent content is set as the amount of the solid component concentration of the composition as stated in the "Solid Component Concentration (mass%)" column of the table. Furthermore, the ratio of the amount of each solvent used is set as the content ratio (mass ratio) recorded in the "Ratio" column of the table.

[1004] The obtained resin composition and the comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm.

[1005] Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

[1006] [Table 2]

[1007]

[1008] [Table 3]

[1009]

[1010] [Table 4]

[1011]

[1012] [Table 5]

[1013]

[1014] The detailed information for each component listed in the table is as follows.

[1015] [Resin]

[1016] • A-1 to A-20, AC-1: Polyimides A-1 to A-20, AC-1 synthesized in the above process

[1017] A-1 to A-20 are compounds corresponding to specific resins.

[1018] [Polymerizing compounds]

[1019] ·B-1: SR-209 (manufactured by Sartomer Company, Inc.)

[1020] • B-2: ADPH: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1021] •B-3: Compounds with the following structures

[1022] •B-4: Compounds with the following structures

[1023] [Chemical Formula 76]

[1024]

[1025] [Polymerization initiator]

[1026] •C-1: IRGACURE OXE 01 (Made by BASF)

[1027] •C-2: IRGACURE OXE 02 (manufactured by BASF)

[1028] • C-3: IRGACURE 369 (manufactured by BASF)

[1029] • C-4: Compounds with the following structures

[1030] • C-5: Compounds with the following structures

[1031] • C-6: Compounds with the following structures

[1032] • C-7: Omnirad 1312 (made by IGM)

[1033] • C-8: Omnirad TP0 H (Made by IGM Corporation)

[1034] • C-9: CPI-310FG (manufactured by San-Apro Ltd.)

[1035] • C-10: CPI-310B (manufactured by San-Apro Ltd.)

[1036] • C-11: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1037] [Chemical Formula 77]

[1038]

[1039] [Heat-generated alkali agent]

[1040] • D-1 to D-7: Compounds represented by formulas (D-1) to (D-7) below

[1041] [Chemical Formula 78]

[1042]

[1043] [Polymerization inhibitor]

[1044] E-1: 2-Nitrosamino-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1045] E-2: p-Benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1046] E-3: p-Methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1047] E-4: Compounds with the following structure

[1048] E-5: Compounds with the following structures

[1049] [Chemical Formula 79]

[1050]

[1051] [Migration Inhibitor]

[1052] • F-1~F-8: Compounds with the following structures.

[1053] [Chemical Formula 80]

[1054]

[1055] [Silane coupling agent]

[1056] • G-1~G-4: Compounds with the following structures. In the following structural formulas, Et represents the ethyl group.

[1057] ·G-5: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1058] ·G-6: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1059] [Chemical Formula 81]

[1060]

[1061] [Solvent]

[1062] ·GBL: Y-Dingneiyouzhi

[1063] DMSO: Dimethyl sulfoxide

[1064] NMP: N-methyl-2-pyrrolidone

[1065] ·EL: lactate ethidium

[1066] • GVL: γ-valerolactone

[1067] • MDMPA: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.)

[1068] ·CP: Cyclopentanone

[1069] CH: Cyclohexanone

[1070] 〔additive〕

[1071] H-1: Compounds with the following structure

[1072] H-2: N-Phenylonamine

[1073] H-3: Compounds with the following structure

[1074] H-4: Compounds with the following structure

[1075] H-5: Compounds with the following structure

[1076] [Chemical Formula 82]

[1077]

[1078] H-5 was synthesized according to the following synthesis method.

[1079] [Synthesis method of H-5]

[1080] 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-naphthoquinone diazido-5-sulfonyl chloride and 17.9 g of triethylamine were dissolved in 300 g of acetone by stirring. This solution was added dropwise to the flask over 30 minutes using a dropping funnel, and the mixture was stirred at 30°C for 30 minutes. Then, hydrochloric acid was added dropwise, followed by stirring for another 30 minutes. Next, a solution of 1640 g of pure water and 30 g of hydrochloric acid was prepared in a beaker. A filtrate containing the hydrochloride salt from the reaction solution was added dropwise to this solution. The precipitate was filtered, washed with water, and dried under vacuum at 40°C for 50 hours to obtain the diazonoquinone compound H-5.

[1081] [Titanium compounds]

[1082] I-1: TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1083] I-2: TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1084] I-3: TC-800 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1085] I-4: TC-810 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1086] I-5~I-8: Compounds with the following structures

[1087] [Chemical Formula 83]

[1088]

[1089] <Evaluation>

[1090] [Evaluation of dielectric loss tangent (Df)]

[1091] By spin coating, each resin composition or comparative composition prepared in the various examples and comparative examples was applied to a 12-inch silicon wafer to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes, forming a resin composition layer of uniform thickness as recorded in the "Film Thickness (μm)" column of the table on the silicon wafer. Using a stepper (Nikon NSR 2005i9C), the resin composition layer on the silicon wafer was exposed to the entire surface at an exposure energy of 500 mJ / cm². The exposed resin composition layer (resin layer) was heated in a nitrogen atmosphere at a heating rate of 10°C / min for the time specified in the "Curing Temperature (°C)" column of the table, thereby obtaining a cured layer (resin layer) of the resin composition layer.

[1092] The cured layer (resin film) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution and then peeled off from the silicon wafer.

[1093] For the thin film samples, the relative permittivity (Dk) and dielectric loss tangent (Df) at 28 GHz were determined using the resonator perturbation method. The dielectric loss tangent (Df) was evaluated according to the following criteria, and the evaluation results are recorded in the "Df" column of the table.

[1094] <Determination Method>

[1095] Split cylindrical resonator (CR-728)

[1096] (Device Structure)

[1097] Network Analyzer: N5230A (manufactured by KEYSIGHT)

[1098] (Evaluation Criteria)

[1099] Dielectric loss tangent (Df)

[1100] A: The dielectric loss tangent (Df) is less than 0.015.

[1101] B: Dielectric loss tangent (Df) is less than 0.015 to 0.02.

[1102] C: Dielectric loss tangent (Df) is above 0.02.

[1103] [Evaluation of metal seal]

[1104] Each resin composition or comparative composition prepared in the respective examples and comparative examples was applied in a layered manner onto a copper substrate using a spin-coating method to form a resin composition layer or comparative composition layer. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes, resulting in a resin composition layer or comparative composition layer of uniform thickness as described in the "Film Thickness (μm)" column of the table on the copper substrate. A stepper (Nikon NSR 2005 i9C) was used at 500 mJ / cm². 2 Using an exposure energy of [specific value], and employing a mask with a non-mask portion forming a square of 100 μm, the resin composition layer or comparative composition layer on a copper substrate is exposed to I-rays. Then, it is developed for 60 seconds with the developer listed in the "Developer" column of the table, and rinsed with propylene glycol monomethyl ether acetate (PGMEA), thereby obtaining a resin layer with a square of 100 μm. Furthermore, under a nitrogen atmosphere, the resin layer (pattern) is formed by heating in a heated oven at the temperature listed in the "Curing Temperature (°C)" column of the table for the time listed in the "Curing Time (minutes)" column of the table.

[1105] For a 100 μm square resin layer on a copper substrate, the shear force was measured using an adhesive strength tester (XYZTEC, CondorSigma) at 25°C and 65% relative humidity (RH). It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. In all embodiments and comparative examples, the shear force exceeded 30 gf.

[1106] [Evaluation of sealing strength after HTS (High Temperature Storage-test)]

[1107] The resin layer and copper substrate were heated to the temperature listed in the "Curing Temperature (°C)" column of the table and for the time listed in the "Curing Time (min)" column of the table. The mixture was then kept in a constant temperature bath at 175°C for 1000 hours. In addition, the shear force was measured using the same evaluation method as described in the evaluation of metal adhesion, and the metal adhesion after heating was evaluated. Based on the measured shear force, the evaluation was conducted according to the following evaluation criteria, and the evaluation results are recorded in the "Reliability (Adhesion Force after HTS)" column of the table. It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film, and the better the adhesion force after HTS, thus preventing peeling between the cured film and the metal even after a long period of time.

[1108] (Evaluation Criteria)

[1109] A: The shear force exceeded 30gf.

[1110] B: Shear force exceeding 25gf and below 30gf.

[1111] C: Shear force is below 25gf.

[1112] Furthermore, 1gf is 0.00980665N.

[1113] [Elongation at break]

[1114] In each embodiment and comparative example, the resin composition or the comparative composition was applied in a layered manner onto a silicon wafer by spin coating to form a resin composition layer or a comparative composition layer. The silicon wafer to which the obtained resin composition layer or comparative composition layer was applied was dried on a hot plate at 100°C for 5 minutes, forming a resin composition layer or comparative composition layer of uniform thickness as shown in the "Film Thickness (μm)" column of the table on the silicon wafer. A stepper (Nikon NSR 2005i9C) was used at 500 mJ / cm². 2 The resin composition layer or comparative composition layer on the silicon wafer was exposed using the specified exposure energy. Using a heating plate under nitrogen atmosphere, the exposed resin composition layer or comparative composition layer was heated at a rate of 10°C / min. After reaching the temperature listed in the "Curing Temperature (°C)" column of the table, this temperature was maintained for the time listed in the "Curing Time (minutes)" column of the table to obtain a cured resin layer. The cured resin layer was then immersed in a 4.9% by mass hydrofluoric acid solution and peeled off from the silicon wafer to obtain resin film 1.

[1115] A 10 mm wide and 50 mm long film was prepared by punching resin film 1 using a punching tool. The elongation at break of the film was measured using a tensile testing machine (TENSILON) at a crosshead speed of 300 mm / min, along both the length and width directions of the film, at 25°C and 65% relative humidity (RH), according to JIS-K6251:2017. The elongation at break was calculated using Eb(%) = (Lb-L0) / L0×100 (Eb: elongation at cut, L0: length of the test piece before testing, Lb: length of the test piece when cut). Ten measurements of the elongation at break along the length direction were taken, and the arithmetic mean of the ten elongation at break (Eb) values ​​was used as the evaluation index. The evaluation was conducted according to the following evaluation criteria. Generally speaking, the higher the value of the above index, the better the elongation at break. The evaluation results are recorded in the "Elongation at Break" column of the table.

[1116] -Evaluation Criteria-

[1117] A: The above indicator value exceeds 60%.

[1118] B: The above indicator values ​​exceed 40% but are below 60%.

[1119] C: The above indicator value is below 40%.

[1120] <Example 101>

[1121] The resin composition used in Example 1 was applied in a layered manner to the surface of a resin substrate with a copper thin layer formed thereon using a spin-coating method. After drying at 100°C for 5 minutes to form a photosensitive film with a thickness of 20 μm, exposure was performed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 linewidth and spacing pattern and a linewidth of 10 μm). After the above exposure, the layer pattern was obtained by developing with cyclopentanone for 2 minutes and rinsing with PGMEA for 30 seconds.

[1122] Next, under nitrogen atmosphere, the temperature was increased at a rate of 10°C / min to 230°C, and then maintained at 230°C for 180 minutes to form an interlayer insulating film for the rewiring layer. This interlayer insulating film for the rewiring layer exhibits excellent insulation properties.

[1123] Furthermore, the results of using this rewiring layer to manufacture semiconductor devices with interlayer insulating film confirmed normal operation.

Claims

1. A resin composition comprising: A resin comprising repeating units represented by formula (1-1), including groups having olefinic unsaturated bonds, and having a phenolic hydroxyl content of 0.250 mmol / g or less; and Polymerizable compounds that contain olefinically unsaturated bonds. In equation (1-1), X 1 Y represents a tetravalent organic group. 1 This indicates a divalent organic group.

2. The resin composition according to claim 1, wherein, The resin is a resin that contains repeating units represented by the following formula (1-2) as repeating units represented by the formula (1-1). In equation (1-2), X 1 Y represents a tetravalent organic group. 2 This refers to a group that contains the group represented by the following formula (2-1). In equation (2-1), R 1 and R 2 Each group independently represents a group with an olefinic unsaturated bond, L represents a single bond or a divalent linking group that does not contain an imide bond, and * represents a bonding site with other structures.

3. The resin composition according to claim 1, wherein, The resin contains a vinylphenyl group as the group having an olefinic unsaturated bond.

4. A resin composition comprising: A resin comprising repeating units represented by formulas (1-3) below and comprising vinylphenyl; and Polymerizable compounds that contain olefinically unsaturated bonds. In equation (1-3), X 1 Y represents a tetravalent organic group. 3 This refers to a group that contains the group represented by the following formula (2-2). In equation (2-2), R 1 and R 2 Each group independently represents a group with an olefinic unsaturated bond, L represents a single bond, -C(CH3)2- or -C(CF3)2-, and * represents the bonding site with other structures.

5. The resin composition according to any one of claims 1 to 4, wherein, The resin has a structure represented by any of the following formulas (3-1) to (3-3). In equation (3-1), R 31 Y represents a tetravalent organic group. 31 R represents a divalent organic group. 31 * indicates a group containing an olefinic unsaturated bond, and * indicates a bonding site with other structures. In equation (3-2), X 31 Y represents a tetravalent organic group. 31 R represents a divalent organic group. 31 * indicates a group containing an olefinic unsaturated bond, and * indicates a bonding site with other structures. In equation (3-3), X 31 Y represents a tetravalent organic group. 31 R represents a divalent organic group. 32 and R 33 R represents an organic group that is either -OH or monovalent, respectively. 32 and R 33 At least one of them is a group with an olefinic unsaturated bond, and * indicates a bonding site with other structures.

6. The resin composition according to any one of claims 1 to 4, wherein, The resin is one in which the change rate of the imide group value, calculated by the following formula, before and after heating at 350°C and 1 atmosphere for 1 hour is less than 25%. Change rate (%) = (Im2 - Im1) × 100 / Im1, Iml: Imidamine group value before heating, in mmol / g. Im2: The imide group value after heating at 350℃ and 1 atmosphere for 1 hour, in mmol / g.

7. The resin composition according to any one of claims 1 to 4, wherein, The X 1 An organic group containing an organic group with a structure formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-4). In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group. In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can be optionally bonded to form a ring structure.

8. The resin composition according to any one of claims 1 to 4, wherein it contains an azole compound.

9. A diamine compound represented by the following formula (4-1), In equation (4-1), R 3 and R 4 Each group independently represents a group having an olefinic unsaturated bond, R 3 and R 4 At least one of them has an aromatic hydrocarbon group, where L represents a single bond, -C(CH3)2- or -C(CF3)2-.

10. The diamine compound according to claim 9, wherein, The R 3 and R 4 Each has a vinylphenyl group independently.

11. A resin composition comprising: The resin is a reaction product of the diamine compound of claim 9 and a compound or its derivative having a total of two or more carboxyl groups and carboxylic anhydride groups; and Polymers that have olefinic unsaturated bonds.

12. The resin composition according to any one of claims 1 to 4 and 11, used for forming an interlayer insulating film for a rewiring layer.

13. A cured product formed by curing the resin composition according to any one of claims 1 to 4 and 11.

14. A laminate comprising two or more layers formed from the cured material of claim 13, and comprising a metal layer between any of the layers formed from the cured material.

15. A method for manufacturing a cured product, comprising a film forming step of applying the resin composition of any one of claims 1 to 4 and 11 onto a substrate to form a film.

16. The method for manufacturing a cured product according to claim 15, comprising: The exposure process selectively exposes the film; and In the developing process, the film is developed using a developing solution to form a pattern.

17. The method for manufacturing a cured material according to claim 15, comprising a heating step of heating the film at a temperature of 50°C to 450°C.

18. A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in claim 15.

19. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in claim 15.

20. A semiconductor device comprising the cured material of claim 13.

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