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

Abstract

The present invention provides: a resin composition comprising a polyimide precursor and a solvent, wherein a cured product obtained by heating the resin composition at 300°C for 60 minutes exhibits a diffraction peak in the range of 5°-15° in an X-ray diffraction spectrum, and the crystallite size derived from the diffraction peak is 30 Å or more; a cured product obtained by curing the resin composition; a laminate comprising the cured product; and a method for producing the cured product.

Description

Resin composition, cured product, laminate, and method for producing the cured product

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

[0002] Polyimides have excellent heat resistance and insulating properties and are therefore used in a variety of fields, such as as insulating films for electronic devices. Patent Document 1 describes a composition comprising a polyimide polymer containing a reaction product of (a) a specific diamine, (b) a specific diamine, and (c) at least one tetracarboxylic dianhydride, a reactive functional compound, an initiator, and a solvent.

[0003] Japan Special Table No. 2020-502291

[0004] Polyimides are used in various fields, including semiconductors and aerospace, and improving their thermal properties is important. Among these, improved thermal conductivity and a lower coefficient of thermal expansion (CTE) are required.

[0005] An object of the present invention is to provide a resin composition capable of forming a cured product having high thermal conductivity and a low thermal expansion coefficient, a cured product obtained by curing the resin composition, a laminate including the cured product, and a method for producing the cured product.

[0006] Representative embodiments of the present invention are described below: [1] A resin composition comprising a polyimide precursor and a solvent, wherein a cured product obtained by heating the resin composition at 300°C for 60 minutes has a diffraction peak in the range of 5 to 15° in an X-ray diffraction spectrum, and a crystallite size derived from the diffraction peak is 30 Å or more.

[0007] [2] A resin composition comprising: a polyimide precursor having a repeating unit represented by the following formula (1); and a solvent, wherein the content of the repeating unit represented by the following formula (1) is 40 mol% or more based on all repeating units of the polyimide precursor.

[0008]

[0009] In formula (1), X２ represents a group represented by any one of formulas (V-1) to (V-7).

[0010]

[0011] In formula (V-1), R １ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n1 represents an integer of 0 to 2. In formula (V-2), R ２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n2 represents an integer of 0 to 4. In formula (V-3), R ３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n3 represents an integer of 0 to 4. In formula (V-4), R ４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n4 represents an integer of 0 to 4. In formula (V-5), R ５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n5 represents an integer of 0 to 4. R ６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n6 represents an integer of 0 to 4. In formula (V-6), R ７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n7 represents an integer of 0 to 3. R ８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n8 represents an integer of 0 to 3. In formula (V-7), R ９ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n9 represents an integer of 0 to 3. R １０ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n10 represents an integer of 0 to 3. * represents a bonding position. L each independently represents a group represented by any one of formulas (L-1) to (L-18).

[0012]

[0013] In formula (L-1), n ​​represents 0 or 1. In formula (L-4), R each independently represents a hydrogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. In formula (L-9), R １１ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n11 represents an integer of 0 to 4. In formula (L-10), R １２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n12 represents an integer of 0 to 6. In formula (L-11), R １３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n13 represents an integer of 0 to 4. R １４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n14 represents an integer of 0 to 4. In formula (L-16), R １５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n15 represents an integer of 0 to 4. R １６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n16 represents an integer of 0 to 4. In formula (L-17), R １７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n17 represents an integer of 0 to 4. In formula (L-18), R １８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n18 represents an integer of 0 to 4. L １ each independently represents a group represented by any one of formulas (L-1) to (L-15). * represents a bonding position. Y ２ represents a divalent linking group containing a structure represented by the following formula (2): １ and A ２ are each independently an oxygen atom or —NR Ｚ - represents. Ｚ represents a hydrogen atom or a monovalent organic group. １ and Z ２ each independently represents a hydrogen atom or a monovalent organic group.

[0014]

[0015] In formula (2), R ２１ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２２ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２３ , R ２４ each independently represents a hydrogen atom or a methyl group. m1 represents an integer of 0 or more and 4 or less. m2 represents an integer of 0 or more and 4 or less. * represents a bonding position.

[0016] [3] The resin composition according to [1], wherein a cured film having a thickness of 20 μm obtained from the resin composition has a dissolution rate in N-methyl-2-pyrrolidone of 0.01 to 1.00 μm / sec.

[0017] [4] Z in the above formula (1) １ and Z ２ The resin composition according to [2], wherein at least one of the following represents a group represented by the following formula (3):

[0018]

[0019] In formula (3), R ｘ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ represents -, a cycloalkylene group, or a polyalkyleneoxy group. ２８ and R ２９ represents a hydrogen atom. ３０ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group. * represents a bonding position.

[0020] [5] The resin composition according to any one of [1] to [4], further comprising a polymerization initiator. [6] The resin composition according to any one of [1] to [5], further comprising a polymerizable compound. [7] The resin composition according to [1], wherein the diffraction peak is derived from a polyimide.

[0021] [8] The resin composition according to [1], wherein the crystallite size of a cured product obtained by heating the resin composition at 300°C for 60 minutes is less than 300 Å. [9] The resin composition according to any one of [1] to [8], wherein the orientation coefficient fzx of the resin composition before heating is greater than -0.20, and the orientation coefficient fzx of a cured product obtained by heating the resin composition at 300°C for 60 minutes is -0.20 or less.

[0022]

[10] The resin composition according to any one of [1] to [9], wherein the resin composition is a negative photosensitive resin composition.

[11] The resin composition according to any one of [1] to

[10] , wherein the resin composition is used for forming an interlayer insulating film for a rewiring layer.

[0023]

[12] A cured product obtained by curing the resin composition according to any one of [1] to

[11] .

[13] A laminate comprising two or more layers each made of the cured product according to

[12] , and a metal layer between any two adjacent layers made of the cured product.

[14] A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of [1] to

[11] onto a substrate to form a film.

[0024]

[15] A method for producing a cured product, comprising: forming a film from a resin composition containing a polyimide precursor having a repeating unit represented by the following formula (1) and a solvent; and heating the film to obtain a cured product, wherein the cured product has a diffraction peak in the range of 5 to 15° in an X-ray diffraction spectrum, and a crystallite size derived from the diffraction peak is 30 Å or more, and the content of the repeating unit represented by the formula (1) is 40 mol % or more based on all repeating units:

[0025]

[0026] In formula (1), X ２ represents a group represented by any one of formulas (V-1) to (V-7).

[0027]

[0028] In formula (V-1), R １are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n1 represents an integer of 0 to 2. In formula (V-2), R ２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n2 represents an integer of 0 to 4. In formula (V-3), R ３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n3 represents an integer of 0 to 4. In formula (V-4), R ４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n4 represents an integer of 0 to 4. In formula (V-5), R ５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n5 represents an integer of 0 to 4. R ６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n6 represents an integer of 0 to 4. In formula (V-6), R ７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n7 represents an integer of 0 to 3. R ８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n8 represents an integer of 0 to 3. In formula (V-7), R ９ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n9 represents an integer of 0 to 3. R １０ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n10 represents an integer of 0 to 3. * represents a bonding position. L each independently represents a group represented by any one of formulas (L-1) to (L-18).

[0029]

[0030] In formula (L-1), n ​​represents 0 or 1. In formula (L-4), R each independently represents a hydrogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. In formula (L-9), R １１are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n11 represents an integer of 0 to 4. In formula (L-10), R １２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n12 represents an integer of 0 to 6. In formula (L-11), R １３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n13 represents an integer of 0 to 4. R １４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n14 represents an integer of 0 to 4. In formula (L-16), R １５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n15 represents an integer of 0 to 4. R １６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n16 represents an integer of 0 to 4. In formula (L-17), R １７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n17 represents an integer of 0 to 4. In formula (L-18), R １８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n18 represents an integer of 0 to 4. L １ each independently represents a group represented by any one of formulas (L-1) to (L-15). * represents a bonding position. Y ２ represents a divalent linking group containing a structure represented by the following formula (2): １ and A ２ are each independently an oxygen atom or —NR Ｚ - represents. Ｚ represents a hydrogen atom or a monovalent organic group. １ and Z ２ each independently represents a hydrogen atom or a monovalent organic group.

[0031]

[0032] In formula (2), R ２１R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２２ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２３ , R ２４ each independently represents a hydrogen atom or a methyl group. m1 represents an integer of 0 or more and 4 or less. m2 represents an integer of 0 or more and 4 or less. * represents a bonding position.

[0033]

[16] The method for producing a cured product according to

[15] , further comprising heating at 200° C. or higher in the step of obtaining the cured product.

[17] The method for producing a cured product according to

[15] or

[16] , further comprising an exposure step and a development step.

[0034] According to the present invention, it is possible to provide a resin composition capable of forming a cured product having high thermal conductivity and a low thermal expansion coefficient, a cured product obtained by curing the resin composition, a laminate including the cured product, and a method for producing the cured product.

[0035] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined, for example, by using an HLC-8420GPC (manufactured by Tosoh Corporation) and guard columns SuperAW-H, TSKgel SuperAWM-H, and TSKgel SuperAWM-H (all manufactured by Tosoh Corporation) connected in series in this order as columns. Unless otherwise specified, these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent. If NMP is not suitable as the eluent, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) ray (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower," it is sufficient that there is another layer above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up." Alternatively, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that such up-and-down directions are set for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from the vertically upward direction. Unless otherwise specified in this specification, the composition may contain two or more compounds corresponding to each component contained in the composition. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. Unless otherwise specified in this specification, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, the term "main chain" refers to the relatively longest bonding chain in a resin molecule, and the term "side chain" refers to any other bonding chain. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0036] [Resin composition] The resin composition of the present invention (also referred to as "resin composition") has either the first aspect or the second aspect described below. In the following description, "the resin composition of the present invention (also simply referred to as "resin composition")" may refer to either the resin composition of the first aspect or the resin composition of the second aspect described below.

[0037] <First Aspect> A resin composition (also referred to as "resin composition 1") comprising: a polyimide precursor; and a solvent, wherein the resin composition is heated at 300°C for 60 minutes to obtain a cured product, which has a diffraction peak in the range of 5 to 15° in an X-ray diffraction spectrum, and a crystallite size derived from the diffraction peak is 30 Å or more.

[0038] <Second Aspect> A resin composition (also referred to as "resin composition 2") comprising: a polyimide precursor having a repeating unit represented by the following formula (1); and a solvent, wherein the content of the repeating unit represented by the following formula (1) is 40 mol % or more based on all repeating units of the polyimide precursor.

[0039]

[0040] In formula (1), X ２ represents a group represented by any one of formulas (V-1) to (V-7).

[0041]

[0042] In formula (V-1), R １ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n1 represents an integer of 0 to 2. In formula (V-2), R ２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n2 represents an integer of 0 to 4. In formula (V-3), R ３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n3 represents an integer of 0 to 4. In formula (V-4), R ４are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n4 represents an integer of 0 to 4. In formula (V-5), R ５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n5 represents an integer of 0 to 4. R ６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n6 represents an integer of 0 to 4. In formula (V-6), R ７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n7 represents an integer of 0 to 3. R ８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n8 represents an integer of 0 to 3. In formula (V-7), R ９ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n9 represents an integer of 0 to 3. R １０ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n10 represents an integer of 0 to 3. * represents a bonding position.

[0043] Each L independently represents a group represented by any one of formulas (L-1) to (L-18).

[0044]

[0045] In formula (L-1), n ​​represents 0 or 1. In formula (L-4), R each independently represents a hydrogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. In formula (L-9), R １１ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n11 represents an integer of 0 to 4. In formula (L-10), R １２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n12 represents an integer of 0 to 6. In formula (L-11), R １３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n13 represents an integer of 0 to 4. R １４are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n14 represents an integer of 0 to 4. In formula (L-16), R １５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n15 represents an integer of 0 to 4. R １６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n16 represents an integer of 0 to 4. In formula (L-17), R １７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n17 represents an integer of 0 to 4. In formula (L-18), R １８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n18 represents an integer of 0 to 4. L １ each independently represents a group represented by any one of formulas (L-1) to (L-15). * represents a bonding position. Y ２ represents a divalent linking group containing a structure represented by the following formula (2): １ and A ２ are each independently an oxygen atom or —NR Ｚ - represents. Ｚ represents a hydrogen atom or a monovalent organic group. １ and Z ２ each independently represents a hydrogen atom or a monovalent organic group.

[0046]

[0047] In formula (2), R ２１ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２２ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２３ , R ２４ each independently represents a hydrogen atom or a methyl group. m1 represents an integer of 0 or more and 4 or less. m2 represents an integer of 0 or more and 4 or less. * represents a bonding position.

[0048] The mechanism by which the thermal conductivity of the cured product obtained from the resin composition of the present invention is improved and the thermal expansion coefficient is reduced is not completely clear, but the present inventors speculate as follows, although the present invention is not limited in any way by the speculated mechanism below.

[0049] The present inventors formed a cured polyimide product from a polyimide precursor by curing a resin composition, and focused on the crystallinity and orientation of the cured product. Resin composition 1 results in a cured product with a diffraction peak in the range of 5 to 15° in an X-ray diffraction spectrum, and the crystallite size derived from the diffraction peak is 30 Å or greater. It is believed that such a crystallite size improves crystallinity and rigidity, suppresses phonon scattering, and thereby improves thermal conductivity. Furthermore, improved crystallinity is based on improved orientation, and since improved orientation generally improves rigidity, it is believed that the coefficient of thermal expansion is also reduced. In the polyimide precursor of resin composition 2, a stilbene structure is introduced into the main chain of the polyimide precursor, and X in formula (1) ２ The polyimide precursor of resin composition 2 has a specific structure represented by formula (1). The polyimide precursor of resin composition 2 contains 40 mol % or more of the repeating units represented by formula (1) relative to the total repeating units of the polyimide precursor. By subjecting such a polyimide precursor to heat treatment, a cured polyimide is formed. Introducing a stilbene structure into the main chain of the polyimide precursor increases the linearity of the polymer and the intermolecular interactions. During imidization by heat treatment, the linearity of the stilbene structure and the intermolecular interactions enhance the orientation, and these linearity and interactions also improve the crystallinity. It is believed that the increased crystallinity and suppression of phonon scattering in the resulting cured product improves the thermal conductivity. Furthermore, the improved orientation enhances the rigidity, thereby reducing the coefficient of thermal expansion. Based on the above mechanism, it is believed that the polyimide of the present application can be reduced in stilbene content without any problems, as long as the crystallinity and orientation are not impaired. As described above, X ２When the polymer is mainly composed of the specific structure described above, by setting the content of the repeating unit in formula (1) to 40 mol % or more, it is believed that the crystallinity and orientation will still be high, and an improvement in thermal conductivity and a reduction in thermal expansion coefficient will be confirmed.

[0050] The polyimide precursor in resin composition 1 and the polyimide precursor in resin composition 2 (hereinafter collectively referred to as "specific resins") preferably have a polymerizable group, more preferably a radically polymerizable group, and even more preferably a group having an ethylenically unsaturated bond. When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator. It may further contain a sensitizer as needed. From such a resin composition, for example, a negative-type photosensitive film is formed. Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed. Resin compositions 1 and 2 may be negative-type photosensitive resin compositions (resin compositions capable of forming a negative-type photosensitive film) or positive-type photosensitive resin compositions (resin compositions capable of forming a positive-type photosensitive film), but are preferably negative-type photosensitive resin compositions. The resin composition of the present invention can be used to form, for example, an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a rewiring layer.

[0051] <Resin Composition 1> In Resin Composition 1, a cured product obtained by heating Resin Composition 1 at 300°C for 60 minutes has a diffraction peak in the range of 5 to 15° in an X-ray diffraction spectrum, and a crystallite size derived from the diffraction peak is 30 Å or more.

[0052] The crystallite size is determined as follows.

[0053] (Preparation of film for measuring X-ray diffraction spectrum) Resin composition 1 was applied to a silicon wafer by spin coating to form a coating film. The silicon wafer with the obtained coating film was dried on a hot plate at 100°C for 5 minutes to obtain a film of uniform thickness on the silicon wafer. The film was heated at a heating rate of 10°C / min, heated to 300°C for 60 minutes, and cured to obtain a cured product (cured film). The cured product was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid and peeled from the silicon wafer to obtain a film of 20 μm in thickness.

[0054] (Measurement of X-ray diffraction spectrum) The X-ray diffraction spectrum was measured in a transmission configuration using a common X-ray diffractometer (SmartLab manufactured by Rigaku Corporation, D8 Discover manufactured by Bruker, etc.). X-rays (Cukα rays, wavelength: 1.54 Å) were irradiated in a direction parallel to the thermal conduction direction of the film, and the XRD pattern was detected using a two-dimensional detector or an imaging plate. The obtained two-dimensional image was integrated in all directions to obtain a 2θ profile.

[0055] (Calculation of Crystallite Size) A 2θ profile (background) obtained under similar conditions without a sample was subtracted from the 2θ profile obtained above. Baseline processing was performed on the obtained profile. Baseline processing was performed by utilizing the area where no peaks were observed in the range of 5 to 15° (around 5 to 6° or 12 to 13°) and subtracting using a spline function method. Other baselines can also be processed using the Sonneveld-Visser method, etc. Diffraction peaks in the baseline-processed spectrum were fitted using a split pseudo-Voigt function to calculate the full width at half maximum. The crystallite size D was calculated from the full width at half maximum of the obtained peak using the Scherrer formula. D = Kλ / β cos θ D: crystallite size K: Scherrer constant 0.97 λ: X-ray wavelength 1.54 Å β: full width at half maximum θ: diffraction angle of the peak

[0056] The crystallite size is 30 Å or more, preferably 50 Å or more, and more preferably 70 Å or more. There is no particular upper limit to the crystallite size, but it is preferably less than 300 Å.

[0057] If the heating conditions in <Preparation of Film for Measuring X-ray Diffraction Spectrum> (300°C, 60 minutes) are changed (for example, to 230°C, 120 minutes) and the resulting cured product has a diffraction peak in the range of 5 to 15° in the X-ray diffraction spectrum and a crystallite size derived from the diffraction peak of 30 Å or more, then the cured product produced in the above <Preparation of Film for Measuring X-ray Diffraction Spectrum> has a diffraction peak in the range of 5 to 15° in the X-ray diffraction spectrum and a crystallite size derived from the diffraction peak of 30 Å or more. In one preferred embodiment, the resin composition of the present invention contains a base generator, which can promote imidization of the polyimide precursor, thereby making it possible to lower the curing temperature (for example, 230°C, 120 minutes).

[0058] The diffraction peak in the range of 5 to 15° in the X-ray diffraction spectrum used to derive the above crystallite size is derived from polyimide.

[0059] A polyimide precursor refers to a resin that undergoes a change in chemical structure in response to an external stimulus to become a polyimide. A resin that undergoes a change in chemical structure in response to heat to become a polyimide is preferred, and a resin that undergoes a ring-closing reaction in response to heat to form a ring structure to become a polyimide is more preferred. The polyimides formed from the polyimide precursors in resin compositions 1 and 2 are preferably insoluble in a developer primarily composed of an organic solvent. The polyimide precursor contained in resin composition 1 is not particularly limited as long as it can form the cured product, but examples include the polyimide precursor in resin composition 2 described below. Using such a polyimide precursor makes it easier to obtain the diffraction peak of the cured product and a crystallite size of 30 Å or more derived from the diffraction peak. One type of polyimide precursor may be used, or two or more types may be used.

[0060] <Resin Composition 2> The polyimide precursor contained in Resin Composition 2 is a polyimide precursor having a repeating unit represented by the above formula (1), and the content of the repeating unit represented by the above formula (1) is 40 mol% or more based on the total repeating units of the polyimide precursor. ２ represents a group represented by any one of formulas (V-1) to (V-7).

[0061]

[0062] In formula (V-1), R １ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n1 represents an integer of 0 to 2. In formula (V-2), R ２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n2 represents an integer of 0 to 4. In formula (V-3), R ３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n3 represents an integer of 0 to 4. In formula (V-4), R ４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n4 represents an integer of 0 to 4. In formula (V-5), R ５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n5 represents an integer of 0 to 4. R ６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n6 represents an integer of 0 to 4. In formula (V-6), R ７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n7 represents an integer of 0 to 3. R ８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n8 represents an integer of 0 to 3. In formula (V-7), R ９ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n9 represents an integer of 0 to 3. R １０are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n10 represents an integer of 0 to 3. * represents a bonding position.

[0063] R １ ~R １０ The organic group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a carbonyl group, an ester group, an amide group, an ether group, or a group formed by combining these. When the organic group is a "group formed by combining these," the number of carbon atoms in the organic group having 1 to 4 carbon atoms represents the total number of carbon atoms in the "group formed by combining these."

[0064] As the alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms is preferred, and an alkyl group having 1 to 2 carbon atoms is more preferred. As the alkenyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 3 carbon atoms is preferred, and an alkenyl group having 2 carbon atoms is more preferred. As the alkynyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 3 carbon atoms is preferred, and an alkynyl group having 2 carbon atoms is more preferred. R １ ~R １０ As the organic group having 1 to 4 carbon atoms, an organic group having 1 to 3 carbon atoms is preferred, and an organic group having 1 to 2 carbon atoms is more preferred. １ ~R １０ The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0065] Each of n1 to n10 is preferably an integer of 0 to 1.

[0066] The four bonding positions in formula (V-1) to formula (V-7) correspond to X in formula (1), respectively. ２ It may be bonded to any of the carbon atoms in the four carbonyl groups bonded to

[0067] X ２ Specific examples of the X include tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydride. ２The tetracarboxylic acid dianhydride may contain only one kind or two or more kinds of tetracarboxylic acid dianhydride residues as a structure corresponding to the formula (I). The tetracarboxylic acid dianhydride is preferably represented by the following formula (O).

[0068]

[0069] In formula (O), X ２ represents a group represented by any one of formulas (V-1) to (V-7).

[0070] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, Examples include 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

[0071] Each L independently represents a group represented by any one of formulas (L-1) to (L-18).

[0072]

[0073] In formula (L-1), n ​​represents 0 or 1. In formula (L-4), R each independently represents a hydrogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. In formula (L-9), R １１are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n11 represents an integer of 0 to 4. In formula (L-10), R １２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n12 represents an integer of 0 to 6. In formula (L-11), R １３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n13 represents an integer of 0 to 4. R １４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n14 represents an integer of 0 to 4. In formula (L-16), R １５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n15 represents an integer of 0 to 4. R １６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n16 represents an integer of 0 to 4. In formula (L-17), R １７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n17 represents an integer of 0 to 4. In formula (L-18), R １８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n18 represents an integer of 0 to 4. L １ each independently represents a group represented by any one of formulas (L-1) to (L-15), and * represents a bonding position.

[0074] In formula (L-1), when n is 0, formula (L-1) represents a single bond. In formula (L-4), the organic group having 1 to 2 carbon atoms represented by R is not particularly limited, but examples thereof include an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 carbon atoms, an alkynyl group having 2 carbon atoms, a carbonyl group, an ester group, an amide group, an ether group, or a group formed by combining these. When the organic group is a "group formed by combining these," the number of carbon atoms in the organic group having 1 to 2 carbon atoms represents the total number of carbon atoms in the "group formed by combining these." In formula (L-4), the alkyl group in the halogenated alkyl group represented by R is preferably an alkyl group having 1 to 2 carbon atoms. The halogen atom in the halogenated alkyl group represented by R is not particularly limited, but a fluorine atom is preferred.

[0075] R １１ ~R １８ The organic group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a carbonyl group, an ester group, an amide group, an ether group, or a group formed by combining these. When the organic group is a "group formed by combining these," the number of carbon atoms in the organic group having 1 to 4 carbon atoms represents the total number of carbon atoms in the "group formed by combining these."

[0076] As the alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms is preferred, and an alkyl group having 1 to 2 carbon atoms is more preferred. As the alkenyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 3 carbon atoms is preferred, and an alkenyl group having 2 carbon atoms is more preferred. As the alkynyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 3 carbon atoms is preferred, and an alkynyl group having 2 carbon atoms is more preferred. R １１ ~R １８ As the organic group having 1 to 4 carbon atoms, an organic group having 1 to 3 carbon atoms is preferred, and an organic group having 1 or 2 carbon atoms is more preferred.

[0077] R １１ ~R １８ The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0078] Each of n11 to n18 is preferably an integer of 0 to 1.

[0079] Y ２ represents a divalent linking group containing a structure represented by the following formula (2).

[0080]

[0081] In formula (2), R ２１ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２２ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２３ , R ２４ each independently represents a hydrogen atom or a methyl group. m1 represents an integer of 0 or more and 4 or less. m2 represents an integer of 0 or more and 4 or less. * represents a bonding position.

[0082] R ２１ , R ２２ The organic group having 1 to 2 carbon atoms as is not particularly limited, and examples thereof include an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 carbon atoms, an alkynyl group having 2 carbon atoms, a carbonyl group, an ester group, an amide group, an ether group, or a group formed by combining these. When the organic group is a "group formed by combining these," the number of carbon atoms in the organic group having 1 to 2 carbon atoms represents the total number of carbon atoms in the "group formed by combining these."

[0083] R ２１ , R ２２ The alkyl group in the halogenated alkyl group represented by R is preferably an alkyl group having 1 to 2 carbon atoms. The halogen atom in the halogenated alkyl group represented by R is not particularly limited, but a fluorine atom is preferred. m1 is preferably an integer of 0 or more and 2 or less, more preferably 0 or 1. m2 is preferably an integer of 0 or more and 2 or less, more preferably 0 or 1.

[0084] Y ２ is not particularly limited as long as it is a divalent linking group containing the structure represented by the above formula (2), but may be the structure represented by the above formula (2) itself.

[0085] Y ２ is preferably derived from a diamine. Only one type of diamine may be used, or two or more types may be used. The two bonding positions in formula (2) are respectively the same as those of Y in formula (1). ２ It may be bonded to either of the nitrogen atoms in the two —NH— groups bonded to

[0086] A in formula (1) １ and A ２ are each independently an oxygen atom or —NR ｚ -, and an oxygen atom is preferred. ｚ represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.

[0087] In formula (1), X ２ and Y ２ At least one of X may have an OH group. ２ Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0088] Z in formula (1) １ and Z ２ each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. The number of carbon atoms in the monovalent organic group is not particularly limited, but is preferably 1 to 12. In addition, Z １ and Z ２ Preferably, at least one of Z contains a polymerizable group, and more preferably, both contain a polymerizable group. １ and Z ２It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group possessed by the polyamic acid ester is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (3), with the group represented by the following formula (3) being preferred.

[0089]

[0090] In formula (3), R ｘ represents an alkylene group having 2 to 9 carbon atoms, —CH ２ CH(OH)CH ２ represents -, a cycloalkylene group, or a polyalkyleneoxy group. ２８ and R ２９ represents a hydrogen atom. ３０ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group. * represents a bonding position.

[0091] Suitable R ｘ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an octamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 8, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 12, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0092] In formula (3), R ３０represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and a hydrogen atom or a methyl group is preferred. １ and Z ２ It is preferable that at least one of these groups represents a group represented by the above formula (3).

[0093] In formula (1), Z １ and Z ２ At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group. Preferred examples include an acetal group, a ketal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. From the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0094] The polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0095] Furthermore, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include embodiments using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.

[0096] The polyimide precursor may contain one type of repeating unit represented by formula (1), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (1). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit of formula (1).

[0097] The content of the repeating unit represented by the formula (1) is 40 mol% or more relative to all repeating units. By ensuring the crystallinity and orientation of the cured polyimide obtained by heat-treating the polyimide precursor as described above, it is believed that the thermal conductivity of the cured polyimide obtained is improved and the thermal expansion coefficient is reduced.

[0098] In one embodiment of the polyimide precursor, the content of the repeating unit represented by formula (1) is 50 mol% or more relative to all repeating units. The content of the repeating unit represented by formula (1) is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the content of the repeating unit represented by formula (1) is not particularly limited, and may be 100 mol%. In one embodiment, the upper limit of the content of the repeating unit represented by formula (1) is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (1).

[0099] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and even more preferably 15,000 to 50,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 80,000, more preferably 3,000 to 40,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. When the resin composition contains multiple polyimide precursors, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as a single resin are within the above-mentioned ranges.

[0100] [Method for Producing Polyimide Precursor] The polyimide precursor can be obtained by, for example, reacting a tetracarboxylic dianhydride with a diamine at low temperature, reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and then esterifying the polyamic acid using a condensing agent or an alkylating agent, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diester with a diamine in the presence of a condensing agent, or obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine with the diamine. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine with the diamine is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing a polyimide precursor, it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used. The organic solvent can be appropriately selected depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing a polyimide precursor, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0101] -End-capping agent- In order to further improve storage stability during the production method of a polyimide precursor, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor. Examples of end-capping agents for capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal include monoalcohols, phenols, thiols, thiophenols, and monoamines. From the perspective of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Preferred examples of the monoamine compound include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of suitable end-capping agents 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-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple end-capping agents may be reacted to introduce multiple different end groups. Furthermore, when capping the amino groups at the resin ends, they can be capped with a compound having a functional group capable of reacting with the amino group. Preferred examples of the capping agent for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic acid anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0102] -Solid Precipitation- The method for producing a polyimide precursor may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain a polyimide precursor. To improve the degree of purification, the polyimide precursor may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0103] The content of the polyimide precursor in resin composition 1 and resin composition 2 is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of resin composition 1 and resin composition 2. Furthermore, the content of the polyimide precursor in resin composition 1 and resin composition 2 is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of resin composition 1 and resin composition 2. Resin composition 1 and resin composition 2 may contain only one type of polyimide precursor, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0104] Resin composition 1 and resin composition 2 may contain at least two types of resins. Specifically, resin composition 1 and resin composition 2 may contain a total of two or more types of polyimide precursors and other resins (resins other than polyimide precursors), or may contain two or more types of polyimide precursors. When the polyimide precursor contains two or more types of polyimide precursors, for example, a polyimide precursor having a structure derived from a dianhydride (X in the above formula (1)) ２ It is preferable that the composition contains two or more polyamic acid esters having different molecular weights. Examples of other resins include polyimide, polyamic acid, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can also be obtained. For example, a resin composition having a high polymerizable group value (for example, a polymerizable group content of 1×10 per 1 g of resin) with a weight average molecular weight of 20,000 or less can be used. －３ By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0105] When resin composition 1 and resin composition 2 contain other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total solid content of resin composition 1 and resin composition 2. The content of the other resins is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 7% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less, relative to the total solid content of resin composition 1 and resin composition 2. A preferred embodiment of resin composition 1 and resin composition 2 may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin 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, relative to the total solid content of resin composition 1 and resin composition 2. The lower limit of the content is not particularly limited as long as it is 0% by mass or more. Resin composition 1 and resin composition 2 may contain only one type of other resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.

[0106] <Solvent> The resin composition of the present invention contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0107] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionates, Preferred examples of the alkyl cypropionate include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0108] Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate (PGMEA), 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.

[0109] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0110] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0111] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0112] Preferred examples of the 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.

[0113] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0114] 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, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0115] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0116] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of approximately 1 to 10% by mass, based on the total mass of the solvent, is also a preferred embodiment of the present invention. In particular, from the viewpoint of the storage stability of the resin composition, an embodiment in which γ-butyrolactone is included as a solvent is also a preferred embodiment of the present invention. In such an embodiment, the content of γ-butyrolactone 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. The upper limit of the above content is not particularly limited and may be 100% by mass. The above content may be determined taking into consideration the solubility of components such as the specific resin contained in the resin composition, etc. Furthermore, when dimethyl sulfoxide and γ-butyrolactone are used in combination, the solvent preferably contains 60 to 90 mass% of γ-butyrolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-butyrolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-butyrolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0117] The solvent preferably does not substantially contain water. Specifically, the water content in the solvent is 10% by mass or less, more preferably 3% by mass or less, and preferably 1% by mass or less, based on the total mass of the solvent. In one preferred embodiment, the solvent does not contain water.

[0118] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total amount of the solvents is preferably within the above range.

[0119] The dissolution rate of a 20 μm thick film obtained from the resin composition of the present invention in N-methyl-2-pyrrolidone is preferably 0.01 to 1.00 μm / sec. A 20 μm thick film can be obtained by curing the resin composition. Specifically, it can be obtained by the following method. <Preparation of Cured Product> The resin composition of the present invention was applied to a silicon wafer by spin coating to form a coating film. The silicon wafer with the obtained coating film was dried on a hot plate at 100°C for 5 minutes, obtaining a film of uniform thickness on the silicon wafer. The film was heated at a heating rate of 10°C / min, heated to 300°C for 60 minutes, and cured to obtain a 20 μm thick cured product (cured film).

[0120] <Measurement of Dissolution Rate> The dissolution rate of the cured film in N-methyl-2-pyrrolidone can be calculated by immersing a silicon wafer on which the cured film has been formed in N-methyl-2-pyrrolidone for 15 seconds and measuring the film thickness before and after immersion using an ellipsometer. The film is immersed in N-methyl-2-pyrrolidone without being subjected to any heating other than the drying step. The amount of N-methyl-2-pyrrolidone used for immersion is 30 times the volume of the film. The temperature of N-methyl-2-pyrrolidone, the film, and the silicon wafer during immersion is 23°C. In cases where the film dissolves completely or where the film thickness remains unchanged, the immersion time can be appropriately adjusted to calculate the dissolution rate. γ-Butyrolactone can be used as a solvent for dissolving the specific resin used in preparing the composition (solution). In cases where γ-butyrolactone is difficult to use, such as when the specific resin does not dissolve, the solvent may be changed to a solvent that dissolves the specific resin, such as cyclopentanone or dimethyl sulfoxide.

[0121] The dissolution rate of the membrane in N-methyl-2-pyrrolidone is preferably 0.01 to 1.00 μm / sec, since the resulting membrane is hydrophobic. The dissolution rate of the membrane in N-methyl-2-pyrrolidone is preferably 0.03 to 0.80 μm / sec, and more preferably 0.05 to 0.50 μm / sec.

[0122] The dissolution rate of a 20 μm-thick film obtained from the resin composition of the present invention in N-methyl-2-pyrrolidone is preferably 0.01 to 1.00 μm / sec. If the heating conditions (300°C, 60 minutes) in <Preparation of Cured Product> are changed (for example, to 230°C, 120 minutes) and the dissolution rate of the resulting cured product is measured in the same manner as in <Measurement of Dissolution Rate> above, and the resulting value is 0.01 to 1.00 μm / sec, then the dissolution rate of the cured product produced in the <Preparation of Cured Product> above will also be 0.01 to 1.00 μm / sec. In one preferred embodiment, the resin composition of the present invention contains a base generator, which can promote imidization of the polyimide precursor, thereby making it possible to lower the curing temperature (for example, 230°C, 120 minutes).

[0123] Furthermore, it is preferable that the orientation coefficient fzx of the resin composition of the present invention before heating is greater than −0.20, and that the orientation coefficient fzx of the cured product obtained by heating the resin composition for 60 minutes at 300° C. is −0.20 or less. By satisfying these orientation coefficient characteristics, it is more likely that the cured product obtained by heating Resin Composition 1 for 60 minutes at 300° C. will have a diffraction peak in the range of 5 to 15° in the X-ray diffraction spectrum, and that the crystallite size derived from the diffraction peak will be 30 Å or more.

[0124] The orientation coefficient fzx of the cured product was measured as follows.

[0125] <Cured Product Preparation> The resin composition was applied to a silicon wafer by spin coating to form a coating film. The silicon wafer with the resulting coating film was dried on a hot plate at 100°C for 5 minutes to obtain a film of uniform thickness on the silicon wafer. The film was heated at a rate of 10°C / min, and then heated to 300°C for 60 minutes to cure, obtaining a cured product (cured film) with a thickness of 20 μm.

[0126] <Polarized ATR-IR Measurement> Polarized ATR-IR measurement was performed under the following conditions. A general macro ATR-IR device can be used as the measurement device, but it is preferable to use an MCT detector to obtain sufficient detection sensitivity. Prism: Germanium Pressure between prism and sample: 20 cN m Incident angle: 45° Number of reflections: 1 Resolution: 4 cm －１ Measurement was performed after confirming that the cured product (sample) was sufficiently adhered to the entire surface of the prism. The FTIR-ATR spectrum was measured by irradiating perpendicularly polarized light (s-polarized light; transverse electric, TE) and horizontally polarized light (transverse magnetic, TM) onto the incident surface, which is composed of light incident on the sample surface and light reflected from it, using a wire grid polarizer. The absorption spectrum when perpendicularly polarized light was incident was measured as S ＴＥ , the absorption spectrum when horizontally polarized light is incident is S ＴＭ The obtained spectrum was subjected to atmospheric correction so that the signal derived from water vapor was below the noise level.

[0127] <Calculation of absorbance (peak area)> S ＴＥ , S ＴＭ In each spectrum, 1765 to 1790 cm －１ The area A enclosed by the spectrum and the baseline for the imide C=O group symmetric stretching peak having a maximum absorption point in the range ＴＥ , A ＴＭ The endpoints on the low wavenumber side and the high wavenumber side of the baseline at this time were calculated by dividing the endpoint on the low wavenumber side by 1750 to 1775 cm －１ Between the high wavenumber end points, 1780 and 1815 cm －１ The spectrum was set on the spectrum between the above values ​​so that the baseline did not intersect with the spectrum and the area enclosed by the spectrum and the baseline was maximized.

[0128] <Calculation of orientation coefficient fzx> In this sample, the absorption coefficient k in the x direction ｘ and the absorption coefficient in the y direction k ｙ can be considered equal (k ｘ = k ｙ ).

[0129] A mentioned in the preceding paragraph ＴＥ , A ＴＭ Using the above, the absorption coefficient k is calculated according to the formulas ([Formula 1], [Formula 2] and [Formula 3]) described in the reference document (JP-A 2004-126109). ｘ and k ｚ The infrared dichroic ratio D ｚｘ = k ｚ / k ｘ As the orientation coefficient in the film thickness direction, f ｚｘ was calculated using the following formula:

[0130]

[0131] where

[0132]

[0133] where δ is the angle between the transition moment vector formed by molecular vibration and the molecular axis. The imide C=O group symmetric stretching mode used here is a vibration mode parallel to the molecular axis, and δ can be calculated as 0°. The resulting orientation coefficient f ｚｘis based on the film thickness direction (axis perpendicular to the film surface, z-axis), is 1 when the molecular chains are completely oriented parallel, is 0 when they are randomly oriented, and is -0.5 when they are completely oriented perpendicular.

[0134] Furthermore, the orientation coefficient fzx of the resin composition of the present invention before heating was set to 0 because the resin composition was in a dissolved state in a solvent.

[0135] The orientation coefficient fzx of the resin composition of the present invention before heating is preferably greater than -0.20. In a preferred embodiment, the orientation coefficient fzx of the resin composition of the present invention before heating is preferably 0. The orientation coefficient fzx of the cured product obtained by heating the resin composition at 300°C for 60 minutes is preferably -0.20 or less, more preferably -0.22 or less, and even more preferably -0.25 or less. The orientation coefficient fzx of the cured product is not particularly limited, but is -0.5 or more.

[0136] If the orientation coefficient fzx of the cured product (hereinafter also referred to as "cured product 1") obtained by changing "300°C, 60 minutes" to "230°C, 120 minutes" in the above "Formation of cured product (film)" is -0.20 or less, then the orientation coefficient fzx of the cured product obtained in the above "Formation of cured product (film)" (300°C, 60 minutes) is -0.20 or less.

[0137] <Polymerizable Compound> The resin composition of the present invention preferably further contains a polymerizable compound. Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents.

[0138] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0139] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. From the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0140] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0141] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0142] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0143] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0144] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include 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 products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these agents can also be used.

[0145] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such an ester include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0146] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0147] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group. Particularly preferred is a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0148] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. Furthermore, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0149] From the viewpoints of pattern resolution and film elasticity, it is preferable to use a bifunctional methacrylate or acrylate for the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, isocyanuric acid-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of approximately 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent in the resin composition of the present invention.Preferred examples of monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0150] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, based on the total solid content of the resin composition. 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.

[0151] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0152] [Other Crosslinking Agents] The resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. It is preferably a compound having multiple groups in its molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products upon exposure to light by a photoacid generator or a photobase generator. It is preferable that the compound have multiple groups in its molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products under the action of an acid or base. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator during the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0153] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0154] The photoradical polymerization initiator has a capacity of at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0155] Any known compound can be used as the photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details of these compounds, please refer to paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

[0151] of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A can be mentioned, the contents of which are incorporated herein by reference.

[0156] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0157] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0158] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

[0159] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0160] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0161] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0162] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232) described compounds, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515 and the like, the contents of which are incorporated herein.

[0163] Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0164]

[0165] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito ChemiX Co., Ltd.), and SpeedCure PDO (SARTOMER Also, an oxime compound having the following structure can be used.

[0166]

[0167] Examples of photoradical polymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169 to 0171 of WO 2021 / 112189. Also usable are oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359. The contents of these compounds are incorporated herein by reference.

[0168] As the photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring can be used. ＯＸ１ It is also possible to use an oxime compound having the aromatic ring group Ar ＯＸ１Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred, and an acyl group is more preferred because it is easier to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group is more preferred, and an alkoxy group, an alkylsulfanyl group, or an amino group is even more preferred.

[0169] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2).

[0170]

[0171] In the formula, R Ｘ１ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group; R Ｘ２ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group; R Ｘ３ ~R Ｘ１４each independently represents a hydrogen atom or a substituent. Ｘ１０ ~R Ｘ１４ At least one of the groups is an electron-withdrawing group.

[0172] In the above formula, R Ｘ１２ is an electron-withdrawing group, and R Ｘ１０ , R Ｘ１１ , R Ｘ１３ , R Ｘ１４ is preferably a hydrogen atom.

[0173] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0174] Particularly preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0175] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0176] The photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound, and even more preferably a metallocene compound or an oxime compound.

[0177] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of WO 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469 can also be used, the contents of which are incorporated herein by reference.

[0178] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thereby obtaining good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, and improving the stability of the resin composition over time. Specific examples of the bifunctional or trifunctional or higher functional photoradical polymerization initiator include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO 2015 / 004565, WO 2016-532675, paragraphs 0407 to 0412, and WO 2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-T-2013-522445; oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0179] When the resin composition contains a photopolymerization initiator, the content thereof 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, based on the total solid content of the resin composition. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0180] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, and Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include soamyl, 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, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0181] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and still more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0182] [Chain Transfer Agent] 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, 2005), pages 683-684. Examples of chain transfer agents include those having -S-S-, -SO ２ Compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthate compounds, and the like having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization can be used. These compounds can donate hydrogen to a low-activity radical to generate a radical, or can be oxidized and then deprotonated to generate a radical. In particular, thiol compounds can be preferably used.

[0183] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0184] 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 solid content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0185] <Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in excellent performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0186] Examples of the base generator include, but are not limited to, the following compounds:

[0187]

[0188] The molecular weight of the nonionic base 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.

[0189] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0190] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0191]

[0192] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0193]

[0194] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0195] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[0196] [Silane Coupling Agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compound as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0197]

[0198] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0199] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0200] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935, the contents of which are incorporated herein by reference.

[0201] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern are improved. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0202] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0203] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0204] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0205] Other migration inhibitors, for example, other migration inhibitors, the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compounds described in paragraph 0166 of WO 2015 / 199219, and the like can be used, the contents of which are incorporated herein by reference.

[0206] Specific examples of the migration inhibitor include the following compounds.

[0207]

[0208] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition.

[0209] The migration inhibitor may be one kind or two or more kinds. When two or more kinds of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0210] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0211] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and phenoxazine, the contents of which are incorporated herein by reference.

[0212] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass%, more preferably 0.02 to 15 mass%, and even more preferably 0.05 to 10 mass%, based on the total solid content of the resin composition.

[0213] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0214] <Other Additives> The resin composition of the present invention may contain various additives, such as surfactants, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, within the scope of obtaining the effects of the present invention. By appropriately incorporating these components, properties such as film physical properties can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101 to 0104, 0107 to 0109, etc. of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0215] [Surfactant] Various surfactants can be used as the surfactant, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0216] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared can be further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a uniform film with little thickness unevenness.

[0217] Examples of fluorine-based surfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, fluorine-containing polymer compounds containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

[0218]

[0219] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0220] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0221] Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0222] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0223] [Thermal Polymerization Initiator] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals by thermal energy and initiate or promote the polymerization reaction of a polymerizable compound. Addition of a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. In addition, photopolymerization initiators may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0224] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0225] When a thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, it is preferable that the total amount is in the above range.

[0226] [Inorganic Particles] Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, boron nitride, aluminum nitride, graphene oxide, and nanodiamond.

[0227] 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 particularly preferably 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured, for example, by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0228] [Ultraviolet absorber] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, etc. Specific examples of the ultraviolet absorber include the compounds described in paragraphs 0341 to 0342 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0229] The ultraviolet absorbers may be used singly or in combination of two or more. When the resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid mass of the resin composition.

[0230] [Organotitanium Compound] When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0231] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0232] Among these, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0233] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0234] [Antioxidant] By including an antioxidant as an additive, the elongation properties of the cured film and adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0235] The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By adding an amount of 0.1 part by mass or more, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials even in high-temperature, high-humidity environments, and by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.

[0236] <Characteristics of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２ If the viscosity is 1 / s or less, a coating film having excellent coating surface condition can be obtained.

[0237] <Restrictions on substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and 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. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0238] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0239] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0240] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, those present in the form of halogen ions are 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. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned range. Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

[0241] A conventionally known container can be used as a container for storing the resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0242] <Cured Product of Resin Composition> A cured product of the resin composition can be obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the resin composition. The resin composition is preferably cured by heating, with the heating temperature being more preferably 150°C to 500°C, even more preferably 180°C to 450°C, and particularly preferably 200°C to 400°C. The form of the cured product of the resin composition is not particularly limited, and can be selected depending on the application, such as a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the shape of the cured product can be selected depending on the application, such as forming a protective film on a wall surface, forming via holes for electrical conductivity, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of change in volume of the resin composition before and after curing, and can be calculated by the following formula: Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0243] <Characteristics of cured product of resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or more, more preferably 210°C or more, and even more preferably 230°C or more.

[0244] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0245] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more 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 preferable. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtering under pressure, the pressure to be 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. In addition to filtering using a filter, a process of removing impurities using an adsorbent may be performed. Filter filtration and a process of removing impurities using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering using a filter, the resin composition filled in a bottle may be subjected to a degassing process by placing it under reduced pressure.

[0246] (Method for Producing a Cured Product) The method for producing a cured product of the present invention preferably includes a film-forming step of applying a resin composition to a substrate to form a film. The method for producing a cured product may include the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a development step of developing the film exposed in the exposure step using a developer to form a pattern. The method for producing a cured product may include the film-forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step. Furthermore, the method for producing a cured product preferably includes the film-forming step and a step of heating the film. Details of each step will be described below.

[0247] <Film Forming Step> The resin composition of the present invention can be used in a film forming step of applying the resin composition to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0248] [Substrate] The type of substrate can be appropriately determined depending on the application and is not particularly limited. In particular, a substrate for producing a semiconductor is preferred, and a silicon substrate, a Cu substrate, or a mold substrate is more preferred.

[0249] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0250] Coating is preferred as a means for applying the resin composition to a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and coating conditions depending on the application method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be used in which a coating film formed by applying the coating composition to a temporary support in advance using the above-described application method is transferred onto the substrate. Regarding the transfer method, the preparation methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. A step of removing excess film from the edge of the substrate may also be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate, improving the wettability of the substrate and then applying the resin composition.

[0251] <Drying Step> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film-forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be carried out under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0252] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed to light. The method for producing a cured product may include an exposure step in which the film formed in the film formation step is selectively exposed to light. Selective exposure means that a portion of the film is exposed to light. Furthermore, selective exposure forms exposed regions (exposed portions) and unexposed regions (unexposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. ２ is preferred, and 200 to 8,000 mJ / cm ２ is more preferred.

[0253] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0254] The exposure wavelengths, in relation to the light source, are: (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.); (2) metal halide lamp; (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line); (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２Examples of such light include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0255] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a cured product of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0256] <Development step> The above-mentioned film after exposure may be subjected to a development step in which it is developed using a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. By carrying out development, one of the exposed and unexposed parts of the film is removed to form a pattern. Here, development in which the unexposed parts of the film are removed in the development step is called negative development, and development in which the exposed parts of the film are removed in the development step is called positive development.

[0257] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0258] When the developer is an alkaline aqueous solution, the basic compound that the alkaline aqueous solution may contain may be the compounds described in paragraph

[0256] of WO 2023 / 190062, preferably TMAH. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0259] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph

[0387] of WO 2021 / 112189, the contents of which are incorporated herein by reference. Suitable examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and suitable examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0260] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0261] 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. Alternatively, the content may be 100% by mass.

[0262] When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates into the pattern, the performance of the pattern, such as breaking elongation, may be improved.

[0263] As the basic compound, from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated), an organic base is preferred. As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. However, to promote the imidization reaction, primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines, or ammonium salts are more preferred, secondary amines or tertiary amines are even more preferred, and tertiary amines are particularly preferred. As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferred that it is difficult for the amount remaining to decrease before heating due to vaporization, etc., is preferred. Therefore, the boiling point of the basic compound is preferably 30°C to 350°C at normal pressure (101,325 Pa), more preferably 80°C to 270°C, and even more preferably 100°C to 230°C. The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer. For example, when the boiling point of the organic solvent is 100° C., the boiling point of the basic compound used is preferably 80° C. or higher, and more preferably 100° C. or higher. The developer may contain only one type of basic compound, or may contain two or more types.

[0264] Specific examples of the basic compound include the compounds described in paragraph 0262 of WO 2023 / 190062.

[0265] The preferred embodiments of the base generator are the same as those of the base generator contained in the composition described above. In particular, the base generator is preferably a thermal base generator.

[0266] When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more. When the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the developer. The developer may contain only one type of basic compound or base generator, or two or more types. When two or more types of at least one of the basic compound and base generator are used, the total content thereof is preferably within the above-mentioned range.

[0267] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0268] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form the desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to the film formed on the substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer using a straight nozzle or a method of continuously supplying the developer using a spray nozzle is preferred, and from the viewpoint of the permeability of the developer to the image areas, a method of supplying using a spray nozzle is more preferred. In addition, a process may be adopted in which the developer is continuously supplied using a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again using a straight nozzle, and the substrate is spun to remove the developer from the substrate, or this process may be repeated multiple times. Methods of supplying the developer in the development process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a combination thereof.

[0269] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0270] In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be employed in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0271] [Rinse Solution] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse solution. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse solution. For details of the rinse solution, see paragraphs 0270 to 0280 of WO 2023 / 190062.

[0272] <Heating Step> The pattern obtained by the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the development step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a development step, or a film obtained by a film formation step is heated. In the heating step, a resin such as a polyimide precursor is cyclized to form a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is more preferably 150 to 500°C, even more preferably 180 to 450°C, and particularly preferably 200 to 400°C.

[0273] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0274] The heating step is preferably carried out at a temperature increase rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0275] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0276] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0277] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher. The upper limit of the heating temperature is preferably 400° C. or lower, more preferably 350° C. or lower, and even more preferably 300° C. or lower.

[0278] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed at a temperature in the range of 100 to 150°C, followed by a second pretreatment step at a temperature in the range of 150 to 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5°C / min.

[0279] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means used in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0280] <Post-development exposure step> The pattern obtained in the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern obtained in the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. The post-development exposure step can promote, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator. In the post-development exposure step, it is sufficient that at least a portion of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. ２ is preferred, and 100 to 15,000 mJ / cm ２ The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0281] <Metal Layer Forming Step> The pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0282] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0283] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0284] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0285] The present invention also relates to a method for producing a cured product, which includes the steps of: forming a film from a resin composition containing a polyimide precursor having a repeating unit represented by the following formula (1) and a solvent; and heating the film to obtain a cured product, wherein the cured product has a diffraction peak in the range of 5 to 15° in an X-ray diffraction spectrum, and a crystallite size derived from the diffraction peak is 30 Å or more, in which the content of the repeating unit represented by the following formula (1) is 40 mol % or more based on all repeating units (also referred to as "method 2 for producing a cured product").

[0286]

[0287] In formula (1), X ２ represents a group represented by any one of formulas (V-1) to (V-7).

[0288]

[0289] In formula (V-1), R １are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n1 represents an integer of 0 to 2. In formula (V-2), R ２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n2 represents an integer of 0 to 4. In formula (V-3), R ３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n3 represents an integer of 0 to 4. In formula (V-4), R ４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n4 represents an integer of 0 to 4. In formula (V-5), R ５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n5 represents an integer of 0 to 4. R ６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n6 represents an integer of 0 to 4. In formula (V-6), R ７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n7 represents an integer of 0 to 3. R ８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n8 represents an integer of 0 to 3. In formula (V-7), R ９ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n9 represents an integer of 0 to 3. R １０ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n10 represents an integer of 0 to 3. * represents a bonding position. L each independently represents a group represented by any one of formulas (L-1) to (L-18).

[0290] In formula (L-1), n ​​represents 0 or 1. In formula (L-4), R each independently represents a hydrogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. In formula (L-9), R １１are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n11 represents an integer of 0 to 4. In formula (L-10), R １２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n12 represents an integer of 0 to 6. In formula (L-11), R １３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n13 represents an integer of 0 to 4. R １４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n14 represents an integer of 0 to 4. In formula (L-16), R １５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n15 represents an integer of 0 to 4. R １６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n16 represents an integer of 0 to 4. In formula (L-17), R １７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n17 represents an integer of 0 to 4. In formula (L-18), R １８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n18 represents an integer of 0 to 4. L １ each independently represents a group represented by any one of formulas (L-1) to (L-15). * represents a bonding position. Y ２ represents a divalent linking group containing a structure represented by the following formula (2): １ and A ２ are each independently an oxygen atom or —NR Ｚ - represents. Ｚ represents a hydrogen atom or a monovalent organic group. １ and Z ２ each independently represents a hydrogen atom or a monovalent organic group.

[0291]

[0292] In formula (2), R ２１R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２２ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２３ , R ２４ each independently represents a hydrogen atom or a methyl group. m1 represents an integer of 0 or more and 4 or less. m2 represents an integer of 0 or more and 4 or less. * represents a bonding position.

[0293] Examples of the polyimide precursor having a repeating unit represented by formula (1) and the solvent include the same polyimide precursor and solvent as those in resin composition 2, and the preferred ranges are also the same. The resin composition is also resin composition 2, and may contain components that resin composition 2 may contain.

[0294] An example of the process for forming a film using the resin composition of the present invention is a film formation process in which the resin composition of the present invention is applied onto a substrate to form a film on the substrate. The film formation process is as described above.

[0295] The step of heating the film to obtain a cured product can be exemplified by the above-mentioned <heating step>. In a preferred embodiment, in the step of obtaining a cured product, the film is heated at 180° C. or higher, and particularly preferably at 200° C. or higher. Heating at 180° C. or higher makes it easier to form a cured product.

[0296] The cured product has a diffraction peak in the range of 5 to 15° in an X-ray diffraction spectrum, and the crystallite size derived from the diffraction peak is 30 Å or more.

[0297] The crystallite size is determined as follows.

[0298] (Preparation of film for measuring X-ray diffraction spectrum) Resin composition 2 was applied to a silicon wafer by spin coating to form a coating film. The silicon wafer with the obtained coating film was dried on a hot plate at 100°C for 5 minutes to obtain a film of uniform thickness on the silicon wafer. The film was heated at a temperature increase rate of 10°C / min, heated at a predetermined temperature for a predetermined time, and cured to obtain a cured product (cured film). The cured product was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid and peeled from the silicon wafer to obtain a film with a thickness of 20 mm.

[0299] (Measurement of X-ray diffraction spectrum) The X-ray diffraction spectrum was measured in a transmission configuration using a common X-ray diffractometer (SmartLab manufactured by Rigaku Corporation, D8 Discover manufactured by Bruker, etc.). X-rays (Cukα rays, wavelength: 1.54 Å) were irradiated in a direction parallel to the thermal conduction direction of the film, and the XRD pattern was detected using a two-dimensional detector or an imaging plate. The obtained two-dimensional image was integrated in all directions to obtain a 2θ profile.

[0300] (Calculation of Crystallite Size) A 2θ profile (background) obtained under similar conditions without a sample was subtracted from the 2θ profile obtained above. Baseline processing was performed on the obtained profile. Baseline processing was performed by utilizing the area where no peaks were observed in the range of 5 to 15° (around 5 to 6° or 12 to 13°) and subtracting using a spline function method. Other baselines can also be processed using the Sonneveld-Visser method, etc. Diffraction peaks in the baseline-processed spectrum were fitted using a split pseudo-Voigt function to calculate the full width at half maximum. The crystallite size D was calculated from the full width at half maximum of the obtained peak using the Scherrer formula. D = Kλ / β cos θ D: crystallite size K: Scherrer constant 0.97 λ: X-ray wavelength 1.54 Å β: full width at half maximum θ: diffraction angle of the peak

[0301] The predetermined temperature in the preparation of the film for measuring the X-ray diffraction spectrum is not particularly limited, but in one embodiment, it is 230° C. or 300° C. The predetermined time in the preparation of the film for measuring the X-ray diffraction spectrum is not particularly limited, but in one embodiment, it is 60 minutes or 120 minutes.

[0302] If the heating conditions in <Preparation of Film for Measuring X-ray Diffraction Spectrum> (300°C, 60 minutes) are changed (for example, to 230°C, 120 minutes) and the resulting cured product has a diffraction peak in the range of 5 to 15° in the X-ray diffraction spectrum and a crystallite size derived from the diffraction peak of 30 Å or more, then the cured product produced in the above <Preparation of Film for Measuring X-ray Diffraction Spectrum> has a diffraction peak in the range of 5 to 15° in the X-ray diffraction spectrum and a crystallite size derived from the diffraction peak of 30 Å or more. In one preferred embodiment, the resin composition of the present invention contains a base generator, which can promote imidization of the polyimide precursor, thereby making it possible to lower the curing temperature (for example, 230°C, 120 minutes).

[0303] The method for producing a cured product 2 of the present invention may further include an exposure step and a development step. The exposure step and the development step are steps that are performed before the step of heating the film to obtain a cured product. Examples of the exposure step and the development step include the same steps as those described above in the <exposure step> and <development step>, respectively.

[0304] <Applications> Examples of fields to which the cured product manufacturing method of the present invention (including "Cured Product Manufacturing Method 2"; the same applies hereinafter) or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the formation of patterns by etching of insulating films for the above-mentioned mounting applications. For these applications, reference can be made to, for example, "High Performance Polyimide and Application Technology" (Science & Technology Co., Ltd., April 2008), edited by Masaaki Kakimoto, CMC Technical Library, "Fundamentals and Development of Polyimide Materials" (published November 2011), and "Latest Polyimides: Fundamentals and Applications" (NTS, August 2010), edited by the Japan Polyimide and Aromatic Polymer Research Association.

[0305] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0306] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate is a laminate including two or more layers each made of the cured product, and may be a laminate including three or more layers. At least one of the two or more layers each made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0307] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

[0308] The laminate of the present invention preferably includes two or more layers made of a cured product and a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on a layer made of a cured product between multiple cured product production processes. A preferred embodiment of the metal layer-forming step is as described above. Examples of the laminate include a laminate having at least a layer structure in which three layers are stacked in this order: a layer made of a first cured product, a metal layer, and a layer made of a second cured product. It is preferred that both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring, such as a rewiring layer.

[0309] <Lamination Step> The method for producing a laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step and a post-development exposure step again on the surface of the pattern (resin layer) or the metal layer in this order. However, at least one of (a) the film formation step and (d) the heating step and the post-development exposure step may be repeated. Furthermore, after at least one of (d) the heating step and the post-development exposure step, (e) a metal layer formation step may be included. It goes without saying that the lamination step may further include the above-mentioned drying step or the like as appropriate.

[0310] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

[0311] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a structure having 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure having 2 to 9 resin layers is even more preferred. Each of the layers may be the same or different in composition, shape, film thickness, etc.

[0312] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.Specific examples include an embodiment in which the steps of (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order, or an embodiment in which the steps of (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order.By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0313] (Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be surface-activated before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or may be performed on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is to be formed. In this way, by performing the surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on the surface can be improved. The surface activation treatment is also preferably performed on part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion with the metal layer or resin layer provided on the surface that has been surface-activated can be improved. In particular, when negative development is performed, when the resin composition layer is cured, it is less susceptible to damage due to surface treatment and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. The contents of this specification are incorporated herein by reference.

[0314] (Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a manufacturing method for a semiconductor device comprising the manufacturing method for the cured product or the manufacturing method for the laminate of the present invention. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0315] The cured product of the present invention has excellent thermal conductivity and can therefore also be used as a thermally conductive material. Thermally conductive materials (e.g., thermally conductive sheets) can be used as heat dissipation materials, such as heat-dissipating sheets, for heat dissipation applications in various devices. More specifically, a device with a thermally conductive layer can be fabricated by disposing a thermally conductive layer containing the thermally conductive material (e.g., thermally conductive sheet) of the present invention on the device, and heat generated by the device can be efficiently dissipated through the thermally conductive layer. Thermally conductive materials (e.g., thermally conductive sheets) have sufficient thermal conductivity and high heat resistance, making them suitable for heat dissipation applications in power semiconductor devices used in various electrical appliances, such as personal computers, general home appliances, and automobiles. Furthermore, because thermally conductive materials have sufficient thermal conductivity even in a semi-cured state, they can also be used as heat dissipation materials to be placed in areas where light for photocuring is difficult to reach, such as gaps between components of various devices. Furthermore, because they have excellent adhesive properties, they can also be used as thermally conductive adhesives.

[0316] The thermally conductive material (such as a thermally conductive sheet) may be used in combination with a member other than the member (cured product) formed from the composition of the present invention. For example, the thermally conductive material may be combined with a sheet-like support other than the layer formed from the composition of the present invention. Examples of the sheet-like support include a plastic film, a metal film, or a glass plate. Examples of plastic film materials include polyesters such as polyethylene terephthalate (PET), polycarbonates, acrylic resins, epoxy resins, polyurethanes, polyamides, polyolefins, cellulose derivatives, and silicones. Examples of metal films include copper films.

[0317] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing 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 based on mass.

[0318] <Resin Synthesis Examples> [Synthesis Example 1: Synthesis of P-1] P-1 was synthesized using M-1 as Monomer 1 and A-1 as Monomer 2. Details of the synthesis method for P-1 are shown below.

[0319]

[0320] 3.65 g (11.3 mmol) of M-1, 2.42 g (11.5 mmol) of A-1, 2.33 g of triethylamine (23.1 mmol), and 30 mL of N-methylpyrrolidone were mixed and stirred at 60°C for 6 hours. The reaction solution was cooled to room temperature and added dropwise to 1 L of 0.1 mol / L hydrochloric acid to precipitate a polyimide precursor. The polyimide precursor was collected by filtration and washed three times with 500 mL of water. The resulting polyimide precursor was dried under reduced pressure at 45°C for 24 hours. 5.8 g of the dried powder was dissolved in 30 mL of N-methylpyrrolidone, followed by the addition of 1.0 g of water and 5.0 g of ion exchange resin UP6040 (AmberTec Corporation) and stirring for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 1 L of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45°C for 24 hours to obtain 5.6 g of P-1. The molecular weight of P-1 was measured by gel permeation chromatography (GPC), and the weight average molecular weight (Mw) was 20,000 and the dispersity (Mw / Mn) was 2.0.

[0321] Synthesis Example 2: Synthesis of P-5 3.65 g (11.3 mmol) of M-1, 2.95 g (22.7 mmol) of 2-hydroxyethyl methacrylate (R-1), 3.58 g (45.2 mmol) of pyridine, and 20 mL of N-methylpyrrolidone were mixed and stirred at 60°C for 4 hours to synthesize the diester of M-1 and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 2.83 g (23.8 mmol) of thionyl chloride was added over 5 minutes while maintaining the temperature at -10±5°C. After dilution with 5 mL of N-methylpyrrolidone, a solution of 2.42 g (11.5 mmol) of A-1 dissolved in 15 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 5 minutes at -10±5°C, and the mixture was stirred at room temperature for 2 hours. After that, 1.0 g of ethanol was added and stirred at room temperature for 1 hour. The reaction solution was then added to 1 L of water to precipitate a polyimide precursor. The precipitate (solid polyimide precursor) was collected by filtration and dissolved in 40 mL of N-methylpyrrolidone. The resulting solution was added dropwise to 1 L of water to precipitate a polyimide precursor. The precipitate (solid polyimide precursor) was again filtered and dried at 45°C under reduced pressure for 24 hours. 8.6 g of the dried powder was dissolved in 40 mL of N-methylpyrrolidone, after which 0.2 g of triethylamine was added and stirred at room temperature for 35 minutes. The solution was then added to 1 L of water, and the precipitate was collected by filtration. The resulting precipitate was dissolved in 40 mL of N-methylpyrrolidone. 1.0 g of water and 5.0 g of ion exchange resin UP6040 (AmberTec) were added to the solution and stirred for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 1 L of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45°C for 24 hours to obtain 8.4 g of P-5. The molecular weight of P-5 was measured by gel permeation chromatography (GPC) to find that the weight average molecular weight (Mw) was 20,000 and the dispersity (Mw / Mn) was 2.0.

[0322] Synthesis Example 3: Synthesis of P-37: 3.65 g (11.3 mmol) of M-1 and 15 mL of N-methylpyrrolidone were mixed and stirred for 1 hour. A solution prepared by mixing 2.33 g of triethylamine (23.1 mmol), 0.97 g (4.61 mmol) of A-1, and 0.75 g (6.92 mmol) of A-7 in 15 mL of N-methylpyrrolidone was added dropwise to the above solution at room temperature. The mixture was then stirred at 60°C for 6 hours. The reaction solution was cooled to room temperature and added dropwise to 1 L of 0.1 mol / L hydrochloric acid to precipitate a polyimide precursor. The polyimide precursor was collected by filtration and washed three times with 500 mL of water. The resulting polyimide precursor was dried under reduced pressure at 45°C for 24 hours. After dissolving 5.2 g of the dried powder in 30 mL of N-methylpyrrolidone, 1.0 g of water and 5.0 g of ion exchange resin UP6040 (AmberTec) were added and stirred for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 1 liter of water to obtain a precipitate. The precipitate was collected by filtration and dried at 45°C under reduced pressure for 24 hours to obtain 5.0 g of P-37. The molecular weight of P-37 was measured using gel permeation chromatography (GPC), and the weight average molecular weight (Mw) was 20,000 and the polydispersity (Mw / Mn) was 2.0.

[0323] The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using gel permeation chromatography (GPC) and expressed as polystyrene equivalent values. Mw and Mn were determined using an HLC-8220GPC (manufactured by Tosoh Corporation) and 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. NMP (N-methyl-2-pyrrolidone) was used as the eluent. Detection in the GPC measurement was performed using a UV (ultraviolet) detector at a wavelength of 254 nm.

[0324] Examples and Comparative Examples Resin compositions were obtained by mixing the components (resins and other components) listed in Tables 1 to 8 below. The other components were used in the amounts (parts by mass) listed in Tables 1 to 8 below. Tables 1 to 8 below list the resin content (% by mass) and the other component content (% by mass) relative to the mass of each resin composition. In each of the Examples and Comparative Examples, a resin was synthesized using the compounds listed in "Monomer 1," "Monomer 2," and "Side Chain Component" listed in Tables 1 to 8 below in the amounts (parts by mass) listed in Tables 1 to 8 below, respectively, and had the structure listed in "Resin Structure" and the weight-average molecular weight listed in "Mw." The "ratio" of the solvent refers to the mass ratio (% by mass) of each solvent relative to the total solvent amount. The resulting resin composition was pressure-filtered using a polytetrafluoroethylene filter with a pore width of 20.0 μm. In the tables, a "-" in the "Resin" column indicates that the corresponding compound was not used during resin synthesis. Furthermore, the notation "-" in the "Other Components" column indicates that the resin composition does not contain the corresponding component.

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333] Details of each component listed in the above table are as follows:

[0334] <Monomer 1> The structural formula of the compound used as Monomer 1 is shown below.

[0335]

[0336]

[0337] <Monomer 2> The structural formula of the compound used as Monomer 2 is shown below.

[0338]

[0339] <Side Chain Component> R-1 was used as the side chain component.

[0340]

[0341] <Resin> The structures of the resins used (resin structures) are shown below. Each resin contains the structure bracketed in [ ] as a repeating unit. The content of each repeating unit in each resin varies depending on the amount of raw materials used when synthesizing the resin. The weight average molecular weight (Mw) of the resin can be adjusted by increasing or decreasing the amount of added Monomer 1 and Monomer 2 used (particularly the amount of added Monomer 2). For resins containing two types of repeating units, the content of each repeating unit (molar ratio (mol %) to all repeating units) is indicated by a subscript to the right of each [ ]. The composition ratio (mol %) of the resin is １ The molecular weights of the resins used in the examples and comparative examples were measured by H-NMR (nuclear magnetic resonance). The Mw of the resins used in the examples and comparative examples is shown in Tables 1 to 8. The dispersity (Mw / Mn) of the resins used in the examples and comparative examples is also shown in Tables 1 to 8.

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351] For the above P-1 to P-54, Q-1 to Q-14 and Q-16 to Q-36 are shown below, which are the resin structures ("resin structures after curing") after curing in the "Formation of a cured product (film)" section described below. Each resin contains the structure enclosed in square brackets [ ] as a repeating unit. For resins containing two types of repeating units, the content of each repeating unit (molar ratio (mol %) relative to all repeating units) is indicated by a subscript to the right of each square bracket [ ].

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359] <Polymerizable Compound> The polymerizable compounds used are as follows: D-1: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) D-2: SR-209 (manufactured by Sartomer) D-3: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0360] <Polymerization initiator> The polymerization initiators used are as follows: C-1: IRGACURE OXE 01 (manufactured by BASF) C-2: IRGACURE OXE 02 (manufactured by BASF) C-3: IRGACURE 369 (manufactured by BASF) C-4: Compound represented by the following structural formula

[0361]

[0362] <Polymerization inhibitor> The following polymerization inhibitors were used: E-1: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) E-2: parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) E-3: paramethoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0363] <Silane Coupling Agent> The silane coupling agents used are shown below, where Et represents an ethyl group.

[0364]

[0365] <Migration Inhibitor> The migration inhibitors used are shown below.

[0366]

[0367]

[0368] <Base Generator> The base generators used are shown below.

[0369]

[0370] <Solvent> As the solvent, for example, the following solvents can be used, and in the examples, the solvents selected from the following were used: DMSO: dimethyl sulfoxide GBL: γ-butyrolactone NMP: N-methylpyrrolidone

[0371] (Formation of cured product (film)) Each resin composition was applied to a silicon wafer by spin coating to form a coating film. The silicon wafer with the resulting coating film was dried on a hot plate at 100°C for 5 minutes to obtain a film of uniform thickness on the silicon wafer. The film was heated at a temperature increase rate of 10°C / min, and heated at the "cure temperature" (°C) shown in Tables 1 to 8 for the "cure time" (min) shown in Tables 1 to 8 to cure, thereby obtaining a cured product (cured film). The film thickness of each film (cured film) is shown in Tables 1 to 8.

[0372] The X-ray diffraction spectrum of the obtained cured product was measured as follows. (Preparation of film for measuring X-ray diffraction spectrum) The above cured product was immersed in a 4.9 mass% aqueous solution of hydrofluoric acid and peeled from the silicon wafer to obtain a film with a thickness of 20 μm. Note that in Comparative Examples 7 and 8, a cured film could not be formed.

[0373] (Measurement of X-ray diffraction spectrum) The X-ray diffraction spectrum was measured in a transmission configuration using a common X-ray diffractometer (SmartLab manufactured by Rigaku Corporation, D8 Discover manufactured by Bruker, etc.). X-rays (Cukα rays, wavelength: 1.54 Å) were irradiated in a direction parallel to the thermal conduction direction of the film, and the XRD pattern was detected using a two-dimensional detector or an imaging plate. The obtained two-dimensional image was integrated in all directions to obtain a 2θ profile.

[0374] (Calculation of Crystallite Size) A 2θ profile (background) obtained under similar conditions without a sample was subtracted from the 2θ profile obtained above. Baseline processing was performed on the obtained profile. Baseline processing was performed by utilizing the area where no peaks were observed in the range of 5 to 15° (around 5 to 6° or 12 to 13°) and subtracting using a spline function method. Other baselines can also be processed using the Sonneveld-Visser method, etc. Diffraction peaks in the baseline-processed spectrum were fitted using a split pseudo-Voigt function to calculate the full width at half maximum. The crystallite size D was calculated from the full width at half maximum of the obtained peak using the Scherrer formula. D = Kλ / β cos θ D: crystallite size K: Scherrer constant 0.97 λ: X-ray wavelength 1.54 Å β: full width at half maximum θ: diffraction angle of the peak

[0375] The X-ray diffraction spectrum of the obtained cured film was confirmed to have a diffraction peak in the range of 5 to 15°. The X-ray diffraction spectra of the cured films obtained in Comparative Examples 1 to 6 and 9 to 12 were also confirmed, but no diffraction peak in the range of 5 to 15° was confirmed. In Comparative Examples 7 and 8, a cured film could not be formed, and therefore no diffraction spectrum could be confirmed.

[0376] In the above "formation of a cured product (film)", if a cured product obtained by heating at a "cure temperature" of 230°C for a "cure time" of 120 (min (minutes)" has a diffraction peak in the range of 5 to 15° in the X-ray diffraction spectrum and the crystallite size derived from the diffraction peak is 30 Å or more, then in the above "formation of a cured product (film)", a cured product obtained by heating at a "cure temperature" of 300°C for a "cure time" of 60 (min (minutes)" also has a diffraction peak in the range of 5 to 15° in the X-ray diffraction spectrum and the crystallite size derived from the diffraction peak is 30 Å or more.

[0377] The orientation coefficient fzx of the resin composition before heating and the orientation coefficient fzx of the resulting cured product were determined as follows.

[0378] <Polarized ATR-IR Measurement> Polarized ATR-IR measurement was performed under the following conditions. A general macro ATR-IR device can be used as the measurement device, but it is preferable to use an MCT detector to obtain sufficient detection sensitivity. Prism: Germanium Pressure between prism and sample: 20 cN m Incident angle: 45° Number of reflections: 1 Resolution: 4 cm －１ Measurement was performed after confirming that the cured product (sample) was sufficiently adhered to the entire surface of the prism. The FTIR-ATR spectrum was measured by irradiating perpendicularly polarized light (s-polarized light; transverse electric, TE) and horizontally polarized light (transverse magnetic, TM) onto the incident surface, which is composed of light incident on the sample surface and light reflected from it, using a wire grid polarizer. The absorption spectrum when perpendicularly polarized light was incident was measured as S ＴＥ , the absorption spectrum when horizontally polarized light is incident is S ＴＭ The obtained spectrum was subjected to atmospheric correction so that the signal derived from water vapor was below the noise level.

[0379] <Calculation of absorbance (peak area)> S ＴＥ , S ＴＭ In each spectrum, 1765 to 1790 cm －１ The area A enclosed by the spectrum and the baseline for the imide C=O group symmetric stretching peak having a maximum absorption point in the range ＴＥ , AＴＭ The endpoints on the low wavenumber side and the high wavenumber side of the baseline at this time were calculated by dividing the endpoint on the low wavenumber side by 1750 to 1775 cm －１ Between the high wavenumber end points, 1780 and 1815 cm －１ The spectrum was set on the spectrum between the above values ​​so that the baseline did not intersect with the spectrum and the area enclosed by the spectrum and the baseline was maximized.

[0380] <Calculation of orientation coefficient fzx> In this sample, the absorption coefficient k in the x direction ｘ and the absorption coefficient in the y direction k ｙ can be considered equal (k ｘ = k ｙ ).

[0381] A mentioned in the preceding paragraph ＴＥ , A ＴＭ Using the above, the absorption coefficient k is calculated according to the formulas ([Formula 1], [Formula 2] and [Formula 3]) described in the reference document (JP-A 2004-126109). ｘ and k ｚ The infrared dichroic ratio D ｚｘ = k ｚ / k ｘ As the orientation coefficient in the film thickness direction, f ｚｘ was calculated using the following formula:

[0382]

[0383] where

[0384]

[0385] where δ is the angle between the transition moment vector formed by molecular vibration and the molecular axis. The imide C=O group symmetric stretching mode used here is a vibration mode parallel to the molecular axis, and δ can be calculated as 0°. The resulting orientation coefficient f ｚｘ is based on the film thickness direction (axis perpendicular to the film surface, z-axis), is 1 when the molecular chains are completely oriented parallel, is 0 when they are randomly oriented, and is -0.5 when they are completely oriented perpendicular.

[0386] Furthermore, the orientation coefficient fzx of the resin composition of the present invention before heating was in a state where it was dissolved in a solvent, so the orientation coefficient fzx was set to 0. The orientation coefficient fzx of the resin compositions of Comparative Examples 1 to 6 and 9 to 12 before heating was in a state where it was dissolved in a solvent, so the orientation coefficient fzx was set to 0. The orientation coefficient fzx of the resin compositions of Comparative Examples 7 to 8 before heating was in a state where it was not dissolved in a solvent, so the orientation coefficient fzx was not measurable. Since no cured products were obtained with the resin compositions of Comparative Examples 7 to 8, the orientation coefficient fzx of the obtained cured products was not measurable.

[0387] In the above "formation of a cured product (film)", if the orientation coefficient fzx of the cured product obtained by heating at a "cure temperature" of 230°C for a "cure time" of 120 (min (minutes)" in the above "formation of a cured product (film)" is -0.20 or less, then the orientation coefficient fzx of the cured product obtained by heating at a "cure temperature" of 300°C for a "cure time" of 60 (min (minutes)" in the above "formation of a cured product (film)" is -0.20 or less.

[0388] (Dissolution rate of cured film in N-methyl-2-pyrrolidone)

[0389] As shown in Tables 1 to 8, the thickness of the cured film was 20 μm.

[0390] <Measurement of Dissolution Rate> The dissolution rate of the cured film in N-methyl-2-pyrrolidone can be calculated by immersing a silicon wafer on which a cured film has been formed in N-methyl-2-pyrrolidone for 15 seconds and measuring the film thickness before and after immersion using an ellipsometer. The film is immersed in N-methyl-2-pyrrolidone without being subjected to any heating other than the drying step. The amount of N-methyl-2-pyrrolidone used for immersion is 30 times the volume of the film. The temperature of N-methyl-2-pyrrolidone, the film, and the silicon wafer during immersion is 23°C. In cases where the film is completely dissolved or where the film thickness does not change at all, the immersion time can be appropriately changed to calculate the dissolution rate.

[0391] The dissolution rates in N-methyl-2-pyrrolidone of 20 μm thick films obtained from the resin compositions of the examples of the present invention and the resin compositions of Comparative Examples 1 to 6 and 9 to 12 were all within the range of 0.01 to 1.00 μm / sec. As described above, in Comparative Examples 7 and 8, it was not possible to form a cured film, and therefore it was not possible to measure the dissolution rates in N-methyl-2-pyrrolidone of 20 μm thick films obtained from the resin compositions of Comparative Examples 7 and 8. If the heating conditions in <Preparation of Cured Product> (300°C, 60 minutes) were changed (e.g., to 230°C, 120 minutes) and the dissolution rates of the resulting cured products were measured in the same manner as in <Measurement of Dissolution Rate> above, and the obtained value was 0.01 to 1.00 μm / sec, then the dissolution rate of the cured product produced in the above <Preparation of Cured Product> would also be 0.01 to 1.00 μm / sec.

[0392] In the above "formation of a cured product (film)", if the dissolution rate in N-methyl-2-pyrrolidone of a cured product (cured film) obtained by heating at a "cure temperature" of 230°C for a "cure time" of 120 (min (minutes)" in the above "formation of a cured product (film)" is within the range of 0.01 to 1.00 μm / sec, then the dissolution rate in N-methyl-2-pyrrolidone of a cured product obtained by heating at a "cure temperature" of 300°C for a "cure time" of 60 (min (minutes)" in the above "formation of a cured product (film)" is within the range of 0.01 to 1.00 μm / sec.

[0393] <Evaluation> Evaluation was carried out as follows, and the results are shown in Tables 1 to 8 above.

[0394] [CTE Measurement] The cured product was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, peeled from the silicon wafer, and punched out using a punching machine to obtain test specimens measuring 50 mm in length, 20 mm in width, and 20 μm in thickness. The CTE of the prepared test specimens at 25°C to 125°C was measured using a TMA450 (TA Instruments). The heating and cooling conditions for evaluation were as follows (1) to (4): (1) Heating from room temperature (23°C) to 130°C at a heating rate of 5°C / min. (2) Cooling from 130°C to 10°C at a cooling rate of 5°C / min. (3) Heating from 10°C to 220°C at a heating rate of 5°C / min. (4) Natural cooling to room temperature. The elongation (displacement) of the sample was measured during the temperature increase and decrease processes (1) to (4) above, and the elongation (displacement) of the sample at 25°C and 125°C in process (3) was divided by the temperature to calculate the CTE. (For example, if the length of the sample at 25°C was 50 mm and the length of the sample at 125°C was 50.175 mm, the displacement was 0.35% = 3500 ppm, and the CTE was calculated as 3500 / (125-25) = 35 ppm / °C.) The obtained CTE was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "CTE" column of Tables 1 to 8 above. -Evaluation criteria- A: CTE is less than 35 ppm / °C B: CTE is 35 ppm / °C or more and less than 45 ppm / °C C: CTE is 45 ppm / °C or more and less than 55 ppm / °C D: CTE is 55 ppm / °C or more E: Unmeasurable

[0395] [Measurement of Thermal Conductivity] Test specimens were prepared using a method similar to that used to measure CTE, and thermal conductivity was evaluated. Here, thermal conductivity was calculated from the product of three physical properties: thermal diffusivity, density, and specific heat. Thermal diffusivity was measured using a thermal diffusivity measuring device FTC-RT (manufactured by Advance Riko) based on the cyclic heating method (in accordance with the international standard for plastics, ISO 22007-3), by acquiring reference data from a silicon wafer of the same thickness and calculating the difference. Thermal diffusivity was measured by contacting the device with the sample. Density was measured using a density gradient tube method specific gravity measuring device Type B (manufactured by Shibayama Scientific Instruments) based on density measurement using the density gradient tube method (in accordance with JIS K 7112). A calcium nitrate solution was used as the density gradient liquid. Specific heat was measured using a Q2000 (manufactured by TA Instruments) based on the specific heat capacity measurement method (in accordance with JIS K 7123). At the same time as the sample, measurements were also taken on a sample-free (empty pan) and sapphire (a standard substance with a known specific heat, 0.779 J / (g·K) at 25°C). The specific heat of the sample was calculated from the difference in DSC (Differential Scanning Calorimetry) heat flux (heat flow) between the sample and the empty pan at 25°C. The results are shown in the "Thermal Conductivity" column in Tables 1 to 8 above. - Evaluation Criteria - A: Thermal conductivity is 0.50 W / m·K or more B: Thermal conductivity is 0.40 W / m·K or more but less than 0.50 W / m·K C: Thermal conductivity is 0.25 W / m·K or more but less than 0.40 W / m·K D: Thermal conductivity is less than 0.25 W / m·K E: Unmeasurable

[0396] From the above results, it was found that the examples of the present invention can provide a resin composition that can form a cured product having high thermal conductivity and low CTE.

[0397] Example 201 [Preparation of Redistribution Layer Insulating Film] The resin composition used in Example 1 was applied in the form of a layer by spin coating to the surface of the thin copper layer of a resin substrate having a thin copper layer formed on its surface. The resulting layer was dried at 100°C for 5 minutes to form a 20 μm-thick photosensitive film, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After the exposure, the film was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern. The temperature was then increased at a rate of 10°C / min in a nitrogen atmosphere until it reached 230°C, at which point it was maintained at 230°C for 180 minutes to form a redistribution layer interlayer insulating film. This redistribution layer interlayer insulating film had excellent insulating properties. Furthermore, a semiconductor device was manufactured using this redistribution layer interlayer insulating film, and it was confirmed to function without any problems.

[0398] According to the present invention, it is possible to provide a resin composition capable of forming a cured product having high thermal conductivity and a low thermal expansion coefficient, a cured product obtained by curing the resin composition, a laminate including the cured product, and a method for producing the cured product.

[0399] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2024-020708) filed on February 14, 2024, the contents of which are incorporated herein by reference.

Claims

1. A resin composition comprising: a polyimide precursor; and a solvent, wherein the resin composition is heated at 300°C for 60 minutes to obtain a cured product, which has a diffraction peak in the range of 5 to 15° in an X-ray diffraction spectrum, and the crystallite size derived from the diffraction peak is 30 Å or more.

2. A resin composition comprising: a polyimide precursor having a repeating unit represented by the following formula (1); and a solvent, wherein the content of the repeating unit represented by the following formula (1) is 40 mol% or more based on the total repeating units of the polyimide precursor. In formula (1), X ２ represents a group represented by any one of formulas (V-1) to (V-7). In formula (V-1), R １ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n1 represents an integer of 0 to 2. In formula (V-2), R ２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n2 represents an integer of 0 to 4. In formula (V-3), R ３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n3 represents an integer of 0 to 4. In formula (V-4), R ４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n4 represents an integer of 0 to 4. In formula (V-5), R ５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n5 represents an integer of 0 to 4. R ６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n6 represents an integer of 0 to 4. In formula (V-6), R ７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n7 represents an integer of 0 to 3. R ８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n8 represents an integer of 0 to 3. In formula (V-7), R ９ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n9 represents an integer of 0 to 3. R １０ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n10 represents an integer of 0 to 3. * represents a bonding position. L each independently represents a group represented by any one of formulas (L-1) to (L-18). In formula (L-1), n ​​represents 0 or 1. In formula (L-4), R each independently represents a hydrogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. In formula (L-9), R １１ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n11 represents an integer of 0 to 4. In formula (L-10), R １２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n12 represents an integer of 0 to 6. In formula (L-11), R １３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n13 represents an integer of 0 to 4. R １４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n14 represents an integer of 0 to 4. In formula (L-16), R １５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n15 represents an integer of 0 to 4. R １６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n16 represents an integer of 0 to 4. In formula (L-17), R １７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n17 represents an integer of 0 to 4. In formula (L-18), R １８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n18 represents an integer of 0 to 4. L １ each independently represents a group represented by any one of formulas (L-1) to (L-15). * represents a bonding position. Y ２ represents a divalent linking group containing a structure represented by the following formula (2): １ and A ２ are each independently an oxygen atom or —NR Ｚ - represents. Ｚ represents a hydrogen atom or a monovalent organic group. １ and Z ２ each independently represents a hydrogen atom or a monovalent organic group. In formula (2), R ２１ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２２ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２３ , R ２４ each independently represents a hydrogen atom or a methyl group. m1 represents an integer of 0 or more and 4 or less. m2 represents an integer of 0 or more and 4 or less. * represents a bonding position.

3. The resin composition according to claim 1, wherein a cured film having a thickness of 20 μm obtained from said resin composition has a dissolution rate in N-methyl-2-pyrrolidone of 0.01 to 1.00 μm / sec.

4. Z in the formula (1) １ and Z ２ The resin composition according to claim 2, wherein at least one of the following represents a group represented by the following formula (3): In formula (3), R ｘ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ represents -, a cycloalkylene group, or a polyalkyleneoxy group. ２８ and R ２９ represents a hydrogen atom. ３０ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group. * represents a bonding position.

5. The resin composition according to any one of claims 1 to 4, further comprising a polymerization initiator.

6. The resin composition according to any one of claims 1 to 4, further comprising a polymerizable compound.

7. The resin composition according to claim 1, wherein the diffraction peak is derived from polyimide.

8. The resin composition according to claim 1, wherein the crystallite size of the cured product obtained by heating the resin composition at 300°C for 60 minutes is less than 300 Å.

9. The resin composition according to any one of claims 1 to 4, wherein the orientation coefficient fzx of the resin composition before heating is greater than -0.20, and the orientation coefficient fzx of a cured product obtained by heating the resin composition at 300°C for 60 minutes is -0.20 or less.

10. The resin composition according to any one of claims 1 to 4, wherein the resin composition is a negative photosensitive resin composition.

11. The resin composition according to any one of claims 1 to 4, which is used to form an interlayer insulating film for a rewiring layer.

12. A cured product obtained by curing the resin composition according to any one of claims 1 to 4.

13. A laminate comprising two or more layers of the cured product according to claim 12, and a metal layer between any of the layers of the cured product.

14. A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of claims 1 to 4 onto a substrate to form a film.

15. A method for producing a cured product, comprising: forming a film from a resin composition containing a polyimide precursor having a repeating unit represented by the following formula (1) and a solvent; and heating the film to obtain a cured product, wherein the cured product has a diffraction peak in the range of 5 to 15° in an X-ray diffraction spectrum, and a crystallite size derived from the diffraction peak is 30 Å or more, and the content of the repeating unit represented by formula (1) is 40 mol% or more of all repeating units. In formula (1), X ２ represents a group represented by any one of formulas (V-1) to (V-7). In formula (V-1), R １ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n1 represents an integer of 0 to 2. In formula (V-2), R ２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n2 represents an integer of 0 to 4. In formula (V-3), R ３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n3 represents an integer of 0 to 4. In formula (V-4), R ４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n4 represents an integer of 0 to 4. In formula (V-5), R ５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n5 represents an integer of 0 to 4. R ６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n6 represents an integer of 0 to 4. In formula (V-6), R ７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n7 represents an integer of 0 to 3. R ８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n8 represents an integer of 0 to 3. In formula (V-7), R ９ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n9 represents an integer of 0 to 3. R １０ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n10 represents an integer of 0 to 3. * represents a bonding position. L each independently represents a group represented by any one of formulas (L-1) to (L-18). In formula (L-1), n ​​represents 0 or 1. In formula (L-4), R each independently represents a hydrogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. In formula (L-9), R １１ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n11 represents an integer of 0 to 4. In formula (L-10), R １２ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n12 represents an integer of 0 to 6. In formula (L-11), R １３ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n13 represents an integer of 0 to 4. R １４ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n14 represents an integer of 0 to 4. In formula (L-16), R １５ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n15 represents an integer of 0 to 4. R １６ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n16 represents an integer of 0 to 4. In formula (L-17), R １７ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n17 represents an integer of 0 to 4. In formula (L-18), R １８ are each independently an organic group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. n18 represents an integer of 0 to 4. L １ each independently represents a group represented by any one of formulas (L-1) to (L-15). * represents a bonding position. Y ２ represents a divalent linking group containing a structure represented by the following formula (2): １ and A ２ are each independently an oxygen atom or —NR Ｚ - represents. Ｚ represents a hydrogen atom or a monovalent organic group. １ and Z ２ each independently represents a hydrogen atom or a monovalent organic group. In formula (2), R ２１ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２２ R each independently represents a halogen atom, an organic group having 1 to 2 carbon atoms, or a halogenated alkyl group. ２３ , R ２４ each independently represents a hydrogen atom or a methyl group. m1 represents an integer of 0 or more and 4 or less. m2 represents an integer of 0 or more and 4 or less. * represents a bonding position.

16. The method for producing a cured product according to claim 15, wherein the cured product is obtained by heating at 200°C or higher.

17. The method for producing a cured product according to claim 15 or 16, further comprising an exposure step and a development step.

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