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

Abstract

Provided are: a resin composition containing (a) an oxime polymerization initiator, (b) a polyimide, and (c) a polymerizable compound, wherein the polymerization initiator does not contain a sulfur atom, and the total content of the polymerization initiator and the sensitizer is 0.1-2.8 mass% with respect to the total solid content of the composition; a cured product obtained by curing the resin composition; a laminate containing the cured product; and a method for producing the cured product.

Description

Resin composition, cured product, laminate, method for manufacturing a cured product, method for manufacturing a laminate, method for manufacturing a semiconductor device, and semiconductor device

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

[0002] Polyimide is used in various fields, such as insulating films for electronic devices, due to its excellent heat resistance and insulating properties. Patent Document 1 describes a soluble photosensitive polyimide resin composition characterized by containing (A) a water-soluble photosensitive polyimide polymer having a duplicate structure represented by a specific formula (I), (B) a (meth)acrylic acid monomer diluent, and (C) a photoinitiator, wherein the weight ratio of component (A) to component (B) is 100:10 to 200, and the content of component (C) the photoinitiator is 0.1 to 15.0% by weight relative to 100% by weight of component (A). Patent Document 2 describes a method for producing a film, which includes a step of applying a photosensitive resin composition containing (A) a resin, (C) a photopolymerization generator, a specific (D) radical polymerization inhibitor, and (E) a solvent onto a substrate, and then drying it under a pressure of 5000 Pa or less.

[0003] Japanese Patent Publication No. 2010-155962, International Publication No. 2024 / 070963

[0004] Polyimide is used in a variety of fields, including semiconductors and aerospace. In recent years, there has been a demand for further improvements in reliability and resolution in cured films (e.g., interlayer insulating films for redistribution layers) formed by curing polyimide-containing resin compositions used in semiconductor packaging (back-end processes).

[0005] The present invention aims to provide a resin composition capable of forming a cured product with high reliability and excellent resolution, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product.

[0006] Examples of typical embodiments of the present invention are shown below. [1] A resin composition comprising (a) an oxime polymerization initiator, (b) a polyimide, and (c) a polymerizable compound, wherein the polymerization initiator does not contain sulfur atoms, and the total amount of the polymerization initiator and the sensitizer is 0.1 to 2.8% by mass with respect to the total solid content of the composition.

[0007] [2] The resin composition according to [1], wherein the C=C value of the polymerizable compound (c) is 7.00 mmol / g or more. [3] The resin composition according to [2], wherein the polymerizable compound (c) is a chain-like bifunctional monomer.

[0008] [4] The resin composition according to any one of [1] to [3], wherein the polymerizable compound in (c) above is a compound represented by the following formula (M1).

[0009]

[0010] In formula (M1), R represents either a hydrogen atom or an alkyl group, independently. n represents an integer between 2 and 3.

[0011] [5] The resin composition according to any one of [1] to [4], wherein the C=C value of the polyimide in (b) above is 0.40 to 2.00 mmol / g.

[0012] [6] The resin composition according to any one of [1] to [5], wherein the (b) polyimide has a group represented by the following formula (S).

[0013]

[0014] In formula (S), * indicates the bonding position.

[0015] [7] A resin composition according to any one of [1] to [6], used for forming an interlayer insulating film for a redistribution layer. [8] A cured product obtained by curing a resin composition according to any one of [1] to [7].

[0016] [9] A laminate comprising two or more layers made of the cured product described in [8], wherein a metal layer is included between any of the layers made of the cured product.

[10] A method for producing a cured product, comprising a film-forming step of applying the resin composition described in any one of [1] to [7] onto a substrate to form a film.

[0017]

[11] A method for manufacturing a cured product according to

[10] , comprising an exposure step of selectively exposing the above film, and a developing step of developing the above film using a developer to form a pattern.

[12] A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to

[11] .

[13] A semiconductor device comprising the cured product according to [8].

[0018] According to the present invention, it is possible to provide a resin composition capable of forming a cured product with high reliability and excellent resolution, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product.

[0019] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments explicitly stated. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, 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 connecting Guard Column SuperAW-H, TSKgel SuperAWM-H, and TSKgel SuperAWM-H (all manufactured by Tosoh Corporation) in series in that order as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. If NMP is not suitable as the eluent, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting the laminate is described as "above" or "below," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. In other words, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, 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 this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. Unless otherwise specified in this specification, a composition may contain two or more compounds corresponding to each component in the composition. 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 atm), and the relative humidity is 50% RH. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chains" refers to the other bonding chains. In this specification, a preferred embodiment is a more preferred embodiment.

[0020] [Resin Composition] The resin composition of the present invention (also simply referred to as "resin composition") is a resin composition containing (a) an oxime polymerization initiator, (b) polyimide, and (c) a polymerizable compound, wherein the polymerization initiator does not contain sulfur atoms, and the total amount of the polymerization initiator and the sensitizer is 0.1 to 2.8% by mass with respect to the total solid content of the composition.

[0021] The mechanism by which the reliability and resolution of cured products obtained from the resin composition of the present invention are improved is not fully understood, but the inventors have hypothesized the following. However, the present invention is not limited in any way by the hypothesized mechanism below. First, in resin compositions containing a polymerization initiator, polyimide, and polymerizable compounds, polymerization initiators containing sulfur atoms are widely known as polymerization initiators. As a result of diligent research aimed at improving the performance of resin compositions, the inventors have found that films obtained from resin compositions using polymerization initiators containing sulfur atoms tend to have reduced conductivity of wiring in contact with the film, especially when exposed to high temperatures. Therefore, in the present invention, it is believed that by using an oxime polymerization initiator that does not contain sulfur atoms, the above phenomenon is suppressed and the reliability of cured products obtained from the resin composition is improved. Here, oxime initiators have a high absorption coefficient of the oxime structure and tend to be relatively sensitive to exposure. However, high sensitivity tends to narrow the exposure latitude (even slight fluctuations in the amount of exposure can easily cause the size of the formed pattern (line width, etc.) to deviate from the desired value), resulting in a tendency for lower resolution. Therefore, the inventors have found that by limiting the total amount of the oxime initiator and the sensitizer that may be contained in the resin composition to an appropriate amount relative to the total solid content of the resin composition, sensitivity can be suppressed, the exposure latitude can be broadened, and consequently, the resolution of the cured product can be improved. In other words, by setting the total amount to 0.1 to 2.8% by mass relative to the total solid content of the resin composition, it is possible to suppress the improvement in sensitivity of the resin composition and thereby improve the resolution of the cured product.

[0022] (a) Oxime polymerization initiator The resin composition of the present invention contains (a) an oxime polymerization initiator (hereinafter also referred to as "polymerization initiator (a)"). The polymerization initiator (a) is an aspect of a photo radical polymerization initiator and has an oxime structure (>C=N-O-C(=O)-) in the molecule. The polymerization initiator (a) does not have a sulfur atom.

[0023] As the polymerization initiator (a) used in the present invention, an oxime polymerization initiator having a carbazole skeleton or an oxime polymerization initiator represented by the following general formula (1) is preferable, and more preferably an oxime polymerization initiator having a carbazole skeleton.

[0024]

[0025] In general formula (1), Ar １ represents an aryl group. R １ represents an alkyl group. R ２ represents an alkyl group, an alkoxy group, or an aryl group.

[0026] The aryl group of Ar １ may be monocyclic or polycyclic, and examples thereof include aryl groups having 6 to 14 carbon atoms. The alkyl group of R １ may be linear, branched, or cyclic, and examples thereof include alkyl groups having 1 to 12 carbon atoms. The alkyl group of R ２ may be linear, branched, or cyclic, and examples thereof include alkyl groups having 1 to 6 carbon atoms. The alkyl group of R ２ may have an oxygen atom. The alkyl group in the alkoxy group of R ２ may be linear, branched, or cyclic, and examples thereof include alkyl groups having 1 to 6 carbon atoms. The aryl group of R ２ may be monocyclic or polycyclic, and examples thereof include aryl groups having 6 to 14 carbon atoms.

[0027] Each of the above groups may have substituents. The substituents are not particularly limited, but examples include aryl groups (which may be monocyclic or polycyclic, for example, aryl groups having 6 to 14 carbon atoms), alkyl groups (which may be linear, branched, or cyclic, for example, alkyl groups having 1 to 6 carbon atoms), and alkoxy groups (the alkyl group in the alkoxy group may be linear, branched, or cyclic, for example, alkyl groups having 1 to 6 carbon atoms).

[0028] Examples of oxime polymerization initiators represented by general formula (1) include the following:

[0029]

[0030] Examples of preferred polymerization initiators (a) include 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, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one.

[0031] Commercially available polymerization initiators (a) include IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 05 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Compounds with the following structures can also be used.

[0032]

[0033]

[0034]

[0035] The molecular weight of polymerization initiator (a) is not particularly limited, but is preferably 200 to 3000, and more preferably 350 to 2000.

[0036] The total amount of polymerization initiator (a) and sensitizer is 0.1 to 2.8% by mass relative to the total solid content of the composition. The resin composition of the present invention may or may not contain a sensitizer. If the resin composition of the present invention does not contain a sensitizer, the total amount of polymerization initiator (a) and sensitizer is equal to the amount of polymerization initiator (a). The sensitizer will be described later. If the resin composition of the present invention contains a sensitizer, the mixing ratio of polymerization initiator (a) to sensitizer is preferably 3:1 to 1:3 (by mass ratio), and more preferably 2:1 to 1:2 (by mass ratio).

[0037] The total amount of polymerization initiator (a) and sensitizer is preferably 0.5 to 2.5% by mass, and more preferably 0.9 to 2.4% by mass, relative to the total solid content of the composition.

[0038] <(b) Polyimide> The resin composition of the present invention contains polyimide (hereinafter also referred to as "polyimide (b)" or "polyimide").

[0039] In this specification, polyimide refers to a resin having repeating units containing imide structures within its molecular chain, and preferably a resin having repeating units containing imide ring structures within its molecular chain. Furthermore, if the polyimide is a linear resin, it is preferable that the polyimide is a resin having repeating units containing imide structures within its main chain, and more preferably a resin having repeating units containing imide ring structures within its main chain. In this specification, imide structure refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, imide ring structure refers to a ring structure that includes all two carbon atoms and nitrogen atoms in the above imide structure as ring members. The imide ring structure is preferably a five-membered ring.

[0040] The polyimide in the resin composition preferably has polymerizable groups, more preferably radical polymerizable groups, and even more preferably groups having ethylenically unsaturated bonds. The polyimide may further contain a sensitizer as needed. From such a resin composition, for example, a negative-type photosensitive film can be formed. The polyimide may also have polarity-converting groups such as acid-degradable groups. If the polyimide has acid-degradable groups, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed. The resin composition may be a negative-type photosensitive resin composition (a resin composition capable of forming a negative-type photosensitive film) or a positive-type photosensitive resin composition (a resin composition capable of forming a positive-type photosensitive film), but it is preferably a negative-type photosensitive resin composition. The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers.

[0041] The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, an alkali-soluble polyimide means a polyimide that dissolves at 23°C in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium, and from the viewpoint of pattern formation, it is preferable that the polyimide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. From the viewpoint of film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain.

[0042] -Fluorine Atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have fluorine atoms. Fluorine atoms are, for example, in the R of the repeating unit represented by formula (4) described later. １３２ , or R in the repeating unit represented by formula (4) described later. １３１Preferably, it is included in the repeating unit R represented by formula (4) described later. １３２ , or R in the repeating unit represented by formula (4) described later. １３１ It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0043] -Silicon atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have silicon atoms. For example, silicon atoms are R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit R represented by formula (4) described later. １３１ It is more preferable that the silicon atoms or the organically modified (poly)siloxane structure described later be included. The silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0044] - Ethylene-unsaturated bond - From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has an ethylenically unsaturated bond (C=C). The polyimide may have the ethylenically unsaturated bond at the end of the main chain or in the side chain, but it is preferable that it is in the side chain. It is preferable that the above ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３２ or R １３１ Preferably, it is included in R １３２ or R １３１ It is more preferable that it be included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in R １３１It is more preferable that the group contains an ethylenically unsaturated bond. Examples of groups containing an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups containing a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0045]

[0046] In formula (IV), R ２０ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0047] In formula (IV), R ２１ This is an alkylene group having 2 to 12 carbon atoms, -O-CH ２ CH(OH)CH ２ The characters represent -, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and particularly preferably 2 or 3; the repeating number of the alkylene oxy group preferably has 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be linear, branched, cyclic, or a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0048] Among these, R ２１ It is preferable that the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1).

[0049] In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group having two or more of these bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). ２１This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), a preferred embodiment of L is an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms, as shown in formula (IV) R ２１ The preferred embodiment is the same as that of an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * is the same as * in formula (IV), and the preferred embodiment is the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0050] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0051] The C=C value of polyimide (b) is preferably 0.10 to 3.00 mmol / g, more preferably 0.25 to 2.50 mmol / g, and even more preferably 0.40 to 2.00 mmol / g. The above C=C value represents the amount of C=C (ethylenically unsaturated bonds) relative to the total mass of the polyimide and can be determined as follows.

[0052] The C=C value [mmol / g] of each repeating unit in the polyimide is calculated using the following formula (1). Furthermore, the C=C value of the polyimide is calculated from the sum of the products of the C=C value of each repeating unit calculated from formula (1) and the mass fraction of each repeating unit in the polyimide. C=C value of the repeating unit / Molecular weight of the repeating unit ... Formula (1)

[0053] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimide may have polymerizable groups other than those having ethylenically unsaturated bonds. Examples of polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (4) described later. １３１ It is preferable that it be included in the following. The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0054] -Polarity-Converting Groups- Polyimides may have polarity-converting groups such as acid-degradable groups. The acid-degradable groups in polyimides are not particularly limited as long as they decompose under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl groups, isopropoxycarbonyl groups, tetrahydropyranyl groups, tetrahydrofuranyl groups, ethoxyethyl groups, methoxyethyl groups, ethoxymethyl groups, trimethylsilyl groups, tert-butoxycarbonylmethyl groups, and trimethylsilyl ether groups. From the viewpoint of exposure sensitivity, ethoxyethyl groups or tetrahydrofuranyl groups are preferred. Polarity-converting groups include, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ It is found at the ends of polyimides, etc.

[0055] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more. The above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. When polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development"), the acid value of polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. From the viewpoint of achieving both storage stability and developability, the acid groups contained in polyimides are preferably acid groups with a pKa of 0 to 10, and more preferably acid groups with a pKa of 3 to 8. pKa is the negative common logarithm of the equilibrium constant Ka, considering the dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa is the value calculated by ACD / ChemSketch®. The value of pKa may also be referenced from the value published in the "Revised 5th Edition Chemical Handbook Basic Edition" edited by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. As such acid groups, polyimides preferably contain at least one selected from the group consisting of carboxyl groups and phenolic hydroxyl groups, and more preferably contain phenolic hydroxyl groups.

[0056] -Phenolenic Hydroxyl Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. １３２ or R １３１It is preferable that it be included in [the polyimide]. The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0057] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4).

[0058]

[0059] In formula (4), R １３１ represents a divalent organic group, R １３２ R represents a tetravalent organic group. If it has a polymerizable group, the polymerizable group is R １３１ and R １３２ It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1)

[0060]

[0061] In formula (4-1), R １３３ This is a polymerizable group, and the other groups are equivalent to those in formula (4). Formula (4-2)

[0062] R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is equivalent to formula (4).

[0063] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or polymerizable groups other than those having the ethylenically unsaturated bond described above. １３１R represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably, a group containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. １３１ Examples include groups represented by -Ar- and -Ar-L-Ar-, with the group represented by -Ar-L-Ar- being preferred. However, Ar is independently an aromatic group, and L is a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２ The group consists of - or -NHCO-, or a combination of two or more of the above. The preferred ranges are as described above.

[0064] R １３１ It is preferable that it be derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, R １３１ The diamine is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

[0065]

[0066] In the formula, A represents a single bond or a divalent linking group, and may be a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO ２ Preferably, the group is -, -NHCO-, or a combination thereof, and may be a single bond or a C1-C3 alkylene group substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ２ It is more preferable that the group is selected from -CH ２ -, -O-, -S-, -SO ２ -, -C (CF ３ ) ２ -, or -C(CH ３ ) ２ It is even more preferable that it is -. In the formula, * represents a bonding site with another structure.

[0067] Diamines include, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamines; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4 ,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine N, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,Examples include at least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotidine, and 4,4'-diaminoquaterphenyl, and 3,3'-dihydroxybenzidine.

[0068] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0069] Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, are also preferably used.

[0070] R １３１ From the viewpoint of the flexibility of the resulting organic film, it is preferable that it be represented as -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２ - or -NHCO-, or a group consisting of two or more of the above. Ar is preferably a phenylene group, and L is a carbon-1 or carbon-2 aliphatic hydrocarbon group, -O-, -CO-, -S-, or -SO- which may be substituted with a fluorine atom. ２ - is preferred. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0071] Also, R １３１From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61). Formula (51)

[0072]

[0073] In formula (51), R ５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R ５０ ~R ５７ At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2). ５０ ~R ５７ Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0074]

[0075] In formula (61), R ５８ and R ５９ Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (4). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0076] R １３１ Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include the aliphatic, cyclic aliphatic, or aromatic diamines mentioned above.

[0077] R １３１It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine residue that does not contain an aromatic ring.

[0078] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0079] R １３２ * represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) below is more preferred. In formula (5) or formula (6), * independently represents a bonding site with another structure.

[0080]

[0081] In formula (5), R １１２ The linking group is a single bond or a divalent linking group, and may be a single bond or a carbon-1 to carbon-10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO- which may be substituted with a fluorine atom. ２ Preferably, the group is selected from -, -NHCO-, and combinations thereof, and is a C1- to C3 alkylene group, -O-, -CO-, -S-, and -SO- which may be single-bonded or substituted with a fluorine atom. ２ It is more preferable that the group is selected from -CH ２ -, -C (CF ３ ) ２ -, -C(CH ３ )２ -, -O-, -CO-, -S-, and -SO ２ It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0082] R １３２ Specifically, examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. Polyimide precursors are R １３２ The structure may contain only one tetracarboxylic dianhydride residue, or it may contain two or more. The tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0083] In formula (O), R １１５ R represents a tetravalent organic group. １１５ The preferred range of R in equation (4) is １３２ This is synonymous with the same thing, and the preferred range is also similar.

[0084] 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, and 2,2',3,3'-di Phenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane Dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride Examples include tracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic acid anhydride, and alkyl and alkoxy derivatives of these having 1 to 6 carbon atoms.

[0085] Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0086] For example, R １３２The four bonds of the tetravalent organic group exemplified as such are bonded to the four -C(=O)- moieties in formula (4) to form a condensed ring.

[0087] R １３２ includes, for example, the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Specific examples include R in formula (4) of the polyimide １３２ . From the viewpoint of the strength of the organic film, R １３２ is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0088] R １３１ [[ID=十四]]and R １３２ also preferably have an OH group in at least one of them. More specifically, as R １３１ , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are preferably exemplified, and as R １３２ , the above (DAA-1) to (DAA-5) are more preferably exemplified.

[0089] As described above, the polyimide preferably has an ethylenically unsaturated bond (C=C). As described above, the ethylenically unsaturated bond is preferably contained in R １３２ or R １３１ in the repeating unit represented by formula (4), and more preferably contained as a group having an ethylenically unsaturated bond in R １３２ or R １３１ . The ethylenically unsaturated bond is more preferably contained as a group having an ethylenically unsaturated bond in R １３１ in the repeating unit represented by formula (4).

[0090] In a preferred embodiment, the group having an ethylenically unsaturated bond is preferably a group represented by formula (S).

[0091]

[0092] In formula (S), * indicates the bonding position.

[0093] The polyimide preferably has a group represented by the above formula (S). This structure is preferable because the polyimide is less susceptible to thermal decomposition due to the high depolymerization temperature of polystyrene. The group represented by formula (S) is R in the repeating unit represented by formula (4). １３１ It is more preferable that it be included as a group having an ethylenically unsaturated bond.

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

[0095] To improve adhesion to the substrate, the polyimide may be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0096] In order to improve the storage stability of the resin composition, it is preferable that the main chain terminals of the polyimide are capped with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chlorides, monoactive esters, etc. Among these, it is more preferable to use monoamines. Preferred compounds of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and by reacting a plurality of end-capping agents, a plurality of different end groups may be introduced.

[0097] - Imidization ratio (ring closure ratio)- The imidization ratio (also referred to as "ring closure ratio") of polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more from the viewpoints of the film strength, insulation, etc. of the obtained organic film. The upper limit of the above imidization ratio is not particularly limited and may be 100% or less. The above imidization ratio is measured by, for example, the following method. Measure the infrared absorption spectrum of polyimide, and the absorption peak derived from the imide structure at 1377 cm －１The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. －１ Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated based on the following formula: Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0098] Polyimide is a material in which all repeating units are R １３１ and R １３２ The combination of R may include the repeating unit represented by the above formula (4), which is the same. １３１ and R １３２ The polyimide may contain repeating units represented by formula (4) above, which include two or more different combinations of the elements. In addition to the repeating units represented by formula (4) above, the polyimide may also contain other types of repeating units.

[0099] Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0100] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight-average molecular weight is particularly preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no specific upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple types of polyimide, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimide are treated as a single resin are each within the above range.

[0101] <Other Resins> The resin composition of the present invention may contain the polyimide described above and other resins different from polyimide (hereinafter also simply referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, etc. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, in place of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a resin with a high polymerizability value and a weight-average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups per 1 g of resin is 1 × 10⁻⁶) may be used. －３By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0102] If the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. If the resin composition of the present invention contains other resins, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. As a preferred embodiment of the resin composition of the present invention, the content of other resins can be low. In the above embodiment, the content of other resins 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, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0103] <(c) Polymerizable Compounds> The resin composition of the present invention contains polymerizable compounds (hereinafter also referred to as polymerizable compound (c)). Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0104] [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 (C=C). Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0105] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, it is preferable that it has 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. From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0106] The C=C value of polymerizable compound (c) is preferably 2.00 mmol / g or higher. Increasing the C=C value of the polymerizable compound (typically a radical crosslinking agent) increases the crosslink density and makes the cured film denser, which is preferable because it makes it easier to suppress outgassing. The above C=C value represents the amount of C=C (ethylenically unsaturated bonds) relative to the total mass of polymerizable compound (c) and can be calculated as follows. The C=C value of polymerizable compound (c) is calculated using the following formula (2): Number of C=C bonds in polymerizable compound (c) / Molecular weight of polymerizable compound (c) ... Formula (2)

[0107] The C=C value of polymerizable compound (c) is more preferably 3.00 mmol / g or more, and even more preferably 5.00 mmol / g or more. Furthermore, the C=C value of polymerizable compound (c) is preferably 11.00 mmol / g or less, and more preferably 7.00 mmol / g or less.

[0108] 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.

[0109] 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.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. 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. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0110] 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 International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0111] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0112] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0113] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0114] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0115] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic 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 the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0116] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992. It is preferable that the radical crosslinking agent does not contain silicon atoms.

[0117] As a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is also preferred. In the present invention, urea bonds are defined as *-NR Ｎ -C(=O)-NR Ｎ -* is a combination represented by R Ｎ Each of the symbols independently represents a hydrogen atom or a monovalent organic group, and each of the symbols * represents a bonding site with a carbon atom. In this invention, a urethane bond is defined as *-O-C(=O)-NR Ｎ -* is a combination represented by R Ｎrepresents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. The resin composition may have improved chemical resistance, resolution, etc., due to the inclusion of crosslinking agent U. The mechanism by which the above effects are obtained is unknown, but for example, it is thought that when curing by heating, etc., a portion of the crosslinking agent U is thermally decomposed, generating amines, etc., and these amines, etc., promote the cyclization of the precursor of the cyclized resin, such as the polyimide precursor. The crosslinking agent U may have only one urea bond or one urethane bond, or it may have one or more urea bonds and one or more urethane bonds, or it may have no urethane bonds and two or more urea bonds, or it may have no urea bonds and two or more urethane bonds. The total number of urea bonds and urethane bonds in the crosslinking agent U is one or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. If the crosslinking agent U does not have urethane bonds, the number of urea bonds in the crosslinking agent U is one or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When the crosslinking agent U does not have urea bonds, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0118] The radical polymerizable groups in the crosslinking agent U are not particularly limited, but include vinyl groups, allyl groups, (meth)acryloyl groups, (meth)acryloxy groups, (meth)acrylamide groups, vinylphenyl groups, maleimide groups, etc., with (meth)acryloxy groups, (meth)acrylamide groups, vinylphenyl groups, or maleimide groups being preferred, and (meth)acryloxy groups being more preferred. When the crosslinking agent U has two or more radical polymerizable groups, the structures of each radical polymerizable group may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one, or two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizability value (mass of compound per mole of radical polymerizable groups) in the crosslinking agent U is preferably 150 to 400 g / mol. From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerization value is more preferably 200 g / mol or more, even more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more. From the viewpoint of developability, the upper limit of the radical polymerization value is more preferably 350 g / mol or less, even more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less. In particular, the polymerization value of the crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0119] The crosslinking agent U preferably has a structure represented by the following formula (U-1).

[0120]

[0121] In formula (U-1), R Ｕ１ A is a hydrogen atom or a monovalent organic group, and A is -O- or -NR Ｎ - and R Ｎ is a hydrogen atom or a monovalent organic group, Z Ｕ１ is an m-valent organic group, Z Ｕ２is an n+1 valent organic group, X is a radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 1.

[0122] R Ｕ１ R is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｎ The element is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｕ１ These are hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded together is preferred, and is a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ -, and -NR Ｎ A group bonded with at least one group selected from the group consisting of - is more preferable. The hydrocarbon group is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by the bonding of these. Ｎ Z represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. Ｕ２ These are hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded together is preferred, and is a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ -, and -NR Ｎ A group bonded to at least one group selected from the group consisting of - is more preferable. The hydrocarbon group is Z Ｕ１Similar to those listed above, preferred embodiments are also listed. X is not particularly limited, but examples include vinyl group, allyl group, (meth)acryloyl group, (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, maleimide group, etc., with (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, or maleimide group being preferred, and (meth)acryloxy group being more preferred. n is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, even more preferably 1 or 2, and particularly preferably 1. m is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0123] The crosslinking agent U may also preferably have at least one of a hydroxyl group, an alkylene oxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but it is preferable that it be an alcoholic hydroxyl group. From the viewpoint of the chemical resistance of the resulting cured film, the alkylene oxy group is preferably an alkylene oxy group having 2 to 20 carbon atoms, more preferably an alkylene oxy group having 2 to 10 carbon atoms, even more preferably an alkylene oxy group having 2 to 4 carbon atoms, even more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkylene oxy group may also be included in the crosslinking agent U as a polyalkylene oxy group. In this case, the number of repeating alkylene oxy groups is preferably 2 to 10, and more preferably 2 to 6. The amide group is -C(=O)-NR Ｎ This refers to a combination represented by -. Ｎ As stated above, when the crosslinking agent U has an amide group, the crosslinking agent U is, for example, R-C(=O)-NR Ｎ - A group represented by *, or *-C(=O)-NR ＮIt can be included as a group represented by -R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The crosslinking agent U may have two or more structures selected from the group consisting of a hydroxyl group, an alkylene oxy group (however, if it constitutes a polyalkylene oxy group, it may be a polyalkylene oxy group), an amide group and a cyano group in its molecule, but it is also preferable to have only one in the molecule. The above hydroxyl group, alkylene oxy group, amide group and cyano group may be located at any position of the crosslinking agent U, but from the viewpoint of chemical resistance, it is also preferable that the crosslinking agent U has at least one selected from the group consisting of the above hydroxyl group, alkylene oxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U linked by a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1"). In particular, when the crosslinking agent U contains only one radical polymerizable group, it is preferable that the radical polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxyl group, an alkylene oxy group, an amide group, and a cyano group are linked by a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2"). When the crosslinking agent U contains an alkylene oxy group (however, if it constitutes a polyalkylene oxy group, it is a polyalkylene oxy group) and has the above-mentioned linking group L2-1 or linking group L2-2, the structure on the side opposite to linking group L2-1 or linking group L2-2 of the alkylene oxy group (however, if it constitutes a polyalkylene oxy group, it is a polyalkylene oxy group) is not particularly limited, but a hydrocarbon group, a radical polymerizable group, or a group represented by a combination thereof is preferred. As the above-mentioned hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. Examples of the hydrocarbon groups mentioned above include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by combinations thereof. Furthermore, the preferred embodiment of the radical polymerizable group is the same as the preferred embodiment of the radical polymerizable group in the crosslinking agent U described above.When the crosslinking agent U contains an amide group and has the linking group L2-1 or L2-2, the structure on the side of the amide group opposite to linking group L2-1 or L2-2 is not particularly limited, but a hydrocarbon group, a radical polymerizable group, or a group represented by a combination thereof is preferred. As the hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. As the hydrocarbon group, examples include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by a combination thereof. The preferred embodiment of the radical polymerizable group is the same as the preferred embodiment of the radical polymerizable group in the crosslinking agent U described above. In addition, in the above embodiment, the carbon atom side of the amide group may be bonded to linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to linking group L2-1 or L2-2. Among these, from the viewpoint of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that the crosslinking agent U has a hydroxyl group.

[0124] The crosslinking agent U preferably contains an aromatic group from the viewpoint of compatibility with polyimide. The aromatic group preferably directly bonds with a urea bond or urethane bond contained in the crosslinking agent U. If the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds directly bonds with the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and these may form a fused ring structure, but it is preferable that it be an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group obtained by removing two or more hydrogen atoms from a benzene ring structure. The aromatic heterocyclic group is preferably an aromatic heterocyclic group having 5 or 6 membered rings. Examples of aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, and the like. These rings may be fused with other rings, such as indole and benzimidazole. Preferred heteroatoms in the aromatic heterocyclic group are nitrogen, oxygen, or sulfur atoms. The aromatic group is preferably included in a linking group that connects two or more radical polymerizable groups and contains a urea bond or a urethane bond, or in a linking group that connects at least one selected from the group consisting of the hydroxyl group, alkylene oxy group, amide group, and cyano group with at least one radical polymerizable group contained in the crosslinking agent U.

[0125] The number of atoms (chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. If the crosslinking agent U contains a total of 2 or more urea bonds or urethane bonds, or contains 2 or more radical polymerizable groups, or contains 2 or more urea bonds or urethane bonds and 2 or more radical polymerizable groups, the minimum number of atoms (chain length) between the urea bond or urethane bond and the radical polymerizable group should be within the above range. In this specification, "number of atoms (chain length) between the urea bond or urethane bond and the polymerizable group" refers to the shortest (minimum number of atoms) linking atomic chains on the path connecting two atoms or groups of atoms to be linked. For example, in the structure represented by the following formula, the number of atoms (chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0126]

[0127] [Axis of Symmetry] It is also preferable that the crosslinking agent U is a compound with a structure that does not have an axis of symmetry. The absence of an axis of symmetry in the crosslinking agent U means that it does not have an axis that, when the entire compound is rotated, produces molecules identical to the original molecules, and is therefore an asymmetric compound. Furthermore, when the structural formula of the crosslinking agent U is written on paper, the absence of an axis of symmetry in the crosslinking agent U means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that the absence of an axis of symmetry in the crosslinking agent U suppresses aggregation of the crosslinking agents U within the composition film.

[0128] [Molecular Weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, preferably 150 to 1,500, and more preferably 200 to 900.

[0129] The method for producing the crosslinking agent U is not particularly limited, but for example, it can be obtained by reacting a radical polymerizable compound with a compound having an isocyanate group with a compound having at least one of a hydroxyl group or an amino group.

[0130] Specific examples of crosslinking agent U are shown below, but crosslinking agent U is not limited to these examples.

[0131]

[0132]

[0133]

[0134] The polymerizable compound (c) is preferably a chain-like bifunctional monomer. The above bifunctional monomer is preferably a compound that does not have carbon atoms directly bonded to three or four carbon atoms and has two ethylenically unsaturated bonds (C=C), and is preferably a radical crosslinking agent. A chain-like bifunctional monomer with relatively few monomer crosslinking sites is preferable because it reduces the inhibition of slippage (contributing to elongation) between polyimides, making it easier to obtain elasticity in the cured film. Specific examples include those corresponding to chain-like bifunctional monomers among the specific compounds described later.

[0135] In one preferred embodiment, the polymerizable compound (c) preferably includes a compound represented by the following formula (M1). This is preferable because it provides a good balance between suppressing outgassing in the cured film and elasticity. Furthermore, using a compound represented by the following formula (M1) is also preferable because it can improve compatibility with polyimide.

[0136]

[0137] In formula (M1), R represents either a hydrogen atom or an alkyl group, independently. n represents an integer between 2 and 3.

[0138] The alkyl group R is not particularly limited, but examples include alkyl groups having 1 to 3 carbon atoms. Specific examples include those compounds represented by the above formula (M1) among the specific compounds described later.

[0139] In one preferred embodiment, the resin composition is preferably a bifunctional methacrylate or acrylate, from the viewpoint of pattern resolution and the elasticity of the cured film.

[0140] 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, 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, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other difunctional acrylates and difunctional 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 in which the molecular weight of the polyethylene glycol chain is about 200.

[0141] Furthermore, from the viewpoint of suppressing warping of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional radical crosslinking agent. Preferred 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, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As a monofunctional radical crosslinking agent, compounds having a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0142] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to 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.

[0143] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0144] [Other Crosslinking Agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by photosensitization with the photoacid generator or photobase generator described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. The acid or base is preferably an acid or base generated from the photoacid generator or photobase generator in the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0145] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The other crosslinking agents may be present as one type or as two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0146] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenone, Michlaz ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.Examples of sensitizers include Michla'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-dimethylaminocinnamyrideneindanone, p-dimethylaminobenzylideneindanone, 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, 3-be N-di-di-di-methylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, N-phenylglycine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoic acid Examples include isoamyl acid, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 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, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used.Details of the sensitizing dye can be found in paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, which are incorporated herein by reference.

[0147] Furthermore, as a sensitizer, it is preferable that the film obtained from the resin composition containing the sensitizer tends to reduce the conductivity of the wiring in contact with the film, especially when exposed to high temperatures, and a sensitizer that does not contain sulfur atoms is one preferred embodiment.

[0148] If the resin composition contains a sensitizer, the amount of sensitizer, in total with the oxime polymerization initiator, is as described above. The sensitizer may be used alone or in combination of two or more types.

[0149] [Chain Transfer Agents] The resin compositions of the present invention may contain chain transfer agents. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include -S-S- and -SO2 molecules. ２ Compounds containing -S-, -N-O-, SH, PH, SiH, and GeH, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, are used. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0150] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0151] If 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, based on 100 parts by mass of the total solid content of the resin composition. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0152] <Base Generating Agent> The resin composition of the present invention may contain a base generating agent. Here, a base generating agent is a compound that can generate a base by physical or chemical action. Examples of base generating agents include paragraphs 0015-0057 of International Publication No. 2015 / 199219, paragraphs 0054-0070 of International Publication No. 2018 / 025738, paragraphs 0060-0072 of International Publication No. 2019 / 189110, paragraphs 0013-0028 of International Publication No. 2019 / 189111, and paragraphs 0013-0039 of International Publication No. 2020 / 054226. Examples include the compounds described in paragraphs 0101-0146 of Publication No. 2020 / 066244, paragraphs 0014-0049 of International Publication No. 2020 / 066315, paragraphs 0102-0159 of International Publication No. 2020 / 066416, paragraphs 0013-0050 of International Publication No. 2020 / 066435, and paragraphs 0089-0100 of International Publication No. 2020 / 170997. These contents are incorporated herein by reference.

[0153] When the resin composition contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of 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 generating agents can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0154] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0155] 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, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0156] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0157] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0158] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0159] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0160] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0161] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0162] 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, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0163] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0164] 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, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone, the combination of dimethyl sulfoxide and γ-valerolactone, the combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass relative to the total mass of the solvent. In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as the solvent is also a preferred embodiment of the present invention. In such embodiments, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content can be determined by considering the solubility of components such as polyimide contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferable to contain 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide relative to the total mass of the solvent, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0165] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0166] <Metal Adhesion Enhancers> The resin composition of the present invention preferably contains a metal adhesion enhancer from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion enhancers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0167] [Silane Coupling Agents] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 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 Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferred as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

[0168]

[0169] 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- Examples include (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-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more.

[0170] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0171] Other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0172] 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, per 100 parts by mass of polyimide. A content above the lower limit ensures good adhesion between the pattern and the metal layer, while a content below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total content is within the above range.

[0173] <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, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0174] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (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, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, 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.

[0175] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0176] Other migration inhibitors include, for example, the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the like, which are incorporated herein by reference.

[0177] Specific examples of migration inhibitors include the following compounds.

[0178]

[0179] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition.

[0180] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0181] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0182] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, and the like. This information is incorporated herein by reference.

[0183] If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0184] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0185] <Other Additives> The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-flocculation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these publications are incorporated herein. When these additives are included, it is preferable that their total content be 3% by mass or less of the solid content of the resin composition of the present invention.

[0186] [Surfactants] Various surfactants can be used as surfactants, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0187] By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (especially the fluidity) of the prepared coating liquid composition are further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further enhanced. Specifically, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid decreases, improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, it is possible to more favorably form a uniform film with less thickness variation.

[0188] Examples of fluorinated surfactants include the compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which are incorporated herein by reference. Fluorinated polymer compounds can also be preferably used as fluorinated surfactants, which include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Examples include the following compounds.

[0189]

[0190] 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 a fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

[0191] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0192] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0193] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0194] [Higher Fatty Acid Derivatives] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may contain higher fatty acid derivatives such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the resin composition of the present invention during the drying process after coating.

[0195] Furthermore, higher fatty acid derivatives may also be compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0196] When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition. There may be only one type of higher fatty acid derivative, or there may be two or more types. If there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above range.

[0197] [Thermal Polymerization Initiators] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals in response to thermal energy, initiating or accelerating the polymerization reaction of polymerizable compounds. By adding thermal radical polymerization initiators, the polymerization reaction of resins and polymerizable compounds can be advanced, thereby improving solvent resistance. In addition, photopolymerization initiators may also have the function of initiating polymerization in response to heat, and may be added as thermal polymerization initiators.

[0198] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the details of which are incorporated herein by reference.

[0199] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[0200] [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, and glass.

[0201] The average particle diameter 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 diameter of the inorganic particles is the primary particle diameter and also the volume-average particle diameter. The volume-average particle diameter can be measured, for example, by dynamic light scattering using 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, X-ray transmission, or laser diffraction / scattering.

[0202] [UV absorbers] Examples of UV absorbers include salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazines. Specific examples of UV absorbers include the compounds described in paragraphs 0341-0342 of International Publication No. 2021 / 112189, which are incorporated herein by reference.

[0203] The ultraviolet absorber may be used alone or in combination of two or more types. When the resin composition contains an ultraviolet absorber, the amount of 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 content mass of the resin composition.

[0204] [Organotitanium Compounds] By including organotitanium compounds in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0205] Suitable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), titanium diisopropoxidebis(ethylacetoacetate), etc. II) Tetraalkoxy titanium 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 tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)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-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) 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. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0206] In particular, from the viewpoint of better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0207] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of polyimide. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0208] [Antioxidants] By including antioxidants as additives, the elongation properties of the cured film and its adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348-0357 of International Publication No. 2021 / 112189, which are incorporated herein by reference.

[0209] The antioxidant content is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of polyimide. Adding 0.1 parts by mass or more makes it easier to obtain improved elongation properties and adhesion to metal materials even in high-temperature and high-humidity environments. Adding 10 parts by mass or less improves the sensitivity of the resin composition, for example, through interaction with the photosensitive agent. 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 their total amount falls within the above range.

[0210] [Anti-flocculants] Examples of anti-flocculants include sodium polyacrylate.

[0211] The anti-flocculation agent may be used alone or in combination of two or more types. When the resin composition contains an anti-flocculation agent, the content of the anti-flocculation agent is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid content mass of the resin composition.

[0212] [Phenol compounds] Examples of phenol compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0213] The phenolic compounds may be used individually or in combination of two or more. When the resin composition contains phenolic compounds, the content of the phenolic compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the resin composition.

[0214] [Other Polymer Compounds] Other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified forms into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0215] Other polymer compounds may be used individually or in combination of two or more. When the resin composition contains other polymer compounds, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the resin composition.

[0216] <Organometallic Complexes> The resin composition of the present invention may contain organometallic complexes from the viewpoint of chemical resistance. The organometallic complex is not particularly limited as long as it is an organic complex compound containing a metal atom, but it is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and even more preferably a metallocene compound. A metallocene compound is an organometallic complex having two cyclic pentadienyl anion derivatives, which may have substituents, as η5-ligands. The above organic group is not particularly limited, but a hydrocarbon group or a group consisting of a hydrocarbon group and a heteroatom is preferred. As heteroatoms, oxygen atoms, sulfur atoms, and nitrogen atoms are preferred. At least one of the above organic groups is preferably a cyclic group, and at least two are preferably cyclic groups. The above cyclic group is preferably selected from a five-membered ring cyclic group and a six-membered ring cyclic group, and more preferably a five-membered ring cyclic group. The above cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferred. As a five-membered ring cyclic group, a cyclopentadienyl group is preferred. Organometallic complexes preferably contain 2 to 4 cyclic groups in one molecule.

[0217] The metal included in the organometallic complex is not particularly limited, but it is preferably a metal belonging to Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, even more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

[0218] Organometallic complexes may contain two or more metal atoms, or only one metal atom, but it is preferable that they contain only one metal atom. When organometallic complexes contain two or more metal atoms, they may contain only one type of metal atom, or two or more types of metal atoms.

[0219] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound; more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound; even more preferably a titanocene compound or a zirconocene compound; and particularly preferably a titanocene compound.

[0220] Embodiments in which the organometallic complex has photoradical polymerization initiation ability are also preferred. In the present invention, having photoradical polymerization initiation ability means being able to generate free radicals that can initiate radical polymerization by irradiation with light. For example, the presence or absence of photoradical polymerization initiation ability can be confirmed by irradiating a composition containing a radical crosslinking agent and an organometallic complex with light in a wavelength range in which the organometallic complex absorbs light and in which the radical crosslinking agent does not absorb light, and checking whether or not the radical crosslinking agent disappears. To check whether or not the radical crosslinking agent disappears, an appropriate method can be selected depending on the type of radical crosslinking agent, but for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high-performance liquid chromatography). When the organometallic complex has photoradical polymerization initiation ability, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, even more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound. If the organometallic complex does not have photoradical polymerization initiation ability, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and hafnocene compounds; more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds, and hafnocene compounds; even more preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds; and particularly preferably a titanocene compound.

[0221] The molecular weight of the organometallic complex is preferably 50 to 2,000, and more preferably 100 to 1,000.

[0222] As organometallic complexes, compounds represented by the following formula (P) are preferred.

[0223]

[0224] In formula (P), M is a metal atom, and R is independently a substituent. Preferably, R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

[0225] The metal atom represented by M in formula (P) is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom; more preferably a titanium atom, a zirconium atom, or a hafnium atom; even more preferably a titanium atom or a zirconium atom; and particularly preferably a titanium atom. The aromatic group in R in formula (P) is an aromatic group having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. The alkyl group in R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, or a cyclopentyl group. The halogen atom in R is F, Cl, Br, or I. The alkyl group constituting the alkylsulfonyloxy group in R above is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, etc. R above may further have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl group, carboxyl group, amino group, cyano group, aryl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, monoarylamino group, and diarylamino group, etc.

[0226] Specific examples of organometallic complexes, though not particularly limited, include tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds.

[0227]

[0228] Also mentioned are the compounds described in paragraphs 0078-0088 of International Publication No. 2018 / 025738, which are incorporated herein by reference.

[0229] The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition. The lower limit is more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. One or more organometallic complexes can be used. When two or more are used, it is preferable that the total amount is within the above range.

[0230] <Characteristics of the Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm ２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２ If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, a coating with excellent properties can be obtained on the coated surface.

[0231] <Restrictions on the 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.

[0232] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0233] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0234] When considering the application of the resin composition of the present invention as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, the halogen atoms 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 amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0235] Conventional containers can be used as containers for the resin composition of the present invention. To suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0236] <Cured product of the resin composition> A cured product of the resin composition of the present invention 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 curing of the resin composition is preferably done by heating, with a heating temperature of 120°C to 400°C being more preferably, 140°C to 380°C being even more preferably, and 170°C to 350°C being particularly preferred. The form of the cured product of the resin composition is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By pattern processing of the resin composition, the shape of the cured product can also be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing a heat dissipation function. 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 change in volume of the resin composition before and after curing, and can be calculated using the following formula: Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0237] <Characteristics of the cured resin composition> The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0238] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing methods 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, and more preferably 15 to 25°C.

[0239] For the purpose of removing foreign matter such as dirt and fine particles from the resin composition of the present invention, filtration using a filter is preferable. The filter pore size is preferably, for example, 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. If the filter material is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. As an example of a connection configuration, 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. Furthermore, various materials may be filtered multiple times. When filtering multiple times, circulating filtration may be used. Furthermore, filtration may be performed under pressure. When filtration is performed under pressure, the pressure applied is preferably, for example, 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, even more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa. In addition to filtration using a filter, impurity removal treatment using an adsorbent may also be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, known adsorbents can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the resin composition filled into bottles may be subjected to a degassing step by placing it under reduced pressure.

[0240] (Method for Manufacturing Cured Products) The method for manufacturing cured products of the present invention preferably includes a film-forming step of applying a resin composition onto a substrate to form a film. The method for manufacturing cured products more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a developing step of developing the film exposed in the exposure step using a developer to form a pattern. The method for manufacturing cured products particularly preferably includes the film-forming step, the exposure step, the developing step, and at least one of a heating step of heating the pattern obtained in the developing step and a post-development exposure step of exposing the pattern obtained in the developing step. Furthermore, the method for manufacturing cured products may also preferably include the film-forming step and a step of heating the film. Details of each step will be described below.

[0241] <Membrane Formation Process> The resin composition of the present invention can be used in a membrane formation process in which it is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a membrane formation process in which the resin composition is applied to a substrate to form a film.

[0242] [Substrate] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs). Semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. These substrates may have layers such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) on their surface. The shape of the substrate is not particularly limited and may be circular or rectangular. If the substrate is circular, for example, a diameter of 100 to 450 mm is preferred, and 200 to 450 mm is more preferred. If it is rectangular, for example, the length of the shorter side is preferred to be 100 to 1000 mm, and 200 to 700 mm is more preferred. As the substrate, for example, a plate-shaped, preferably panel-shaped, substrate (substrate) is used.

[0243] When a resin composition is applied to the surface of a resin layer (for example, a layer made of cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0244] Coating is a preferred method for applying the resin composition onto 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 are 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 the coating conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating 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. Furthermore, a method can be applied in which a coating film, which has been previously applied and formed on a temporary support using the above application method, is transferred onto the substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used. In addition, a step of removing excess film at the edges of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may be employed in which the substrate is coated with various solvents to improve the wettability of the substrate before applying the resin composition to the substrate, and then the resin composition is applied.

[0245] <Drying Process> After the film formation process (layer formation process), the film may be subjected to a drying process to remove the solvent from the formed film (layer). That is, the method for producing a cured product of the present invention may include a drying process for drying the film formed in the film formation process. The drying process is preferably performed after the film formation process and before the exposure process. The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0246] <Exposure Process> The above film may be subjected to an exposure process in which the film is selectively exposed. The method for manufacturing the cured product may include an exposure process in which the film formed by the film formation process is selectively exposed. Selective exposure means exposing a part of the film. By selective exposure, exposed areas (exposed parts) and unexposed areas (unexposed parts) are formed in the film. The amount of exposure is not particularly limited as long as the resin composition of the present invention can be cured, but for example, it may be 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0247] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0248] In relation to the light source, the exposure wavelength can be found in: (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths: g, h, i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２Examples of exposures include (5) excimer laser (wavelength 157 nm), (6) extreme ultraviolet light; EUV (wavelength 13.6 nm), (7) YAG laser with 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 the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0249] <Post-exposure heating step> The above film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The heating rate may also be changed as appropriate during heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0250] <Development Process> The film after exposure may be subjected to a development process in which a pattern is formed by developing it with a developer. That is, the method for manufacturing a cured product of the present invention may include a development process in which a pattern is formed by developing the film exposed in the exposure process with a developer. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed part of the film is removed by the development process is called negative development, and development in which the exposed part of the film is removed by the development process is called positive development.

[0251] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0252] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferably, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. The content of basic compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0253] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph 0387 of International Publication No. 2021 / 112189. This is incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0254] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. 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.

[0255] 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 above content may be 100% by mass.

[0256] If the developer contains an organic solvent, it may further contain at least one of a basic compound and a base generator. At least one of the basic compound and base generator in the developer may penetrate the pattern, improving performance such as the pattern's elongation at break.

[0257] As for the basic compound, organic bases are preferred from the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured product is further heated). As for the basic compound, basic compounds having an amino group are preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, but in order to promote the imidation 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 for the basic compound, from the viewpoint of the mechanical properties of the cured product (elongation at break), it is preferable that it does not remain in the cured film (the resulting cured product), and from the viewpoint of promoting cyclization, it is preferable that the amount remaining before heating does not decrease easily due to vaporization, etc. Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at atmospheric pressure (101,325 Pa). The boiling point of the basic compound is preferably higher than the boiling point of the organic solvent contained in the developer, minus 20°C, and more preferably higher than the boiling point of the organic solvent contained in the developer. For example, if the boiling point of the organic solvent is 100°C, the basic compound used is preferably 80°C or higher, and more preferably 100°C or higher. The developer may contain only one basic compound, or it may contain two or more basic compounds.

[0258] Specific examples of basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DACO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, and 1,5-diamino Examples include pentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

[0259] The preferred embodiment of the base generator is the same as the preferred embodiment of the base generator contained in the above-described composition. In particular, the base generator is preferably a thermal base generator.

[0260] 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, and more preferably 5% by mass or less, relative to the total mass of the developer. The lower limit of the above content is not particularly limited, but for example, 0.1% by mass or more is preferred. 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, relative to the total solid content of the developer. The developer may contain only one of the basic compound and the base generator, or it may contain two or more. When there are two or more of the basic compound and the base generator, it is preferable that their total is within the above range.

[0261] The developing solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0262] [Method of supplying developer] There are no particular restrictions on the method of supplying the developer as long as a desired pattern can be formed. These include immersing a substrate on which a film has been formed in the developer, paddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, a method of supplying with a spray nozzle is more preferred. In addition, a step may be adopted in which the developer is continuously supplied with a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is supplied again with a straight nozzle, and the substrate is spun to remove the developer from the substrate. This step may be repeated multiple times. Examples of methods of supplying the developer in the development process include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept in a nearly stationary state on the substrate, a step in which the developer is vibrated on the substrate with ultrasound, etc., and a step that combines these.

[0263] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0264] In the developing process, after processing with the developer, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer in contact with the pattern dries completely may be employed.

[0265] [Rinsing Solution] If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0266] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0267] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. Preferred organic solvents are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA (propylene glycol monomethyl ether acetate), and PGME (propylene glycol monomethyl ether). More preferred are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, with cyclohexanone and PGMEA being even more preferred.

[0268] When the rinsing solution contains an organic solvent, the amount of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0269] The rinsing solution may contain at least one of a basic compound and a base generating agent. While not particularly limited, if the developer contains an organic solvent, a configuration in which the rinsing solution contains an organic solvent and at least one of a basic compound and a base generating agent is also a preferred embodiment of the present invention. Examples of basic compounds and base generating agents included in the rinsing solution include those exemplified above as basic compounds and base generating agents that may be included when the developer contains an organic solvent, and the preferred embodiment is similar. The basic compound and base generating agent included in the rinsing solution should be selected considering factors such as their solubility in the solvent in the rinsing solution.

[0270] When the rinse solution contains at least one of a basic compound and a base generating agent, the content of the basic compound or base generating agent is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the rinse solution. The lower limit of the above content is not particularly limited, but for example, 0.1% by mass or more is preferred. If the basic compound or base generating agent is solid in the environment in which the rinse solution is used, the content of the basic compound or base generating agent is also preferably 70 to 100% by mass, relative to the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generating agent, the rinse solution may contain only one of the basic compound and base generating agent, or it may contain two or more. When there are two or more of the basic compound and base generating agent, it is preferable that their total is within the above range.

[0271] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0272] [Method of supplying rinsing solution] There are no particular restrictions on the method of supplying the rinsing solution as long as a desired pattern can be formed. These include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution, supplying the rinsing solution to the substrate with a shower, and continuously supplying the rinsing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the rinsing solution, the removal of non-image areas, and manufacturing efficiency, there are methods of supplying the rinsing solution with a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuous supply with a spray nozzle is preferred, and from the viewpoint of the penetration of the rinsing solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. That is, the rinsing process is preferably a process of supplying the rinsing solution to the film after exposure using a straight nozzle or continuously supplying it, and it is more preferable to supply the rinsing solution using a spray nozzle. Possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0273] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0274] The developing process may include a step of bringing the processing solution into contact with the pattern after processing with the developer or after washing the pattern with the rinsing solution. Alternatively, methods such as supplying the processing solution before the developer or rinsing solution in contact with the pattern has completely dried may be employed.

[0275] Examples of the above-mentioned treatment solution include a treatment solution containing at least one of water and an organic solvent, and at least one of a basic compound and a base generating agent. Preferred embodiments of the organic solvent and at least one of the basic compound and base generating agent are the same as preferred embodiments of the organic solvent and at least one of the basic compound and base generating agent used in the rinse solution described above. The method of supplying the treatment solution to the pattern can be the same as the method of supplying the rinse solution described above, and the preferred embodiments are also the same.

[0276] The content of basic compounds or base generators in the treatment solution is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment solution. The lower limit of the above content is not particularly limited, but for example, it is preferably 0.1% by mass or more. Furthermore, if the basic compound or base generator is solid in the environment in which the treatment solution is used, the content of basic compounds or base generators is also preferably 70 to 100% by mass, relative to the total solid content of the treatment solution. When the treatment solution contains at least one of basic compounds and base generators, the treatment solution may contain only one type of basic compound or base generator, or it may contain two or more types. When there are two or more types of basic compounds and base generators, it is preferable that their total is within the above range.

[0277] <Heating Step> The pattern obtained by the developing 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 developing 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 developing 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 developing step, or a film obtained by a film formation step is heated. In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0278] The heating step is preferably a step in which the heating promotes the cyclization reaction of the polyimide precursor within the pattern by the action of bases generated from the base generating agent.

[0279] In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute 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 carry out heating at a heating rate of 1 to 8°C / second from the initial heating temperature to the maximum heating temperature, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0280] The starting temperature for 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 starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature is initiated. For example, when the resin composition of the present invention is applied to a substrate and then dried, this is the temperature of the film (layer) after drying, and it is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0281] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0282] 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 especially preferably 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0283] Heating may be carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to treat while irradiating with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such pretreatment steps can improve the properties of the film. The pretreatment step is preferably carried out for a short time of about 10 seconds to 2 hours, and more preferably for 15 seconds to 30 minutes. The pretreatment may consist of two or more steps; for example, the first pretreatment step may be carried out in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 200°C. Furthermore, cooling may be performed after heating, and in this case, the cooling rate is preferably 1 to 5°C / min.

[0284] The heating process is preferably carried out in a low-oxygen atmosphere, such as by flowing an inert gas like nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating means in the heating process is not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0285] <Post-development exposure step> The pattern obtained in the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a post-development exposure step in which the pattern after the development step is exposed, either in place of the heating step 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. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, reactions such as the cyclization of polyimide precursors etc. by photosensitivity of a photobase generator, or the elimination of acid-degradable groups by photosensitivity of a photoacid generator can be promoted. In the post-development exposure step, it is sufficient for at least a part of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The amount of exposure in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. ２ Preferably, 100 to 15,000 mJ / cm² ２ This is more preferable. The post-development exposure step can be performed, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

[0286] <Metal Layer Formation Process> The pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process) may be subjected to a metal layer formation process in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer formation process in which a metal layer is formed on the pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process).

[0287] The metal layer is not particularly limited, and existing metal species can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0288] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of the plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0289] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0290] <Applications> The manufacturing method of the cured product of the present invention, or the fields in which the cured product can be applied, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or etching to form patterns on insulating films for the above-mentioned mounting applications. For more information on these applications, please refer to, for example, Science & Technology Co., Ltd., "High-Functionality and Application Technologies of Polyimides," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimide Fundamentals and Applications," NTS, August 2010.

[0291] The method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used for manufacturing printing plates such as offset plates or screen printing plates, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0292] (Laminate and Method for Manufacturing a Laminate) The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention. The laminate is a laminate containing two or more layers made of the cured product, and may be a laminate with three or more layers. Of the two or more layers made of the cured product included in the above laminate, at least one is 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 due to the above shrinkage, it is also preferable that all the layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0293] In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

[0294] The laminate of the present invention preferably comprises two or more layers made of cured material, with a metal layer preferably included between any of the layers made of cured material. The metal layer is preferably formed by the metal layer formation step described above. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer formation step of forming a metal layer on a layer made of cured material, which is performed multiple times during the manufacturing process of the cured material. The preferred embodiment of the metal layer formation step is as described above. As the laminate, for example, a laminate is preferred that includes at least three layers in which a first layer made of cured material, a metal layer, and a second layer made of cured material are laminated in this order. It is preferable that both the first layer made of cured material and the second layer made of cured material are layers made of cured material of the present invention. The resin composition of the present invention used to form the first layer made of cured material and the resin composition of the present invention used to form the second layer made of cured material may have the same composition or may have different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0295] <Lamination Process> The method for manufacturing a laminate of the present invention preferably includes a lamination process. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of a pattern (resin layer) or metal layer: (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process, and post-development exposure process. However, the method may also involve repeating at least one of the following: (a) film formation process and (d) heating process and post-development exposure process. Furthermore, at least one of the following: (d) heating process and post-development exposure process may be followed by (e) metal layer formation process. Needless to say, the lamination process may further include the above-mentioned drying process and the like as appropriate.

[0296] If further lamination is performed after the lamination process, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0297] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, a configuration with 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration with 2 to 9 resin layers is even more preferred. Each of the above layers may have the same composition, shape, film thickness, etc., or they may be different.

[0298] In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the steps in the order of (a) film formation, (b) exposure, (c) development, (d) heating and post-development exposure, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and post-development exposure, and (e) metal layer formation. By alternately performing the lamination step of stacking the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0299] (Surface Activation Treatment Step) The manufacturing method of the 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 is 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 surface activation treatment step may be performed on the resin composition layer 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 on at least a portion of both the metal layer and the post-exposure resin composition layer. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on its surface can be improved. It is also preferable to perform the surface activation treatment on a portion or all of the post-exposure resin composition layer (resin layer). By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion to the metal layer and resin layer provided on the surface-activated surface can be improved. In particular, when developing negative film, if the resin composition layer is cured, it is less susceptible to damage from surface treatment and adhesion is easily improved. Surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This is incorporated herein by reference.

[0300] (Semiconductor Devices and Methods for Manufacturing the Same) The present invention also discloses semiconductor devices including a cured product or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product or a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0301] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0302] <Examples of Resin (Polyimide) Synthesis> Synthesis Example 1: Synthesis of A-1 The details of the synthesis method for A-1 are shown below. 31.4 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride (BPADA) and 1.0 g of 4,4'-oxydiphthalic anhydride (ODPA) were dissolved in 52 g of N-methylpyrrolidone (NMP) to obtain a solution. Subsequently, 3.0 g of 3,3'-dihydroxybenzidine (HAB), 9.4 g of 4,4'-diaminodiphenyl ether (ODA), and 1.0 g of p-aminophenol were dissolved in 147 g of NMP, and 22 mL of toluene was added. While maintaining a temperature of 40°C or below, the above diamine solution was added dropwise to the acid anhydride solution over 1 hour, and then the reaction was carried out at 200°C for 4 hours. During the reaction, reflux and dehydration were carried out using a Dean-Stark regulator. After the reaction was complete, the mixture was cooled to 25°C. To the reaction solution, 0.90 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 24.3 g of 4-chloromethylstyrene, 26.4 g of potassium carbonate powder, 3.2 g of potassium iodide, and 67 g of NMP were added, and the mixture was reacted at 95°C for 2 hours. After the reaction was complete, the mixture was cooled to 25°C, diluted with 400 mL of tetrahydrofuran, the solids were removed by filtration, and the mixture was further washed with 200 mL of tetrahydrofuran. Subsequently, the reaction solution was added dropwise to a mixture of 2.0 liters of methanol and 0.9 L of water, stirred for 60 minutes, and then the polyimide resin was filtered. After filtration, the mixture was dried under reduced pressure at 40°C for 15 hours. Next, the dried resin was dissolved in 450 mL of tetrahydrofuran, and 0.23 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical was added and dissolved. Then, 65 g of ion exchange resin (MB-1: Organo) was added, and the mixture was stirred for 2 hours. After removing the ion exchange resin by filtration, the polyimide was precipitated in 2.0 liters of methanol and stirred for 60 minutes. The polyimide was obtained by filtration and dried under reduced pressure at 40°C for 20 hours to obtain 45.7 g of polyimide A-1.

[0303] Synthesis Example 2: Synthesis of A-2 Polyimide A-2 was obtained in the same manner as in Synthesis Example 1, except that 3,3'-dihydroxybenzidine and 4-chloromethylstyrene were not added.

[0304] Synthesis Example 3: Synthesis of A-3 to A-5 Polyimides A-3 to A-5 were obtained in the same manner as in Synthesis Example 1, except that the equivalent amounts of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 3,3'-dihydroxybenzidine, 4,4'-diaminodiphenyl ether, and p-aminophenol were appropriately adjusted.

[0305] Synthesis Example 4: Synthesis of A-6 Polyimide A-6 was obtained in the same manner as in Synthesis Example 1, except that methacrylate chloride was added instead of p-chlorostyrene.

[0306] Synthesis Example 5: Synthesis of A-7 to A-8 Polyimides A-7 to A-8 were obtained in the same manner as in Synthesis Example 1, except that 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) was added instead of 3,3'-dihydroxybenzidine.

[0307] Synthesis Example 6: Synthesis of A-9 to A-10 Polyimides A-9 to A-10 were obtained in the same manner as in Synthesis Example 5, except that m-tolidine (m-tol) was added instead of 4,4'-diaminodiphenyl ether.

[0308] Table 1 shows the acid anhydrides and diamines used in the synthesis of each polyimide. Table 1 also shows the number-average molecular weight (Mn), weight-average molecular weight (Mw), dispersion (Mw / Mn), and C=C value for each polyimide (A-1 to A-10).

[0309] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured using gel permeation chromatography (GPC) and expressed as polystyrene equivalents. Mw and Mn were determined using an HLC-8220 GPC (manufactured by Tosoh Corporation), with the following columns connected in series: Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation). NMP (N-methyl-2-pyrrolidone) was used as the eluent. For GPC measurement, a UV (ultraviolet) wavelength 254 nm detector was used.

[0310]

[0311] Details of each component listed in the table above are as follows:

[0312] <Acid anhydrides> BPADA: 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, ODPA: 4,4'-oxydiphthalic anhydride

[0313] <Diamines> HAB: 3,3'-dihydroxybenzidine ODA: 4,4'-diaminodiphenyl ether BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane m-tol: m-tolidine

[0314] <Examples and Comparative Examples> Each component listed in Table 2 below was mixed to obtain each resin composition at the solid content concentration shown in Table 2. The content (amount) of each component other than the solvent in each resin composition is shown as the content (mass%) relative to the total solid content. The "ratio" of the solvent is the mass ratio (mass%) of each solvent to the total amount of solvent. The obtained resin composition was pressure filtered using a polytetrafluoroethylene filter with a pore width of 20.0 μm. In the table, "-" indicates that the composition does not contain the corresponding component.

[0315]

[0316] Details of each component listed in the table above are as follows:

[0317] <Resin (Polyimide)> The various structures (resin structures) of the resins used are shown below. Each resin contains the structures enclosed in [ ] as repeating units. The content of each repeating unit in each resin varies depending on the amount of raw materials used in the synthesis of the resin. In addition, the weight-average molecular weight (Mw) of the resin can be adjusted by increasing or decreasing the amount of each monomer added. For resins containing two or more repeating units, the content of each repeating unit (molar ratio (mol%) to the total number of repeating units) is indicated by a subscript to the right of each [ ]. The composition ratio (molar % ratio) of the resin is: １Measurements were taken using 1H-NMR (nuclear magnetic resonance). The Mn, Mw, and Mw / Mn values ​​of the resins used in each example and comparative example are listed in Table 1.

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328] The C=C values ​​of each polyimide are also shown in Table 1. The C=C values ​​of each polyimide were determined as follows:

[0329] The C=C value [mmol / g] of each repeating unit in the polyimide was calculated using the following formula (1). Furthermore, the C=C value of the polyimide was calculated from the sum of the products of the C=C value of each repeating unit calculated from formula (1) and the mass fraction of each repeating unit in the polyimide. C=C number in the repeating unit / Molecular weight of the repeating unit ... Formula (1)

[0330] <Polymerizable Compounds (Polymerizable Compound (c))> The following polymerizable compounds can be used: B-1: Light acrylate 3EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) (structure shown below) B-2: Light acrylate 4EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) (structure shown below) B-3: A-TMPT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (structure shown below)

[0331]

[0332] Table 2 shows the C=C values ​​of each polymerizable compound. The C=C value of a polymerizable compound is determined as follows: The C=C value of polymerizable compound (c) is calculated using the following formula (2): Number of C=C atoms in polymerizable compound (c) / Molecular weight of polymerizable compound (c) ... Formula (2)

[0333] <Oxime Polymerization Initiators> The following can be used as oxime polymerization initiators: C-1: IRGACURE OXE 02 (manufactured by BASF) (structure shown below) C-2: Compound represented by formula C-2 below C-3: IRGACURE OXE 01 (manufactured by BASF) (structure shown below) C-4: Compound represented by formula C-4 below C-5: SpeedCure PDO (structure shown below) C-6: Compound represented by formula C-6 below C-7: Compound represented by formula C-7 below C-8: Compound represented by formula C-8 below C-9: Compound represented by formula C-9 below C-10: Compound represented by formula C-10 below

[0334]

[0335]

[0336] <Sensitizers> The following can be used as sensitizers: D-1: N-phenylglycine

[0337] <Silane Coupling Agents> The following can be used as silane coupling agents.

[0338]

[0339] <Migration Inhibitors> The following can be used as migration inhibitors.

[0340]

[0341] <Polymerization Inhibitors> The following can be used as polymerization inhibitors: G-1: Paramethoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0342]

[0343] <Surfactant> As the surfactant, the following can be used. H-1: BYK-333 (silicone type) (manufactured by BYK Co., Ltd.)

[0344] <Thermal polymerization initiator> As the thermal polymerization initiator, the following can be used.

[0345]

[0346] <Solvent> As the solvent, for example, the following can be used, and in the examples, it is selected and used from the following. I-1: γ-butyrolactone I-2: Cyclohexanone

[0347] [Reliability (High Temperature Storage - test (HTS)] 1. On a silicon wafer on which copper wiring is formed, each resin composition is formed into a film under the following conditions to obtain a cured product. (1) Spin-coat the composition so that the film thickness of the cured product becomes 7 μm. (2) Perform a drying bake at 110 °C for 5 minutes. (3) Expose with a Canon Stepper exposure machine at 400 mJ / cm ２ (4) Develop with cyclopentanone and rinse with PGMEA. (5) Cure (cure) for 2 hours at the temperature shown in Table 3 in an N ２ oven. 2. Put the obtained cured product into a constant temperature bath at 175 °C and take it out after 8 days. 3. Cut out the cross-section of the wiring on the substrate with an ion milling device. 4. Observe the thickness of the oxide film of the copper wiring with a scanning electron microscope. The thickness of the oxide film is evaluated as follows. 5: Less than 140 nm 4: 140 nm or more and less than 160 nm 3: 160 nm or more and less than 170 nm 2: 170 nm or more and less than 190 nm 1: 190 nm or more

[0348] [Resolution] Regarding the resolution, the exposure latitude is evaluated as follows. 1. On a copper substrate, each resin composition is formed into a film under the following conditions to obtain a cured product. (1) Spin-coat the composition so that the film thickness of the cured product becomes 7 μm. (2) Perform a drying bake at 110 °C for 5 minutes. (3) Expose with a Canon Stepper exposure machine in a hole shape with a diameter of 10 μm at 100 - 1000 mJ / cm ２(4) Expose with cyclopentanone and rinse with PGMEA. (5) N ２ 1. Cure in an oven at the temperature listed in Table 3 for 2 hours. 2. Observe the diameter of the resulting holes using a measuring CD-SEM (Critical Dimension-Scanning Electron Microscope) and evaluate the change in line width with respect to exposure. For the exposure region where the hole diameter is ±10%, evaluate as follows: 5: >400 mJ / cm ２ 4:300mJ / cm ２ Exceeding 400 mJ / cm², ２ Below 3:200mJ / cm ２ Exceeding 300 mJ / cm², ２ Below 2: 100mJ / cm ２ Exceeding 200 mJ / cm², ２ Below 1:100mJ / cm ２ below

[0349] Furthermore, Td and elongation are evaluated for each resin composition as follows.

[0350] [Thermal Decomposition Temperature (Td)] 1. SiO ２ Each resin composition is deposited on a wafer under the following conditions to obtain a cured product: (1) The composition is spin-coated so that the cured product has a thickness of 7 μm. (2) Dry baking is performed at 110°C for 5 minutes. (3) Exposure is performed at 400 mJ / cm using a Canon Stepper exposure machine. ２ (4) Expose with cyclopentanone and rinse with PGMEA. (5) N ２1. Cure in an oven at the temperature listed in Table 3 for 2 hours. 2. Peel off the strip-shaped film by etching with HF gas. 3. Cut the resulting film into 10 mg pieces. 4. Place the sample on an aluminum pan and measure the thermogravimetric analysis temperature (TGA). Evaluate the 1% thermogravimetric analysis temperature (Td1%) as follows: 5: >360°C 4: Above 340°C and below 360°C 3: Above 320°C and below 340°C 2: Above 300°C and below 320°C 1: Below 300°C

[0351] [Growth] 1. SiO ２ Each resin composition is deposited on a wafer under the following conditions to obtain a cured product: (1) The composition is spin-coated so that the cured product has a thickness of 7 μm. (2) Dry baking is performed at 110°C for 5 minutes. (3) Exposure is performed at 400 mJ / cm using a Canon Stepper exposure machine. ２ (4) Expose with cyclopentanone and rinse with PGMEA. (5) N ２ 1. Cure in an oven at the temperature listed in Table 3 for 2 hours. 2. Peel off the strip-shaped film by etching with HF gas. 3. Pull the resulting film with a Tensilon tensile device and evaluate the elongation until breakage. Elongation until breakage is evaluated as follows: 5: >50% 4: greater than 40% and 50% or less 3: greater than 30% and 40% or less 2: greater than 20% and 30% or less 1: 20% or less

[0352] The results obtained are shown in Table 3.

[0353]

[0354] From the above results, it can be seen that the embodiments of the present invention provide a resin composition that can form a cured product with high reliability and excellent resolution. Furthermore, it can be seen that the cured product formed by the resin composition in the embodiments of the present invention has a high thermal decomposition temperature. This is thought to be due to the suppression of outgassing from the resulting cured product. Moreover, it can be seen that the embodiments of the present invention provide a resin composition that can form a cured product with excellent elongation.

[0355] <Example 101> [Preparation of interlayer insulating film for redistribution layer] The resin composition used in Example 1 is applied in layers to the surface of a copper thin layer formed on a resin substrate, which has a copper thin layer formed on its surface, by spin coating. After drying at 110°C for 5 minutes to form a photosensitive film with a thickness of 20 μm, it is exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure is 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 above exposure, it is developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern. Next, under a nitrogen atmosphere, the temperature is increased at a rate of 10°C / min until it reaches 230°C, and then maintained at 230°C for 180 minutes to form an interlayer insulating film for the redistribution layer. This interlayer insulating film for the redistribution layer has excellent insulating properties. Furthermore, a semiconductor device can be manufactured using this interlayer insulating film for the redistribution layer and it will operate without problems.

[0356] <Examples 102-136> Using the resin compositions used in Examples 2-36, interlayer insulating films for each redistribution layer are formed in the same manner as in Example 101. These interlayer insulating films for redistribution layers have excellent insulating properties. Furthermore, semiconductor devices are manufactured using these interlayer insulating films for redistribution layers and operate without problems.

[0357] According to the present invention, it is possible to provide a resin composition capable of forming a cured product with high reliability and excellent resolution, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product.

[0358] 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 invention. This application is based on Japanese Patent Application No. 2024-171089 filed on 30 September 2024, the contents of which are incorporated herein by reference.

Claims

1. A resin composition comprising (a) an oxime polymerization initiator, (b) a polyimide, and (c) a polymerizable compound, wherein the polymerization initiator does not contain sulfur atoms, and the total amount of the polymerization initiator and the sensitizer is 0.1 to 2.8% by mass with respect to the total solid content of the composition.

2. The resin composition according to claim 1, wherein the C=C value of the polymerizable compound (c) is 7.00 mmol / g or more.

3. The resin composition according to claim 2, wherein the polymerizable compound (c) is a chain-like bifunctional monomer.

4. The resin composition according to claim 3, wherein the polymerizable compound (c) comprises a compound represented by the following formula (M1). In formula (M1), R represents either a hydrogen atom or an alkyl group, independently. n represents an integer between 2 and 3.

5. The resin composition according to claim 1, wherein the C=C value of the polyimide (b) is 0.40 to 2.00 mmol / g.

6. The resin composition according to claim 5, wherein the (b) polyimide has a group represented by the following formula (S). In formula (S), * indicates the bonding position.

7. A resin composition according to any one of claims 1 to 6, used for forming an interlayer insulating film for a redistribution layer.

8. A cured product obtained by curing the resin composition according to any one of claims 1 to 6.

9. A laminate comprising two or more layers made of the cured product described in claim 8, wherein a metal layer is included between any of the layers made of the cured product.

10. 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 6 onto a substrate to form a film.

11. A method for producing a cured product according to claim 10, comprising an exposure step of selectively exposing the film, and a developing step of developing the film using a developer to form a pattern.

12. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 11.

13. A semiconductor device comprising the cured product described in claim 8.

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