Method for producing polyimide precursor or polyamideimide precursor, method for producing curable resin composition, curable resin composition, and polyimide precursor or polyamideimide precursor

Abstract

To provide a method for producing a polyimide precursor or a polyamideimide precursor which enables formation of a film that is excellent in breaking elongation and PCT characteristics, and is suitably usable for a curable resin composition.SOLUTION: A method for producing a polyimide precursor or a polyamideimide precursor includes, in this order, a step of reacting a dicarboxylic acid compound represented by general formula (1) or (2) described in the specification with a chlorinating agent containing no sulfur element to obtain a dicarboxylic acid chloride represented by general formula (1)' or (2)' described in the specification, a step of reacting the dicarboxylic acid chloride with diamine, and a step of treating the reaction product with an ion exchange resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polyimide precursor or a polyamideimide precursor, a method for producing a curable resin composition, a curable resin composition, and a polyimide precursor or a polyamideimide precursor. [Background technology]

[0002] Resins such as polyimide and polyamide-imide are used in a variety of fields, including semiconductor devices and the aerospace industry.

[0003] Patent Document 1 describes a resin composition containing a polyimide precursor. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2015 / 52885 Summary of the Invention [Problem to be solved by the invention]

[0005] For example, when a film formed using a resin-containing composition (resin composition) is used in a semiconductor device or the like, the film tends to be required to have excellent elongation at break. Furthermore, a pressure cooker test (PCT) is known as a testing method for environmental reliability testing related to electronic devices, and the resin composition is required to be resistant to corrosion of wiring and the generation of abnormalities and foreign matter in the resin film (also referred to as excellent "PCT characteristics"). In other words, a resin composition that can form a film having excellent elongation at break and excellent PCT characteristics is required.

[0006] An object of the present invention is to provide a method for producing a polyimide precursor or a polyamideimide precursor that can be suitably used in a curable resin composition that can form a film that has excellent elongation at break and excellent PCT properties. Another object of the present invention is to provide a method for producing a curable resin composition, including the method for producing a polyimide precursor or a polyamideimide precursor, a curable resin composition, and a polyimide precursor or a polyamideimide precursor. [Means for solving the problem]

[0007] Examples of typical embodiments of the present invention are given below.

[0008] [1] a step of reacting a dicarboxylic acid compound represented by the following general formula (1) or (2) with a chlorinating agent not containing a sulfur element to obtain a dicarboxylic acid chloride represented by the following general formula (1)' or (2'): a step of reacting the dicarboxylic acid chloride with a diamine; treating with an ion exchange resin; A method for producing a polyimide precursor or a polyamideimide precursor, comprising the steps of:

[0009] [ka]

[0010] (In general formulas (1) and (2), X1 represents a tetravalent organic group, Y1 represents a trivalent organic group, and Z1 to Z3 each independently represent an oxygen atom or -NR z R1 to R3 each independently represent a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a group having an ethylenically unsaturated bond, and R3 is a group having an ethylenically unsaturated bond. z represents a hydrogen atom or a monovalent organic group, and R z may be bonded to R1, R2, or R3 to form a ring.

[0011] [ka]

[0012] (In general formulas (1)' and (2)', X1, Y1, Z1, Z2, Z3, R1, R2, and R3 are the same as X1, Y1, Z1, Z2, Z3, R1, R2, and R3 in general formulas (1) and (2).)

[0013] [2] The method for producing a polyimide precursor or a polyamideimide precursor according to [1], wherein the sulfur-free chlorinating agent is at least one selected from the group consisting of oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, and phenylphosphonic dichloride. [3] The method for producing a polyimide precursor or a polyamideimide precursor according to [1] or [2], wherein R1, R2, and R3 in the general formulas (1), (1)', (2), and (2)' each independently represent a group represented by the following formula (3):

[0014] [ka]

[0015] (In formula (3), A represents a (q+1)-valent organic group, R4 to R6 each independently represent a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, q represents an integer of 1 to 4, and * represents a bonding site to another structure.)

[0016] [4] The method for producing a polyimide precursor or a polyamideimide precursor according to any one of [1] to [3], wherein one of -Z1-R1 and -Z2-R2 in the above general formulas (1) and (1)' is a group having an ethylenically unsaturated bond, and the other is a group represented by the following formula (4):

[0017] [ka]

[0018] (In formula (4), Z4 and Z5 each independently represent a monovalent organic group, and * represents a bonding site to another structure. Z4 and Z5 may be bonded to form a ring.

[0019] [5] The method for producing a polyimide precursor or a polyamideimide precursor according to [4], wherein the group represented by the formula (4) is a group represented by the following formula (5):

[0020] [ka]

[0021] In formula (5), Cy represents a nitrogen-containing heterocycle or aromatic ring, and * represents a bonding site to another structure.

[0022] [6] The method for producing a polyimide precursor or a polyamideimide precursor according to any one of [1] to [5], wherein the content of elemental sulfur contained in the polyimide precursor or polyamideimide precursor is less than 0.5 mass % based on the total mass of the polyimide precursor or polyamideimide precursor. [7] The method for producing a polyimide precursor or a polyamideimide precursor according to any one of [1] to [6], wherein the weight average molecular weight of the polyimide precursor or the polyamideimide precursor is 5,000 to 50,000.

[0023] [8] (1) A polyimide precursor or a polyamideimide precursor produced by the method according to any one of [1] to [7]. (2) Solvent (3) Polymerization initiator A method for producing a curable resin composition, comprising mixing

[0024] [9] (1) A polyimide precursor or a polyamideimide precursor produced by the method according to any one of [1] to [7]. (2) Solvent (3) Polymerization initiator A curable resin composition comprising:

[10] A polyimide precursor or a polyamideimide precursor having a repeating unit represented by the following general formula (11) or (12): the content of elemental sulfur contained in the polyimide precursor or polyamideimide precursor is less than 5 ppm based on the total mass of the polyimide precursor or polyamideimide precursor; the content of chloride ions contained in the polyimide precursor or polyamideimide precursor is less than 3 ppm based on the total mass of the polyimide precursor or polyamideimide precursor; Polyimide precursor or polyamideimide precursor.

[0025] [ka]

[0026] In general formula (11) and general formula (12), R 115 represents a tetravalent organic group, and R 117 represents a trivalent organic group, A 1 ~A 3 each independently represents an oxygen atom or -NR z1 - represents R 111 , R 116 each independently represents a divalent organic group, R 113 , R 114 , and R 118 each independently represents a hydrogen atom or a monovalent organic group, R z1 represents a hydrogen atom or a monovalent organic group. R 113 and R 114 at least one of R is a group having an ethylenically unsaturated bond; 118 is a group having an ethylenically unsaturated bond. z1 represents a hydrogen atom or a monovalent organic group, and R z1 is R 113 , R 114 , or R 118may be bonded to form a ring.) [Effects of the Invention]

[0027] According to the present invention, it is possible to provide a method for producing a polyimide precursor or a polyamideimide precursor that can be suitably used in a curable resin composition that can form a film that is excellent in breaking elongation and PCT characteristics. Furthermore, according to the present invention, it is possible to provide a method for producing a curable resin composition including the method for producing a polyimide precursor or a polyamideimide precursor, a curable resin composition, and a polyimide precursor or a polyamideimide precursor. DETAILED DESCRIPTION OF THE INVENTION

[0028] The main embodiments of the present invention will be described below, but the present invention is not limited to the embodiments explicitly described. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit, respectively. In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved. In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, and electron beams. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", "(meth)acrylic" means either or both of "acrylic" and "methacrylic", and "(meth)acryloyl" means either or both of "acryloyl" and "methacryloyl". In this specification, Me in the 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, the term "total solids content" refers to the total mass of all components of the composition excluding the solvent, and the term "solids concentration" refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is not suitable as the eluent, such as when the solubility is low, THF (tetrahydrofuran) can also be used. Unless otherwise specified, detection in GPC measurements is performed using a UV (ultraviolet) ray (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that there is another layer above or below the reference layer among the multiple layers being considered. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above." Alternatively, if a resin composition layer (sometimes referred to as a "resin layer") is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, a composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. As used herein, the term "organic group" refers to a group containing at least one carbon atom. As used herein, combinations of preferred embodiments are more preferred embodiments.

[0029] [Method of producing polyimide precursor or polyamideimide precursor] First, the method for producing the polyimide precursor or polyamideimide precursor of the present invention will be described. The method for producing a polyimide precursor or a polyamideimide precursor of the present invention comprises the steps of: a step of reacting a dicarboxylic acid compound represented by the following general formula (1) or (2) with a chlorinating agent not containing a sulfur element to obtain a dicarboxylic acid chloride represented by the following general formula (1)' or (2'): a step of reacting the dicarboxylic acid chloride with a diamine; treating with an ion exchange resin; a polyimide precursor or a polyamideimide precursor,

[0030] [ka]

[0031] (In general formulas (1) and (2), X1 represents a tetravalent organic group, Y1 represents a trivalent organic group, and Z1 to Z3 each independently represent an oxygen atom or -NR z R1 to R3 each independently represent a hydrogen atom or a monovalent organic group, at least one of R1 and R2 is a group having an ethylenically unsaturated bond, and R3 is a group having an ethylenically unsaturated bond. z represents a hydrogen atom or a monovalent organic group, and R z may be bonded to R1, R2, or R3 to form a ring.

[0032] [ka]

[0033] (In general formulas (1)' and (2)', X1, Y1, Z1, Z2, Z3, R1, R2, and R3 are the same as X1, Y1, Z1, Z2, Z3, R1, R2, and R3 in general formulas (1) and (2).)

[0034] When a resin obtained by the method for producing a polyimide precursor or polyamideimide precursor of the present invention is applied to a curable resin composition, it is possible to form a film having excellent elongation at break and excellent PCT characteristics. The mechanism by which the present invention achieves this effect is not clear, but the present inventors speculate as follows. However, the present invention is not limited in any way by the speculated mechanism below. The above-mentioned effects may be affected by residual impurities in the resin (polyimide precursor or polyamide-imide precursor) used in the curable resin composition. The present inventors focused on reducing the content of sulfur atoms and chlorine atoms (chloride ions) in the resin. In the method for producing a polyimide precursor or a polyamideimide precursor of the present invention, a dicarboxylic acid compound represented by the above general formula (1) or (2) is reacted with a chlorinating agent that does not contain sulfur to obtain a dicarboxylic acid chloride represented by the above general formula (1)' or (2)'. Thionyl chloride is generally used to activate the dicarboxylic acid compound. The use of thionyl chloride in this way tends to produce by-products, such as acidic impurities containing sulfur atoms and highly polar by-products. In the present invention, by using a chlorinating agent that does not contain sulfur element instead of thionyl chloride, it is possible to suppress the production of the above-mentioned impurities and by-products that contain sulfur element. The method for producing a polyimide precursor or a polyamideimide precursor of the present invention includes a step of treating the dicarboxylic acid chloride with an ion exchange resin in addition to the step of reacting the diamine with the dicarboxylic acid chloride, which makes it possible to reduce chloride ions remaining in the reaction system. As described above, the production of impurities containing sulfur element and by-products can be suppressed, and furthermore, the chloride ions remaining in the reaction system can be reduced, so that the generation of foreign matter can be suppressed, and it is considered that when the resin obtained by the above manufacturing method is applied to a curable resin composition, a film with excellent PCT properties can be formed. Furthermore, as described above, by suppressing the production of impurities and by-products containing sulfur element, unnecessary crosslinking reactions in the cured film can be suppressed. Therefore, when the resin obtained by the above-described manufacturing method is applied to a curable resin composition, it is thought that a film having excellent elongation at break can be formed. In the polyimide precursor or polyamideimide precursor obtained in this manner, the sulfur element and chloride ions can be reduced, and it is believed that when the resin obtained by the above-mentioned production method is applied to a curable resin composition, a film having excellent breaking elongation and excellent PCT properties can be formed.

[0035] Each step included in the method for producing a polyimide precursor or a polyamideimide precursor of the present invention will be described in detail. [Step of reacting a dicarboxylic acid compound represented by general formula (1) or (2) with a chlorinating agent not containing sulfur element to obtain a dicarboxylic acid chloride represented by the following general formula (1)' or (2')] (also referred to as "Step 1"). In the general formulas (1) and (2), X1 represents a tetravalent organic group, Y1 represents a trivalent organic group, and Z1 to Z3 each independently represent an oxygen atom or -NR z R1 to R3 each independently represent a hydrogen atom or a monovalent organic group, at least one of R1 and R2 has an ethylenically unsaturated bond, and R3 is a group having an ethylenically unsaturated bond. z represents a hydrogen atom or a monovalent organic group, and R z may be bonded to R1, R2, or R3 to form a ring.

[0036] Z1 to Z3 each independently represent an oxygen atom or -NR z -, and an oxygen atom is preferred. R z represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include the monovalent organic groups R1 to R3 described below, and the preferred ranges are also the same. R z may combine with R1, R2, or R3 to form a ring. The ring formed is not particularly limited and may be a monocyclic ring or a polycyclic ring. In addition, it may be an aromatic ring or a non-aromatic ring (for example, a non-aromatic heterocyclic ring).

[0037] X1 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site to another structure.

[0038] [ka]

[0039] In formula (5), R 112 represents a single bond or a divalent linking group, and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -NHCO-, or a combination thereof; more preferably a single bond, or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, and -CO-; and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, and -CO-.

[0040] Specific examples of X1 include a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic acid dianhydride. The dicarboxylic acid compound represented by general formula (1) may contain only one type of tetracarboxylic acid dianhydride residue or two or more types of tetracarboxylic acid dianhydride residues as the structure corresponding to X1. The tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0041] [ka]

[0042] In formula (O), R 115 represents a tetravalent organic group. 115 The preferred range of is the same as that of X1 in general formula (1), and the preferred range is also the same.

[0043] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis( 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

[0044] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0045] R1 to R3 each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains an alkyl group (linear, branched, or cyclic), an alkenyl group (linear or branched), an aromatic group, or a polyalkyleneoxy group. The number of carbon atoms in the monovalent organic group is not particularly limited, but is, for example, 1 to 30. It is more preferable that at least one of R1 and R2 has a group having an ethylenically unsaturated bond, and that both have groups having an ethylenically unsaturated bond.It is also preferable that at least one of R1 and R2 has a group having two or more ethylenically unsaturated bonds. R3 has a group having an ethylenically unsaturated bond. It is also preferred that R3 has a group having two or more ethylenically unsaturated bonds. The group having an ethylenically unsaturated bond is a polymerizable group, and is a radical polymerizable group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (3), and the group represented by the following formula (3) is preferred.

[0046] [ka]

[0047] In formula (3), A represents a (q+1)-valent organic group, R4 to R6 each independently represent a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and q represents an integer of 1 to 4. * represents a bonding site to other structures.

[0048] A represents a (q+1)-valent organic group. Divalent linking groups when q is 1 are described below. The divalent linking group represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group. Examples of the divalent linking group include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CHCH(OH)CH-, and polyalkyleneoxy groups, of which alkylene groups such as ethylene and propylene, -CHCH(OH)CH-, cyclohexyl, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are even more preferred. A (q+1)-valent organic group (q is 2 or more) is a group obtained by removing (q-1) hydrogen atoms from a divalent linking group.

[0049] q represents an integer of 1 to 4, preferably an integer of 1 or 2, and more preferably 1.

[0050] In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2. The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating.Preferable embodiments of the number of repeating ethyleneoxy groups in these groups are as described above.

[0051] At least one of R1 and R2 may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred. The aliphatic hydrocarbon groups of R4 to R6 are not particularly limited, but examples thereof include alkyl groups, such as methyl and ethyl groups. The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but for example, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The aliphatic hydrocarbon group may further have a substituent. R4 to R6 preferably represent a hydrogen atom or an aliphatic hydrocarbon group.

[0052] At least one of -Z1-R1 and -Z2-R2 in the above general formula (1) preferably represents a group represented by the following formula (4).

[0053] [ka]

[0054] (In formula (4), Z4 and Z5 each independently represent a monovalent organic group, and * represents a bonding site to another structure. Z4 and Z5 may be bonded to form a ring.

[0055] The monovalent organic groups of Z4 and Z5 include the monovalent organic groups of R1 and R2 described above, and the preferred ranges are also the same. The monovalent organic groups of Z4 and Z5 are preferably alkyl groups or alkenyl groups. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 12. The alkenyl group may be linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 2 to 20, and more preferably 2 to 12. Z4 and Z5 may be bonded to form a ring. The ring formed is not particularly limited and may be a monocyclic ring or a polycyclic ring. In addition, it may be an aromatic ring or a non-aromatic ring (for example, a non-aromatic heterocyclic ring).

[0056] The group represented by the above formula (4) is preferably a group represented by the following formula (5).

[0057] [ka]

[0058] In formula (5), Cy represents a nitrogen-containing heterocycle or aromatic ring, and * represents a bonding site to another structure.

[0059] The nitrogen-containing heterocycle of Cy may be a monocycle or a polycycle. The number of carbon atoms in the nitrogen-containing heterocycle is not particularly limited, but is, for example, 3 to 20, preferably 3 to 15, and more preferably 3 to 10. The nitrogen-containing heterocycle may have a heteroatom other than nitrogen (nitrogen atom). Examples of the nitrogen-containing heterocycle include a pyrrolidine ring, a piperidine ring, and a morpholine ring. The aromatic ring of Cy may be a monocyclic or polycyclic ring. The number of carbon atoms in the aromatic ring is not particularly limited, but is, for example, 5 to 20, preferably 5 to 15, and more preferably 5 to 10. Examples of the aromatic ring include a pyridine ring and an indole ring.

[0060] In general formula (2), Y1 can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group. Y1 is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. The linking group is preferably -O-, -C(=O)-, an alkylene group, an arylene group, or a linking group in which two or more of these are bonded together, and more preferably -O-, an alkylene group, an arylene group, or a linking group in which two or more of these are bonded together. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0061] Y1 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated, and the halogenation is preferably chlorinated. In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be converted into acid anhydrides. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0062] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0063] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, or a phenylene group. These compounds may be compounds in which two carboxy groups are anhydrides (for example, trimellitic anhydride), or may be compounds in which at least one carboxy group is halogenated (for example, trimellitic anhydride chloride).

[0064] The synthesis method of the dicarboxylic acid compound represented by general formula (1) is not particularly limited, and known compounds can be used. Alternatively, the compound can be obtained by removing an anhydride group from a tetracarboxylic dianhydride. The method for removing an anhydride group from a tetracarboxylic dianhydride is not particularly limited, and known methods can be used. The synthesis method of the dicarboxylic acid compound represented by general formula (2) is not particularly limited, and known compounds can be used. It can also be obtained by deriving it from a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound can be converted to acid anhydrides.

[0065] The dicarboxylic acid compounds represented by general formula (1) or (2) may be used singly or in combination of two or more. In a preferred embodiment, the dicarboxylic acid compound represented by the general formula (1) may be used alone or in combination of two or more. In a preferred embodiment, the dicarboxylic acid compound represented by the general formula (2) may be used alone or in combination of two or more.

[0066] The sulfur-free chlorinating agent (hereinafter also referred to as "chlorinating agent A") is not particularly limited, but is preferably at least one selected from the group consisting of oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, and phenylphosphonic acid dichloride. The amount of chlorinating agent A used is preferably 1.00 to 3.00 times by mole, more preferably 1.01 to 1.50 times by mole, and even more preferably 1.02 to 1.04 times by mole, per mole of the dicarboxylic acid compound represented by general formula (1) or (2) (total amount when a plurality of dicarboxylic acid compounds are used).

[0067] Step 1 is preferably carried out in the presence of a solvent. The organic solvent may be one type or two or more types. The organic solvent can be appropriately determined depending on the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (also called diglyme or diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone.

[0068] The temperature at which the dicarboxylic acid compound represented by the general formula (1) or (2) is reacted with the chlorinating agent A is not particularly limited, but may be, for example, from -10 to 10°C. The reaction time is not particularly limited, but may be, for example, 0.5 to 4 hours. After the reaction at the above temperature, the reaction vessel may be further heated and stirred as needed. The temperature for further heating is, for example, 10 to 60° C., and the stirring time is, for example, 1 to 4 hours.

[0069] In step 1, a dicarboxylic acid chloride represented by the above general formula (1)' or (2)' is obtained. In general formulas (1)' and (2)', X1, Y1, Z1, Z2, Z3, R1, R2, and R3 are the same as X1, Y1, Z1, Z2, Z3, R1, R2, and R3 in general formulas (1) and (2).

[0070] It is preferable that R1, R2, and R3 in the above general formulae (1), (1)', (2), and (2)' each independently represent a group represented by the above formula (3). It is preferred that one of -Z1-R1 and -Z2-R2 in the above general formulas (1) and (1)' is a group having an ethylenically unsaturated bond, and the other is a group represented by the above formula (4).

[0071] [Step of reacting dicarboxylic acid chloride with diamine (hereinafter also referred to as "Step 2")] The dicarboxylic acid chloride is as described above. The diamine is not particularly limited, but may be, for example, 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 isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether (also known as "4,4'-oxydianiline"), 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, 4,4'-diaminoparaterphenyl, 4,4'-bis(4 -aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 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, 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, Bis(3-aminopropyl)tetramethyldisiloxane, Bis(p-aminophenyl)octamethylpentasiloxane, 2,7-Diaminofluorene, 2,5-Diaminopyridine, 1,2-Bis(4-aminophenyl)ethane, Diaminobenzanilide, Esters 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, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3- At least one diamine selected from the group consisting of 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'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl may be used.

[0072] Additionally, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598 are also preferred.

[0073] Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598.

[0074] The amount of diamine used is preferably 0.7 to 1.1 times by mole, more preferably 0.8 to 1.0 times by mole, and even more preferably 0.85 to 0.95 times by mole, per mole of dicarboxylic acid chloride (total amount when plural dicarboxylic acid chlorides are used).

[0075] Step 2 is preferably carried out in the presence of a solvent. The organic solvent may be one kind or two or more kinds. The organic solvent can be appropriately selected depending on the raw materials, and examples thereof include the organic solvents described in step 1 above.

[0076] The temperature at which the dicarboxylic acid chloride and the diamine are reacted is not particularly limited, but may be, for example, -10 to 10°C. The reaction time is not particularly limited, but may be, for example, 0.5 to 6 hours. After the reaction at the above temperature, the reaction vessel may be further heated and stirred as needed. The temperature for further heating is, for example, 10 to 60° C., and the stirring time is, for example, 1 to 6 hours.

[0077] It is preferable to add a basic compound during the reaction in step 2. The basic compound may be one type or two or more types. The basic compound can be appropriately determined depending on the raw material, and examples include triethylamine, diisopropylethylamine, pyridine, methylpyridine, dimethylpyridine, trimethylpyridine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine. The method for producing a polyimide precursor or polyamideimide precursor of the present invention may include a step of precipitating a solid after step 2. Specifically, after filtering the reaction solution as necessary, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain a precursor. To improve the degree of purification, the precursor may be repeatedly subjected to procedures such as redissolving, reprecipitation, and drying.

[0078] [Step 3: Treating with an ion exchange resin] Specifically, step 3 represents a step of adding an ion exchange resin to the reaction system (solution) in step 2. Alternatively, the above-mentioned precipitation step may be further carried out in step 2, the obtained precursor may be dissolved in a solvent, and an ion exchange resin may be added to the obtained solution. The solvent is not particularly limited, and it is possible to use tetrahydrofuran (THF) or the like, which is the solvent used in the above step 1. By treating with an ion exchange resin, the amount of chloride ions in the precursor can be reduced.

[0079] The ion exchange resin is not particularly limited, but an amphoteric ion exchange resin or an anion exchange resin can be used. Examples of amphoteric ion exchange resins include MB-1, MB-2, MB-4, EG-4A-HG, EG-5A-HG, ESP-1, and ESP-2 (all manufactured by Organo Corporation). Anion exchange resins include, for example, Amberlyst. TM B20-HG·DRY, Amberist A21, Amberist HPR4780, Amberist IRA67, Amberist IRA96SB, Amberist IRA98, AMBERJET TM UP6040, Amber Jet series (all manufactured by Organo Corporation), Diaion TM Series (manufactured by Mitsubishi Chemical Corporation), Relite TM Examples of suitable solvents include JA450 (manufactured by Mitsubishi Chemical Corporation) and Amberlite IRA96SB (manufactured by Organo Corporation).

[0080] The following products manufactured by Organo Corporation can also be used. https: / / ier.organo.co.jp / product / material.html#product1

[0081] In addition, the following products manufactured by Mitsubishi Chemical Corporation can also be used. https: / / www.m-chemical.co.jp / products / departments / mcc / ion / product / 1200472_7274.html

[0082] The amount of the ion exchange resin used is not particularly limited and can be selected appropriately. The amount of the ion exchange resin used is preferably equal to or greater than the yield of the resin obtained.

[0083] The method for producing a polyimide precursor or polyamideimide precursor of the present invention may include a step of precipitating a solid after step 3. Specifically, after filtering off the ion exchange resin coexisting in the reaction solution, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain a polyimide precursor or polyamideimide precursor. To improve the degree of purification, operations such as redissolving, reprecipitation, and drying of the polyimide precursor or polyamideimide precursor may be repeated.

[0084] Step 3 can reduce the chloride ions present in the reaction system. The amount of chloride ions in the polyimide precursor or polyamideimide precursor is preferably 900 ppm or less from the viewpoint of halogen-free, and more preferably 100 ppm or less, even more preferably 10 ppm or less, and particularly preferably less than 3 ppm from the viewpoint of corrosion prevention.

[0085] The amount of chloride ions in the precursor was measured as the amount of residual chlorine element as follows.

[0086] [Quantitative determination of residual chlorine content in resin (precursor) by combustion ion chromatography] Approximately 50 mg of the sample was placed on a sample board, and after measuring the weight, measurements were carried out by combustion ion chromatography under the following conditions. Sample combustion temperature: 900℃ (inlet) / 1000℃ (outlet) Absorption solution conditions: Approximately 0.01% H2O2 aq. + 2 ppm KH2PO4 aq. (internal standard) Absorbed liquid volume: 5mL Column: Dionex IonPac AS22 Eluent: 4.5mmol / L Na2CO3+ 1.4mmol / L NaHCO3 Flow rate: 1.2mL / min Column temperature: 35℃ Amount of absorbent solution injected: 100uL Concentration correction: Volume check The measurement was carried out twice, and the amount of chlorine element in each sample was quantified, and the average value was used.

[0087] The weight-average molecular weight (Mw) of the polyimide precursor or polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polyimide precursor or polyamideimide precursor preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0088] The content of elemental sulfur contained in the polyimide precursor or polyamideimide precursor is preferably less than 0.5% by mass based on the total mass of the polyimide precursor or polyamideimide precursor.

[0089] The content of elemental sulfur in the precursor was measured as follows.

[0090] [Quantitative determination of sulfur element in resin (precursor) by combustion ion chromatography] Approximately 50 mg of the sample was placed on a sample board, and after measuring the weight, measurements were carried out by combustion ion chromatography under the following conditions. Sample combustion temperature: 900℃ (inlet) / 1000℃ (outlet) Absorption solution conditions: Approximately 0.01% H2O2 aq. + 2 ppm KH2PO4 aq. (internal standard) Absorbed liquid volume: 5mL Column: Dionex IonPac AS22 Eluent: 4.5mmol / L Na2CO3+ 1.4mmol / L NaHCO3 Flow rate: 1.2mL / min Column temperature: 35℃ Amount of absorbent solution injected: 100uL Concentration correction: Volume check The measurement was carried out twice, and the amount of elemental sulfur in each sample was quantified, and the average value was used.

[0091] The content of elemental sulfur contained in the polyimide precursor or polyamideimide precursor is more preferably 100 ppm or less, even more preferably 10 ppm or less, and particularly preferably less than 5 ppm, from the viewpoint of preventing corrosion of metal wiring.

[0092] The present invention relates to the following method for producing a curable resin composition. (1) A polyimide precursor or a polyamideimide precursor produced by the above-mentioned method for producing a polyimide precursor or a polyamideimide precursor. (2) Solvent (3) Polymerization initiator A method for producing a curable resin composition, comprising mixing (1) The polyimide precursor or polyamideimide precursor (hereinafter also referred to as "specific resin") produced by the above-mentioned method for producing a polyimide precursor or polyamideimide precursor is as described above. (2) Solvent and (3) polymerization initiator will be described later. The method for mixing (1) the specific resin, (2) the solvent, and (3) the polymerization initiator is not particularly limited. In addition to (1) the specific resin, (2) the solvent, and (3) the polymerization initiator, the components described below may be mixed as needed.

[0093] The present invention relates to the following curable resin composition. (1) A polyimide precursor or a polyamideimide precursor produced by the above-mentioned method for producing a polyimide precursor or a polyamideimide precursor. (2) Solvent (3) Polymerization initiator A curable resin composition comprising:

[0094] (1) The polyimide precursor or polyamideimide precursor (hereinafter also referred to as "specific resin" or "resin (1)") produced by the above-mentioned method for producing a polyimide precursor or polyamideimide precursor is as described above. (2) Solvent and (3) polymerization initiator will be described later.

[0095] In a preferred embodiment, the specific resin has a repeating unit represented by the general formula (11) or (12) described below.

[0096] In a preferred embodiment, the specific resin is a polyimide precursor or a polyamideimide precursor having a repeating unit represented by the general formula (11) or (12) described below, the content of elemental sulfur contained in the polyimide precursor or polyamideimide precursor is less than 5 ppm based on the total mass of the polyimide precursor or polyamideimide precursor; the content of chloride ions contained in the polyimide precursor or polyamideimide precursor is less than 3 ppm based on the total mass of the polyimide precursor or polyamideimide precursor; A polyimide precursor or a polyamideimide precursor is preferred. The method for measuring the content of elemental sulfur contained in the polyimide precursor or polyamideimide precursor and the method for measuring the content of chloride ions contained in the polyimide precursor or polyamideimide precursor are as described above.

[0097] The curable resin composition in the above-mentioned method for producing a curable resin composition and the curable resin composition containing the above-mentioned (1) specific resin, (2) solvent, and (3) polymerization initiator are collectively referred to as the "curable resin composition of the present invention" or the "resin composition of the present invention."

[0098] The polyimide precursor refers to a resin that changes its chemical structure in response to an external stimulus to become a polyimide. A resin that changes its chemical structure in response to heat to become a polyimide is preferred, and a resin that changes its chemical structure in response to heat to become a polyimide by forming a ring structure through a ring-closing reaction is more preferred. The polyimide produced from the polyimide precursor in the resin composition of the present invention is preferably insoluble in a developer containing an organic solvent as its main component. A polyamideimide precursor refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a polyamideimide. A resin that undergoes a change in chemical structure due to heat to become a polyamideimide is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a polyamideimide is more preferred. The polyamideimide produced from the polyamideimide precursor in the resin composition of the present invention is preferably insoluble in a developer containing an organic solvent as its main component.

[0099] When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator. If necessary, the resin composition of the present invention may further contain a sensitizer. For example, a negative-tone photosensitive film can be formed from the resin composition of the present invention. The specific resin may have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition of the present invention, for example, a chemically amplified positive-type photosensitive film or negative-type photosensitive film is formed. The resin composition of the present invention may be a negative photosensitive resin composition (a resin composition capable of forming a negative photosensitive film) or a positive photosensitive resin composition (a resin composition capable of forming a positive photosensitive film), but is preferably a negative photosensitive resin composition. The resin composition of the present invention can be used to form, for example, an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a rewiring layer.

[0100] The weight-average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polyimide precursor or polyamideimide precursor preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition of the present invention contains multiple specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one specific resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple specific resins as one resin are each within the above-mentioned ranges.

[0101] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.

[0102] The resin composition of the present invention also preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins, or may contain two or more specific resins, but preferably contains two or more specific resins.

[0103] <(2) Solvent> The resin composition of the present invention contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0104] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionates, Preferred examples of the alkyl cypropionate include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0105] Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, 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.

[0106] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0107] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0108] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0109] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0110] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0111] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0112] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0113] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. 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 based on the total mass of the solvents. In particular, from the viewpoint of storage stability of the resin composition, an embodiment in which γ-valerolactone is contained as a solvent is one of the preferred embodiments of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the content is not particularly limited and may be 100% by mass. The content may be determined taking into consideration the solubility of components such as the specific resin contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-butyrolactone are used in combination, the solvent preferably contains 60 to 90 mass% of γ-butyrolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-butyrolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-butyrolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0114] From the viewpoint of coatability, the content of the solvent is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass %, more preferably an amount that results in 5 to 75 mass %, even more preferably an amount that results in 10 to 70 mass %, and even more preferably an amount that results in 20 to 70 mass %. The content of the solvent may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total content thereof is preferably within the above range.

[0115] [(3) Polymerization initiator] The resin composition of the present invention contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable that the resin composition contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0116] The photoradical polymerization initiator has a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm) and a concentration of at least about 50 L·mol -1 ·cm -1Preferably, the composition contains at least one compound having a molar absorption coefficient of 0.01 g / L. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0117] Any known photoradical polymerization initiator can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details, see paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

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

[0118] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0119] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0120] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

[0121] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0122] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0123] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0124] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232) compounds described in, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515, and the like, the contents of which are incorporated herein by reference.

[0125] Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In resin compositions, it is particularly preferred to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group >C=NOC(=O)- within the molecule.

[0126] [ka]

[0127] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Oxime compounds having the following structure can also be used.

[0128] [ka]

[0129] As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021 / 112189, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, or an oxime compound having a fluorine atom can be used. In addition, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359, the contents of which are incorporated herein by reference.

[0130] As a photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring is used. OX1 It is also possible to use an oxime compound having the aromatic ring group Ar OX1 Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred, and an acyl group is more preferred because it is easier to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group is more preferred, and an alkoxy group, an alkylsulfanyl group, or an amino group is even more preferred.

[0131] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2).

[0132] [ka]

[0133] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group, R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group, R X3 ~R X14 each independently represents a hydrogen atom or a substituent. However, R X10 ~R X14 At least one of the groups is an electron-withdrawing group.

[0134] In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 is preferably a hydrogen atom.

[0135] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0136] Particularly preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0137] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0138] The photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound, and even more preferably a metallocene compound or an oxime compound.

[0139] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of WO 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469 can also be used, the contents of which are incorporated herein by reference.

[0140] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, thereby improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, WO-A-2015 / 004565, WO-A-2016-532675, paragraphs 0407 to 0412, and WO-A-2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-A-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Application Publication No. 34963, the oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, the photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0141] When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0142] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound that is a compound different from the resin (1). The polymerizable compound may be a radical crosslinking agent or other crosslinking agent.

[0143] [Radical crosslinking agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0144] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. From the viewpoint of the film strength of the 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 the above-mentioned compound having three or more ethylenically unsaturated bonds.

[0145] 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.

[0146] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. For specific examples, see paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0147] The radical crosslinking agent is preferably a compound having a boiling point of 100 ° C or higher under normal pressure. Examples of compounds having a boiling point of 100 ° C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0148] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0149] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), as well as compounds in which the (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these compounds can also be used.

[0150] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such acrylic acid esters include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0151] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and 1999-105238, can also be used as radical crosslinking agents.

[0152] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers such as M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0153] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0154] The radical crosslinking agent is preferably a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U"). In the present invention, the urea bond is *-NR N -C(=O)-NR N - is a bond represented by *, and R N each independently represents a hydrogen atom or a monovalent organic group, and each * represents a bonding site to a carbon atom. In the present invention, the urethane bond is *-OC(=O)-NR N - is a bond represented by *, and R N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. When the resin composition contains the crosslinking agent U, the chemical resistance, resolution, etc. may be improved. The mechanism by which the above-mentioned effect is obtained is unknown; however, it is thought that, for example, when curing is performed by heating or the like, part of the crosslinking agent U is thermally decomposed to generate amines, etc., which then promote the cyclization of the precursor of the cyclized resin, such as a polyimide precursor. The crosslinking agent U may have only one urea bond or one urethane bond, or may have one or more urea bonds and one or more urethane bonds, or may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds. The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinking agent U has no urethane bond, the number of urea bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinking agent U has no urea bond, the number of urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0155] The radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred. When the crosslinking agent U has two or more radically polymerizable groups, the structures of the radically polymerizable groups may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be one or two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radically polymerizable group value (mass of compound per mole of radically polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol. From the viewpoint of the chemical resistance of the cured product, the lower limit of the radically polymerizable group 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, still more preferably 230 g / mol or more, still 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 radically polymerizable group 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 polymerizable group value of the crosslinking agent U is preferably from 210 to 400 g / mol, and more preferably from 220 to 400 g / mol.

[0156] The crosslinking agent U preferably has a structure represented by the following formula (U-1), for example.

[0157] [ka]

[0158] In formula (U-1), RU1 represents a hydrogen atom or a monovalent organic group, and A represents -O- or -NR N - and R N is a hydrogen atom or a monovalent organic group, and Z U1 is an m-valent organic group, and Z U2 is an (n+1)-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

[0159] R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom. R N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom. Z U1 is a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O)2-, or -NR N A group bonded to at least one group selected from the group consisting of - is more preferred. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination of these. R N 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. Z U2 is a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O)2-, or -NR N A group bonded to at least one group selected from the group consisting of - is more preferred. The hydrocarbon group may be ZU1 The same as those mentioned in the above, and the preferred embodiments are also the same. X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. A (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred. n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1. m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0160] It is also preferred that the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be either an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group. From the viewpoint of the chemical resistance of the resulting cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6. The amide group is -C(=O)-NR N - refers to a bond represented by R N is as described above. When the crosslinker U has an amide group, the crosslinker U may be, for example, RC(═O)—NR N A group represented by -* or *-C(=O)-NR NIt can be contained 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 hydroxy group, an alkyleneoxy group (however, when a polyalkyleneoxy group is formed, the group is a polyalkyleneoxy group), an amide group, and a cyano group in the molecule, but an embodiment in which only one structure is present in the molecule is also preferred. The hydroxy group, alkyleneoxy group, amide group, and cyano group may be present at any position in the crosslinking agent U. However, from the viewpoint of chemical resistance, it is also preferable that the crosslinking agent U is such that at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group, and cyano group is linked to at least one radically polymerizable group contained in the crosslinking agent U via 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 radically polymerizable group, it is preferable that the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via 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 alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) opposite the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. In addition, preferred embodiments of the radically polymerizable group are the same as those of the radically 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 bonded to the side of the amide group opposite the linking group L2-1 or L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. 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, and groups represented by a combination thereof. Preferred embodiments of the radically polymerizable group are the same as those of the radically polymerizable group in the crosslinking agent U described above. In the above embodiments, the carbon atom side of the amide group may be bonded to the linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or L2-2. Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that the crosslinking agent U has a hydroxy group.

[0161] From the viewpoint of compatibility with the specific resin, the crosslinking agent U preferably contains an aromatic group. The aromatic group is preferably directly bonded to a urea bond or a urethane bond contained in the crosslinking agent U. When 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 is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably 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 in which two or more hydrogen atoms have been removed from a benzene ring structure. The aromatic heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. These rings may be further condensed with other rings, such as indole and benzimidazole. The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The aromatic group is preferably contained in, for example, a linking group that links two or more radically polymerizable groups and includes a urea bond or a urethane bond, or a linking group that links at least one radically polymerizable group contained in the crosslinking agent U with at least one group selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group.

[0162] The number of atoms (linking 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. When the crosslinking agent U contains a total of two or more urea bonds or urethane bonds, when it contains two or more radically polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radically polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radically polymerizable group may be within the above range. In this specification, the "number of atoms (linking chain length) between a urea bond or urethane bond and a polymerizable group" refers to the atomic chain on the path connecting two atoms or groups of atoms to be linked that connects these objects with the shortest length (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0163] [ka]

[0164] [Axis of symmetry] It is also preferred that the crosslinking agent U is a compound having a structure without an axis of symmetry. "Crosslinker U does not have an axis of symmetry" means that it is an asymmetric compound, lacking an axis along which the same molecule as the original molecule would be generated by rotating the entire compound. Furthermore, "Crosslinker U does not have an axis of symmetry" means that when the structural formula of crosslinker U is written on paper, the structural formula of crosslinker 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 prevents aggregation of the crosslinking agent U molecules in the composition film.

[0165] [Molecular weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1500, and even more preferably 200 to 900.

[0166] The method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a radical polymerizable compound and a compound having an isocyanate group with a compound having at least one of a hydroxy group and an amino group.

[0167] Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited to these.

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, 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, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain. In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage of the pattern (cured product). Examples of the monofunctional radical crosslinking agent include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds having a boiling point of 100°C or higher under normal pressure are also preferred as the monofunctional radical crosslinking agent. Other examples of the bifunctional or higher functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0172] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass 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.

[0173] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0174] [Other crosslinking agents] The resin composition of the present invention preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent. The other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As the other crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a methylol group, an ethylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compound produced by the above method may be used.Oligomers obtained by self-condensation of the methylol groups of these compounds may also be used. As the amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents, which will be described later.

[0175] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine. The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the compound is preferably 1,500 or less, more preferably 180 to 1,200.

[0176] [ka]

[0177] R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0178] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0179] [ka]

[0180] In the formula, X represents a single bond or a divalent organic group, and each R 104 each independently represents an alkyl group or an acyl group, and R 103represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes under the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated by the action of an acid, -C(R 4 )2COOR 5 A group represented by (R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is eliminated by the action of an acid. R 105 each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a+d represents 5 or less, b+e represents 4 or less, and c+f represents 4 or less. A group that decomposes under the action of an acid to generate an alkali-soluble group, a group that is eliminated under the action of an acid, -C(R 4 )2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ) etc. In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be either linear or branched. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. These groups may further have known substituents.

[0181] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0182] The group that decomposes under the action of an acid to generate an alkali-soluble group or the group that is eliminated under the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.

[0183] Furthermore, as the compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a urea bond and a urethane bond is also preferred. The preferred embodiments of the above compound are the same as the preferred embodiments of the above crosslinking agent U, except that the polymerizable group is not a radical polymerizable group but at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group.

[0184] Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an ethylol group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compound is replaced with an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0185] [ka]

[0186] [ka]

[0187] [ka]

[0188] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be commercially available or may be synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0189] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0190] Specific examples of urea-based crosslinking agents include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; ethyleneurea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea; propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea; Examples include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0191] Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0192] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0193] As other crosslinking agents, commercially available products may be used, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, the same applies hereinafter) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0194] The resin composition of the present invention also preferably contains, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0195] -Epoxy compounds (compounds containing epoxy groups)- The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at 200°C or less, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is unlikely to occur. Therefore, the inclusion of an epoxy compound is effective in curing the resin composition at low temperatures and suppressing warpage.

[0196] The epoxy compound preferably contains a polyethylene oxide group, which further reduces the elastic modulus and suppresses warpage. The polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and preferably has 2 to 15 repeating units.

[0197] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epicron (registered trademark, the same applies below) 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron HP-4770, Epicron EXA-830LVP, Epicron EXA-8183, Epicron EXA-8169, Epicron N-660, Epicron N-665-EXP-S, Epicron N-740 (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark, the same applies below) BEO-20E, Likaresin BEO-60E, Likaresin HBE-100, Likaresin DME-100, Likaresin L-200 (all trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all trade names, manufactured by ADEKA Corporation), Ceroxa Epolead (registered trademark, hereinafter the same) 2021P, Celloxide 2081, Celloxide 2000, EHPE3150, Epolead (registered trademark, hereinafter the same) GT401, Epolead PB4700, Epolead PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-30 00-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.), and the like.The following compounds are also preferably used:

[0198] [ka]

[0199] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0200] Among the above structures, n is preferably 1 to 2 and m is preferably 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0201] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples that can be suitably used include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., and these may be used alone or in combination of two or more.

[0202] -Benzoxazine compounds (compounds having a benzoxazolyl group)- Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress warping.

[0203] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds, which may be used alone or in combination of two or more.

[0204] The content of the other crosslinking agent is preferably 0.1 to 30 mass % relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass %, even more preferably 0.5 to 15 mass %, and particularly preferably 1.0 to 10 mass %. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total content thereof is preferably within the above range.

[0205] [Sensitizer] The resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator or the photoradical polymerization initiator undergoes a chemical change and decomposes, generating a radical, an acid, or a base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isodiethylaminobenzoate amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like. Other sensitizing dyes may also be used. For details about the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0206] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0207] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.

[0208] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0209] When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be one type, or two or more types. When two or more types of chain transfer agents are used, the total amount thereof is preferably within the above range.

[0210] <Base generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of the non-ionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3).

[0211] [ka]

[0212] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3each independently represents an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom, provided that Rb 1 and Rb 2 cannot be hydrogen atoms at the same time. 1 , Rb 2 and Rb 3 None of them have a carboxy group. In this specification, the term "tertiary amine structure" refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to carbon atoms of a hydrocarbon group. Therefore, if the carbon atom bonded to the trivalent nitrogen atom is a carbon atom that constitutes a carbonyl group, that is, if it forms an amide group together with the nitrogen atom, it is not a tertiary amine structure.

[0213] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 Preferably, at least one of these contains a cyclic structure, and more preferably, at least two contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a fused ring, and a monocyclic ring or a fused ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5- or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

[0214] More specifically, Rb 1 and Rb 2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent. 1 and Rb 2 may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and Rb 2is preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

[0215] Rb 3 Examples of the group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and more preferably having 8 to 16 carbon atoms), an alkoxyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. 3 may further have a substituent.

[0216] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2).

[0217] [ka]

[0218] In the formula, Rb 11 and Rb 12 , and Rb31 and Rb 32 respectively represent Rb in formula (B1). 1 and Rb 2 is the same as Rb 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent. 13 is preferably an arylalkyl group.

[0219] Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and still more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0220] Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and still more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and still more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 12 carbon atoms), and an aryl group is preferred.

[0221] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0222] [ka]

[0223] Rb 11 and Rb 12 is Rb in formula (B1-1) 11 and Rb 12 is synonymous with. Rb 15 and Rb 16 represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group. Rb 17 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferred.

[0224] [ka]

[0225] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the linking chain is 3 or more. N1 and R N2 each independently represents a monovalent organic group.

[0226] In this specification, the term "linking chain" refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked, which links these atoms to be linked in the shortest possible manner (with the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as the saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain") is 4.

[0227] [ka]

[0228] The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly progressing the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018 / 038002.

[0229] The base generator also preferably contains a compound represented by the following formula (N1).

[0230] [ka]

[0231] In formula (N1), R N1 and R N2 each independently represents a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0232] L is a divalent linking group, and is preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic sequence that forms the shortest path between the two carbonyl groups in the formula.

[0233] In formula (N1), R N1 and R N2 R each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. N1 and R N2 When an aliphatic hydrocarbon group is used as the base, the basicity of the generated base is high, and this is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, in the aromatic ring, or in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

[0234] R N1 and R N2Examples of the aliphatic hydrocarbon group constituting the formula (I) include a linear or branched chain alkyl group, a cyclic alkyl group, a group containing a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group. The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The group containing a combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the group containing a combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. Among these, from the viewpoint of increasing the boiling point of the decomposition product base described later, R N1 and R N2 is preferably an alkyl group having 5 to 12 carbon atoms. However, in a formulation where importance is placed on adhesion when laminating with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0235] R N1 and R N2may be linked together to form a cyclic structure. The cyclic structure may have an oxygen atom or the like in the chain. N1 and R N2 The cyclic structure formed by may be a monocyclic ring or a fused ring, but is preferably a monocyclic ring. The cyclic structure formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring, and is preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring.

[0236] R C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom. The protecting group is preferably a protecting group that is decomposed by the action of an acid or a base, and a protecting group that is decomposed by an acid is preferred. Specific examples of the protecting group include linear or cyclic alkyl groups, and linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group. Examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and preferred are a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of cyclic alkyl groups having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.

[0237] In formula (N1), the divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent and may have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group containing a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups do not necessarily have to have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. A group containing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

[0238] Specifically, the linking group L is preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group containing a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group. The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. The group containing a combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0239] The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and still more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, more preferably 1 to 4, and even more preferably 1 or 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms. Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cis-vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

[0240] Examples of the base generator include, but are not limited to, the following compounds:

[0241] [ka]

[0242] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0243] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0244] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0245] [ka]

[0246] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0247] [ka]

[0248] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, still 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. The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0249] <Metal adhesion improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0250] [Silane coupling agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compound as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0251] [ka]

[0252] 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 of suitable silanes 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-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more.

[0253] [Aluminum-based adhesion promoter] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0254] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A No. 2013-072935, the contents of which are incorporated herein by reference.

[0255] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the upper limit, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be one type, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0256] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor, which can effectively inhibit migration of metal ions derived from the metal layer (or metal wiring) into the film when the resin composition is applied to the metal layer (or metal wiring) to form a film.

[0257] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.

[0258] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0259] Other migration inhibitors include, for example, the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219. The contents of this specification are incorporated herein by reference.

[0260] Specific examples of the migration inhibitor include the following compounds.

[0261] [ka]

[0262] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total solid content of the resin composition.

[0263] The migration inhibitor may be one type only, or two or more types may be used. When two or more types of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0264] <Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

[0265] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and phenoxazine, the contents of which are incorporated herein by reference.

[0266] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, relative to the total solid content of the resin composition.

[0267] The polymerization inhibitor may be one type only, or two or more types may be used. When two or more types of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0268] <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, UV absorbers, organotitanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as long as the effects of the present invention are achieved. By appropriately incorporating these components, film properties and other characteristics can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104 and 0107-0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, their total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0269] [Surfactant] As the surfactant, various surfactants can be used, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0270] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared can be further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a uniform film with little thickness unevenness.

[0271] Examples of fluorosurfactants include compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

[0272] [ka]

[0273] The weight average molecular weight of the compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. The fluorine-containing surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0274] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and particularly preferably 7 to 25 mass%. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0275] Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0276] The surfactant may be used alone or in combination of two or more kinds. The content of the surfactant is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0277] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during the drying process after application.

[0278] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference.

[0279] When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total content is preferably within the above range.

[0280] [Thermal polymerization initiator] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals by thermal energy and initiate or promote the polymerization reaction of a polymerizable compound. Addition of a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. In addition, photopolymerization initiators may also have the function of initiating polymerization by heat, and may be added as thermal polymerization initiators.

[0281] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, the contents of which are incorporated herein by reference.

[0282] When a thermal polymerization initiator is contained, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0283] [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.

[0284] The average particle size of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, even more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm. The above-mentioned average particle size of the inorganic particles is the primary particle size and also the volume average particle size, which can be measured by dynamic light scattering using, for example, a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurements are difficult, centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method can also be used.

[0285] [Ultraviolet absorber] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. Specific examples of ultraviolet absorbers include the compounds described in paragraphs 0341 to 0342 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0286] The ultraviolet absorbers may be used alone or in combination of two or more. When the resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 mass % or more and 1 mass % or less, and more preferably 0.01 mass % or more and 0.1 mass % or less, relative to the total solid mass of the resin composition.

[0287] [Organotitanium Compounds] By including an organotitanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0288] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are preferred because they provide good storage stability to the resin composition and produce a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0289] Among them, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0290] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is improved.

[0291] [Antioxidants] By including an antioxidant as an additive, the elongation properties of the cured film and adhesion to metal materials can be improved. Examples of antioxidants include phenolic compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0292] The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By adding an amount of 0.1 part by mass or more, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials even in high-temperature, high-humidity environments, and by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.

[0293] [Anti-aggregating agent] Examples of anti-aggregating agents include sodium polyacrylate.

[0294] The anti-aggregating agents may be used singly or in combination of two or more. When the resin composition contains an anti-aggregating agent, the content of the anti-aggregating agent is preferably 0.01 mass % or more and 10 mass % or less, and more preferably 0.02 mass % or more and 5 mass % or less, relative to the total solid mass of the resin composition.

[0295] [Phenol compounds] Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetrith-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0296] The phenolic compounds may be used singly or in combination of two or more. When the resin composition contains a phenolic compound, the content of the phenolic compound is preferably 0.01 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid mass of the resin composition.

[0297] [Other polymer compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified by introducing crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups.

[0298] The other polymer compounds may be used singly 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 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid mass of the resin composition.

[0299] <Characteristics of resin composition> The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content of the resin composition. 2 / s~12,000mm 2 / s is preferred, 2,000 mm 2 / s~10,000mm 2 / s is more preferable, 2,500 mm 2 / s~8,000mm 2 / s is more preferable. Within the above range, it is easy to obtain a highly uniform coating film. 2 / s or more, it is easy to apply it to a thickness required for an insulating film for rewiring, for example, and it is 12,000 mm 2 If the viscosity is less than / s, a coating film with excellent surface condition can be obtained.

[0300] <Restrictions on substances contained in resin compositions> 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 the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

[0301] 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 metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0302] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0303] A conventionally known container can be used as a container for storing the resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0304] <Cured product of resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing a resin composition. The resin composition is preferably cured by heating, with the heating temperature being more preferably 120°C to 400°C, even more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected depending on the application, such as a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the shape of the cured product can be selected depending on the application, such as forming a protective film on the wall surface, forming via holes for electrical continuity, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage percentage of the resin composition of the present invention upon curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of volume change before and after curing of the resin composition, and can be calculated using the following formula. Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0305] <Characteristics of the cured resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0306] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0307] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration step, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtration is performed under pressure, the pressure to be applied is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples of the adsorbent 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 in the bottle may be subjected to a degassing step by placing it under reduced pressure.

[0308] (Method of producing cured product) The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film. The method for producing a cured product more preferably includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern. It is particularly preferable that the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step. The method for producing a cured product preferably includes the film-forming step and the step of heating the film. Each step will be described in detail below.

[0309] <Film formation process> The resin composition of the present invention can be used in a film-forming process in which the resin composition is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film.

[0310] [Base material] The type of substrate can be appropriately determined depending on the application and is not particularly limited. Examples of substrates include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and electrode plates for plasma display panels (PDPs). The substrate is particularly preferably a semiconductor production substrate, and more preferably a silicon substrate, a Cu substrate, or a mold substrate. These substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface. The shape of the substrate is not particularly limited, and may be circular or rectangular. The size of the substrate is preferably, for example, 100 to 450 mm in diameter, more preferably 200 to 450 mm, if it is circular, and preferably, 100 to 1000 mm in short side length, more preferably 200 to 700 mm, if it is rectangular. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0311] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0312] The resin composition is preferably applied to a substrate by coating. Specific examples of the coating method 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 the film thickness, spin coating, slit coating, spray coating, and inkjet coating are preferred, and from the viewpoint of uniformity of the film thickness and productivity, spin coating and slit coating are more preferred. A film of the desired thickness can be obtained by adjusting the solid content concentration of the resin composition and coating conditions depending on the coating method. 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. Spin coating can be applied, for example, at a rotation speed of 500 to 3,500 rpm for approximately 10 seconds to 3 minutes. Alternatively, a coating film may be formed by applying the coating to a temporary support in advance using the above-mentioned application method, and then transferred onto the substrate. As for the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. Additionally, a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing. Before applying the resin composition to the substrate, a pre-wetting step may be employed in which the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.

[0313] <Drying process> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0314] <Exposure process> The film may be subjected to an exposure step to selectively expose the film to light. The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, resulting in exposed and unexposed areas of the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. 2 is preferred, and 200 to 8,000 mJ / cm 2 is more preferred.

[0315] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0316] Examples of exposure wavelengths, in relation to the light source, include: (1) semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps (g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays (EUV) (wavelength 13.6 nm), (6) electron beams, and (7) YAG lasers (second harmonic 532 nm, third harmonic 355 nm). For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0317] <Post-exposure baking process> The film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step in which the film exposed in the exposure step is heated. The post-exposure baking step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure baking step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes. The temperature rise rate in the post-exposure heating step from the starting temperature to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may be changed during heating as needed. The heating means in the post-exposure baking step is not particularly limited, and known means such as a hot plate, an oven, and an infrared heater can be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0318] <Developing process> After exposure, the film may be subjected to a development step in which it is developed with a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. Development removes either the exposed or unexposed portions of the film, forming a pattern. Here, development in which the non-exposed portions of the film are removed by the development process is called negative development, and development in which the exposed portions of the film are removed by the development process is called positive development.

[0319] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0320] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are 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, and more preferred is TMAH. The content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

[0321] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph 0387 of WO 2021 / 112189, the contents of which are incorporated herein by reference. Suitable examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and suitable examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0322] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0323] 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, and may be 100% by mass.

[0324] When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates into the pattern, the performance of the pattern, such as breaking elongation, may be improved.

[0325] As the basic compound, an organic base is preferred from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated). The basic compound is preferably a basic compound having an amino group, and is preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, or a tertiary amide. In order to promote the imidization reaction, a primary amine, a secondary amine, a tertiary amine, or an ammonium salt is preferred, a secondary amine, a tertiary amine, or an ammonium salt is more preferred, a secondary amine or a tertiary amine is even more preferred, and a tertiary amine is particularly preferred. From the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferable that the basic compound is one that is unlikely to remain in the cured film (the obtained cured product), and from the viewpoint of promoting cyclization, it is preferable that the amount of the basic compound that remains is unlikely to decrease before heating due to evaporation or the like. 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 normal pressure (101,325 Pa). The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer. For example, when the boiling point of the organic solvent is 100°C, the basic compound used preferably has a boiling point of 80°C or higher, more preferably 100°C or higher. The developer may contain only one kind of basic compound, or may contain two or more kinds of basic compounds.

[0326] 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), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples of the alkyl amine 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.

[0327] The preferred embodiments of the base generator are the same as those of the base generator contained in the composition described above. In particular, the base generator is preferably a thermal base generator.

[0328] When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more. When the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the developer. The developer may contain only one kind of at least one of a basic compound and a base generator, or may contain two or more kinds. When two or more kinds of at least one of a basic compound and a base generator are used, the total amount thereof is preferably within the above range.

[0329] The developer may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0330] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred. Alternatively, a process may be employed in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate, and this process may be repeated multiple times. Methods for supplying the developer in the development step include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated on the substrate by ultrasonic waves or the like, and a step in which these are combined.

[0331] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0332] In the development step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a rinse liquid may be supplied before the developer in contact with the pattern is completely dried.

[0333] [Rinse solution] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0334] When the rinse liquid contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent. The organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.

[0335] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA (propylene glycol monomethyl ether acetate), or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[0336] When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the total mass of the rinse solution, or may account for 100% by mass of the total mass of the rinse solution.

[0337] The rinse liquid may contain at least one of a basic compound and a base generator. Although not particularly limited, when the developer contains an organic solvent, one preferred embodiment of the present invention is one in which the rinse liquid contains an organic solvent and at least one of a basic compound and a base generator. Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained in the above-mentioned developer containing an organic solvent, and preferred embodiments are also the same. The basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.

[0338] When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more. When the basic compound or base generator is solid in the environment in which the rinse solution is used, the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one kind of at least one of a basic compound and a base generator, or may contain two or more kinds. When there are two or more kinds of at least one of a basic compound and a base generator, the total amount thereof is preferably within the above range.

[0339] The rinse solution may further contain other ingredients. Examples of other components include known surfactants and known defoaming agents.

[0340] [Method of supplying rinse liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid can be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc. That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle. The method of supplying the rinse liquid in the rinsing step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, and a combination of these steps.

[0341] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0342] The developing step may include a step of contacting the pattern with a treatment liquid after treatment with a developer or after washing the pattern with a rinse liquid. Alternatively, a method may be employed in which the treatment liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.

[0343] The treatment liquid may include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator. Preferred aspects of the organic solvent, and at least one of the basic compound and the base generator are the same as the preferred aspects of the organic solvent, and at least one of the basic compound and the base generator used in the rinse liquid described above. The method of supplying the processing liquid to the pattern can be the same as the method of supplying the rinse liquid described above, and the preferred embodiments are also the same.

[0344] The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the treatment liquid. There is no particular lower limit to the content, but it is preferably, for example, 0.1% by mass or more. Furthermore, when the basic compound or base generator is solid in the environment in which the treatment liquid is used, the content of the basic compound or base generator is preferably 70 to 100 mass % relative to the total solid content of the treatment liquid. When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one kind of at least one of a basic compound and a base generator, or may contain two or more kinds. When there are two or more kinds of at least one of a basic compound and a base generator, it is preferable that the total amount thereof is within the above range.

[0345] <Heating process> The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without performing a development step, or a film obtained in the film-forming step. In the heating step, the resin such as the polyimide precursor is cyclized to form a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0346] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0347] In the heating step, heating is preferably carried out at a temperature increase rate of 1 to 12°C / min from the initial temperature to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. Additionally, in the case of a rapid heating oven, the temperature is preferably increased from the initial temperature to the maximum heating temperature at a rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0348] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and is preferably raised from a temperature that is 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0349] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0350] In particular, when forming a multilayer laminate, from the viewpoint of adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0351] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed at a temperature in the range of 100 to 150°C, followed by a second pretreatment step at a temperature in the range of 150 to 200°C. Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C. / min.

[0352] From the viewpoint of preventing decomposition of the specific resin, the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the heating step under reduced pressure, etc. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. The heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0353] <Post-development exposure process> The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include both a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator to light, can be promoted. In the post-development exposure step, it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm, calculated as exposure energy at a wavelength to which the photosensitive compound is sensitive. 2 is preferred, and 100 to 15,000 mJ / cm 2 is more preferred. The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0354] <Metal layer formation process> The pattern obtained by the development step (which is preferably subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step 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 forming step of forming a metal layer on the pattern obtained in the development step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0355] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0356] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations thereof. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0357] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0358] <Application> The cured product manufacturing method of the present invention and the fields to which the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the etching of insulating films for packaging applications such as those mentioned above. For details of these applications, see, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library's "Fundamentals and Development of Polyimide Materials" (November 2011), and the Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimides: Fundamentals and Applications" (NTS, August 2010).

[0359] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0360] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers. Of the two or more layers made of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0361] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

[0362] The laminate of the present invention preferably includes two or more layers made of a cured product, and a metal layer between any two of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on the layer made of the cured product, between the steps for producing a cured product that are performed multiple times. Preferred aspects of the metal layer-forming step are as described above. As the laminate, for example, a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0363] <Lamination process> The method for producing the laminate of the present invention preferably includes a lamination step. The lamination process is a series of processes including (a) a film-forming process (layer-forming process), (b) an exposure process, (c) a development process, and (d) at least one of a heating process and a post-development exposure process, which are performed again on the surface of the pattern (resin layer) or metal layer in this order. However, at least one of the (a) film-forming process and the (d) heating process and the post-development exposure process may be repeated. Furthermore, at least one of the (d) heating process and the post-development exposure process may be followed by the (e) metal layer-forming process. Needless to say, the lamination process may further include the drying process and the like as appropriate.

[0364] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

[0365] The lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times. For example, a structure of 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred. The above layers may be the same or different in composition, shape, film thickness, etc.

[0366] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer. Specific examples include an embodiment in which the following steps are repeated in this order: (a) a film-forming step, (b) an exposure step, (c) a development step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer-forming step; or an embodiment in which the following steps are repeated in this order: (a) a film-forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer-forming step. By alternately performing the lamination step of laminating a resin composition layer (resin layer) of the present invention and the metal layer-forming step, the resin composition layer (resin layer) of the present invention and a metal layer can be alternately laminated.

[0367] (Surface activation treatment process) The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment. The surface activation treatment step is usually carried out after the metal layer formation step, but the surface activation treatment step may be carried out on the resin composition layer after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and then the metal layer formation step may be carried out. The surface activation treatment may be performed on at least a portion of the metal layer, or 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 resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is formed. In this way, by performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesion with the resin composition layer (film) formed on the surface. It is preferable to perform the surface activation treatment on a part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with a metal layer or a resin layer provided on the surface that has been surface-activated. In particular, when negative development is performed, etc., if the resin composition layer is cured, it is less susceptible to damage due to the surface treatment, and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0368] (Semiconductor device and its manufacturing method) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product of the present invention or the method for producing the laminate. For specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer, the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these documents are incorporated herein by reference.

[0369] The present invention also relates to the following polyimide precursor or polyamideimide precursor (hereinafter also referred to as "specific resin A"). A polyimide precursor or a polyamideimide precursor having a repeating unit represented by the following general formula (11) or (12): the content of elemental sulfur contained in the polyimide precursor or polyamideimide precursor is less than 5 ppm based on the total mass of the polyimide precursor or polyamideimide precursor; the content of chloride ions contained in the polyimide precursor or polyamideimide precursor is less than 3 ppm based on the total mass of the polyimide precursor or polyamideimide precursor; Polyimide precursor or polyamideimide precursor.

[0370] [ka]

[0371] In general formula (11) and general formula (12), R 115 represents a tetravalent organic group, and R 117 represents a trivalent organic group, A 1~A 3 each independently represents an oxygen atom or -NR z1 - represents R 111 , R 116 each independently represents a divalent organic group, R 113 , R 114 , and R 118 each independently represents a hydrogen atom or a monovalent organic group, R z1 represents a hydrogen atom or a monovalent organic group. R 113 and R 114 at least one of R is a group having an ethylenically unsaturated bond; 118 is a group having an ethylenically unsaturated bond. z1 represents a hydrogen atom or a monovalent organic group, and R z1 is R 113 , R 114 , or R 118 may be bonded to form a ring.)

[0372] R 115 The tetravalent organic group is the same as the tetravalent organic group as X1 above, and preferred embodiments are also the same. R 117 The trivalent organic group is the same as the trivalent organic group as Y1 above, and preferred embodiments are also the same. R z1 The monovalent organic group is R as Z1 to Z3 above. z The same applies to the monovalent organic group in the above, and the preferred embodiments are also the same. R z1 is R 113 , R 114 , or R 118 The ring formed is not particularly limited and may be a monocyclic ring or a polycyclic ring. The ring may be an aromatic ring or a non-aromatic ring (for example, a non-aromatic heterocyclic ring).

[0373] R 113 , R 114 , and R 118each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains an alkyl group (linear, branched, or cyclic), an alkenyl group (linear or branched), an aromatic group, or a polyalkyleneoxy group. The number of carbon atoms in the monovalent organic group is not particularly limited, but is, for example, 1 to 30. Also, R 113 and R 114 It is more preferable that at least one of R has a group having an ethylenically unsaturated bond, and that both of R have a group having an ethylenically unsaturated bond. 113 and R 114 It is also preferred that at least one of them has a group having two or more ethylenically unsaturated bonds. R 118 R has a group having an ethylenically unsaturated bond. 118 It is also preferred that the alkyl group has a group having two or more ethylenically unsaturated bonds. The group having an ethylenically unsaturated bond is a polymerizable group, and is a radical polymerizable group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the above formula (3), with the group represented by the above formula (3) being preferred.

[0374] R 113 and R 114 At least one of the above may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group are as described above.

[0375] R 111 , R 116 each independently represents a divalent organic group. Examples of divalent organic groups include groups containing straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, and are preferably straight-chain or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms, or groups consisting of a combination thereof, and more preferably groups containing aromatic groups having 6 to 20 carbon atoms. The straight-chain or branched aliphatic groups may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic groups and aromatic groups may have hydrocarbon groups in the ring substituted with groups containing heteroatoms. R 111 , R 116 Examples of the group include groups represented by -Ar- and -Ar-L-Ar-, with the group represented by -Ar-L-Ar- being preferred, where each Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, or -NHCO-, or a group consisting of a combination of two or more of the above.

[0376] R 111 , R 116 is preferably derived from a diamine. Examples of diamines used in producing the polyimide precursor 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 111 , R 116 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 group consisting of 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 a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

[0377] [ka]

[0378] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -NHCO-, or a group selected from a combination thereof; more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, or -C(=O)-; and even more preferably -CH2-, -O-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0379] The diamine is not particularly limited, but examples thereof include the same diamines as those in step 2 above.

[0380] R 111 , R 116 is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic film. Here, each 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-, or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, or -CO-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0381] Also, R 111 , R 116 From the viewpoint of i-line transmittance, is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferably a divalent organic group represented by formula (61). Formula (51)

[0382] [ka]

[0383] In formula (51), R 50 ~R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57 At least one of the above is a fluorine atom, a methyl group or a trifluoromethyl group, and each * independently represents a bonding site to the nitrogen atom in formula (2). R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0384] [ka]

[0385] In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2). 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, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

[0386] The content of elemental sulfur contained in the polyimide precursor or polyamideimide precursor is less than 5 ppm based on the total mass of the polyimide precursor or polyamideimide precursor. The method for measuring the content of elemental sulfur is as described above. The content of chloride ions contained in the polyimide precursor or polyamideimide precursor is less than 3 ppm based on the total mass of the polyimide precursor or polyamideimide precursor. The method for measuring the content of chloride ions is as described above. As described above, the amount of chloride ions in the precursor was measured as the amount of residual chlorine element.

[0387] The specific resin A is preferably produced by the above-mentioned method for producing a polyimide precursor or a polyamideimide precursor.The specific resin A is preferably the above-mentioned specific resin.

[0388] -A in the above general formula (11) 1 -R 114 , -A 2 -R 113 At least one of these preferably represents a group represented by the above formula (4). The group represented by the above formula (4) is preferably a group represented by the above formula (5).

[0389] R in the above general formulas (11) and (12) 113 , R 114 , and R 118 each independently preferably represents a group represented by the above formula (3). -A in the above general formula (11) 1 -R 114 and -A 2 -R 113 It is preferred that one of the groups is a group having an ethylenically unsaturated bond, and the other is a group represented by the above formula (4).

[0390] The weight-average molecular weight (Mw) of the polyimide precursor or polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polyimide precursor or polyamideimide precursor preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. [Example]

[0391] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0392] <Synthesis example of polyimide precursor or polyamideimide precursor (specific resin)> Synthesis Example 1 (Synthesis of A-1) A-1 was synthesized using ODPA as acid anhydride 1, HEMA as side chain component 1, and ODA as diamine. The details of the synthesis method of A-1 are shown below.

[0393] 21.18 g (68.1 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 18.12 g (139 mmol) of 2-hydroxyethyl methacrylate (HEMA), 0.038 g of hydroquinone, 23.93 g (30.3 mmol) of pyridine, and 76.7 g of diglyme were mixed and stirred at 60°C for 3 hours, then cooled to 25°C. Subsequently, the reaction solution was cooled to 0°C, and then 18.16 g (141 mmol) of oxalyl chloride dissolved in 59.35 g of diglyme was added dropwise over 60 minutes, and the temperature was raised to 30°C, followed by stirring for 1.5 hours. The mixture was cooled to 0°C, and 12.27 g (61.2 mmol) of 4,4'-oxydianiline (ODA) dissolved in 92.46 g of NMP was added dropwise over 1 hour, followed by stirring for 1 hour. 12.55 g (272 mmol) of ethanol was then added, and the mixture was stirred for 1 hour. The polyimide precursor resin was precipitated in 4 L of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes.

[0394] The polyimide precursor resin was collected by filtration, dried under vacuum, and then dissolved in 300 g of THF. Next, 50 g of R-1 was added as an ion exchange resin, and the mixture was stirred at 25° C. for 4 hours to carry out an ion exchange treatment. The ion exchange resin was removed by filtration, and the THF solution was precipitated in 4 L of water, and the polyimide precursor resin was filtered. The resulting polyimide precursor resin was then dried under reduced pressure at 45°C for 2 days to obtain a polyimide precursor (A-1). The resulting polyimide precursor (A-1) had a number average molecular weight (Mn) of 7,300 and a weight average molecular weight (Mw) of 22,000. The structure of the polyimide precursor (A-1) is a structure represented by the following formula (A-1).

[0395] [ka]

[0396] Synthesis Example 2 (Synthesis of A-2) A-2 was synthesized using ODPA as acid anhydride 1, BPDA as acid anhydride 2, HEMA as side chain component 1, and ODA as diamine. The details of the synthesis method of A-2 are shown below.

[0397] Polyimide precursor A-2 was synthesized in the same manner as in Synthesis Example 1, except that the 21.18 g (68.1 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) in Synthesis Example 1 was changed to 10.7 g (34.4 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) and 10.15 g (34.4 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA). The polyimide precursor (A-1) thus obtained had a number average molecular weight (Mn) of 8,000 and a weight average molecular weight (Mw) of 27,000. The structure of the polyimide precursor (A-2) is a structure represented by the following formula (A-2).

[0398] [ka]

[0399] Synthesis Example 3 (Synthesis of A-3) A-3 was synthesized using HEMA as the side chain component 1, pyrrolidine as the side chain component 2, and BAPP as the diamine. The details of the synthesis method of A-3 are shown below.

[0400] A-3 was synthesized in the same manner as in Synthesis Example 1, except that the 18.12 g (139 mmol) of 2-hydroxyethyl methacrylate in Synthesis Example 1 was changed to 13.6 g (104.3 mmol) and 2.47 g (34.7 mmol) of pyrrolidine, and the 4,4′-oxydianiline was changed to 25.49 g (62.1 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP). The polyimide precursor (A-3) thus obtained had a number average molecular weight (Mn) of 9,000 and a weight average molecular weight (Mw) of 24,000. The structure of the polyimide precursor (A-3) is a structure represented by the following formula (A-3).

[0401] [ka]

[0402] Synthesis Example 4 (Synthesis of A-4) A-4 was synthesized using ODPA as acid anhydride 1, BPDA as acid anhydride 2, HEMA as side chain component 1, and ODA as diamine. The details of the synthesis method of A-4 are shown below.

[0403] 4,4'-Oxydiphthalic anhydride (ODPA), 10.15 g (34.4 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 18.12 g (139 mmol) of 2-hydroxyethyl methacrylate (HEMA), 0.038 g of hydroquinone, 23.93 g (30.3 mmol) of pyridine, and 76.7 g of diglyme were mixed and stirred at 60 °C for 3 hours, then cooled to 25 °C. Next, the reaction solution was cooled to -10 °C, and 16.77 g (141 mmol) of thionyl chloride dissolved in 59.35 g of diglyme was added dropwise over 60 minutes, followed by stirring for 1 hour.

[0404] Next, 12.27 g (61.2 mmol) of 4,4'-oxydianiline (ODA) dissolved in 92.46 g of NMP was added dropwise over 1 hour and stirred for 1 hour. Next, 12.55 g (272 mmol) of ethanol was added, and the mixture was stirred for 1 hour. The polyimide precursor resin was precipitated in 4 L of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration, dried under vacuum, and then dissolved in 300 g of THF. Next, R-1 was added as an ion exchange resin, and the mixture was stirred at 25 °C for 4 hours to perform an ion exchange treatment. The ion exchange resin was removed by filtration, and the THF solution was precipitated in 4 L of water, and the polyimide precursor resin was filtered. The resulting polyimide precursor resin was then dried under reduced pressure at 45 °C for 2 days to obtain polyimide precursor (A-4). The polyimide precursor (A-4) thus obtained had a number average molecular weight (Mn) of 8,000 and a weight average molecular weight (Mw) of 24,000. The structure of A-4 is a structure represented by the following formula (A-4).

[0405] [ka]

[0406] Synthesis Example 5 (Synthesis of A-5) The details of the synthesis method of A-5 are shown below. A-5 was synthesized in the same manner as in Synthesis Example 2, except that the treatment with ion exchange resin R-1 in Synthesis Example 2 was not carried out. The polyimide precursor (A-5) thus obtained had a number average molecular weight (Mn) of 7,500 and a weight average molecular weight (Mw) of 26,000. The structure of the polyimide precursor (A-5) is a structure represented by the following formula (A-5).

[0407] [ka]

[0408] Synthesis Example 6 (Synthesis of A-6) A-6 was synthesized using TMA as the acid anhydride 1, HEMA as the side chain component 1, and ODA as the diamine. The details of the synthesis method of A-6 are shown below.

[0409] A-6 was synthesized in the same manner as in Synthesis Example 1, except that the 21.18 g (68.1 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) in Synthesis Example 1 was changed to 13.08 g (68.1 mmol) of trimellitic anhydride (TMA) and the 18.12 g (139 mmol) of 2-hydroxyethyl methacrylate (HEMA) was changed to 9.04 g (69.5 mmol). The polyamideimide precursor (A-6) thus obtained had a number average molecular weight (Mn) of 5,110 and a weight average molecular weight (Mw) of 15,400. The structure of the polyamideimide precursor (A-6) is a structure represented by the following formula (A-6).

[0410] [ka]

[0411] Synthesis Example 7 (Synthesis of A-7) The details of the synthesis method of A-7 are shown below. A-7 was synthesized in the same manner as in Synthesis Example 2, except that the treatment with ion exchange resin R-1 in Synthesis Example 1 was changed to ion exchange resin R-2. The polyimide precursor (A-7) thus obtained had a number average molecular weight (Mn) of 7,200 and a weight average molecular weight (Mw) of 23,000. The structure of the polyimide precursor (A-7) is a structure represented by the following formula (A-7).

[0412] [ka]

[0413] Synthesis Example 8 (Synthesis of A-8) The details of the synthesis method of A-8 are shown below. A-8 was synthesized in the same manner as in Synthesis Example 2, except that the treatment with ion exchange resin R-1 in Synthesis Example 2 was changed to ion exchange resin R-3. The polyimide precursor (A-8) thus obtained had a number average molecular weight (Mn) of 7,280 and a weight average molecular weight (Mw) of 24,570. The structure of the polyimide precursor (A-8) is a structure represented by the following formula (A-8).

[0414] [ka]

[0415] Synthesis Example 9 (Synthesis of A-9) The details of the synthesis method of A-9 are shown below. A-9 was synthesized in the same manner as in Synthesis Example 1, except that the treatment with ion exchange resin R-1 in Synthesis Example 1 was changed to ion exchange resin R-4. The polyimide precursor (A-9) thus obtained had a number average molecular weight (Mn) of 6,716 and a weight average molecular weight (Mw) of 20,680. The structure of the polyimide precursor (A-9) is a structure represented by the following formula (A-9).

[0416] [ka]

[0417] Synthesis Example 10 (Synthesis of A-10) A-10 was synthesized using HEMA as the side chain component 1 and pyrrolidine as the side chain component 2. The details of the synthesis method of A-10 are shown below.

[0418] A-10 was synthesized in the same manner as in Synthesis Example 2, except that the 18.12 g (139 mmol) of 2-hydroxyethyl methacrylate in Synthesis Example 2 was changed to 13.6 g (104.3 mmol) and 2.47 g (34.7 mmol) of pyrrolidine. The polyimide precursor (A-10) thus obtained had a number average molecular weight (Mn) of 7,600 and a weight average molecular weight (Mw) of 25,650. The structure of the polyimide precursor (A-10) is a structure represented by the following formula (A-10).

[0419] [ka]

[0420] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured using gel permeation chromatography (GPC) and expressed as polystyrene equivalent values. Mw and Mn were determined using an HLC-8220GPC (manufactured by Tosoh Corporation) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. NMP (N-methyl-2-pyrrolidone) was used as the eluent. A UV (ultraviolet) detector at a wavelength of 254 nm was used for GPC measurement.

[0421] In each of the Examples and Comparative Examples, precursors A-1 to A-10 synthesized in the above Synthesis Examples 1 to 10 were used. Table 1 shows the "acid anhydride 1," "acid anhydride 2," "side chain component 1," "side chain component 2," "diamine," "chlorinating agent," and "ion exchange resin" used in the synthesis of precursors A-1 to A-10. Table 1 also shows the "Mn" and "Mw" of the synthesized precursors A-1 to A-10.

[0422] The amount of chloride ions in the precursor was measured as the amount of residual chlorine element as follows.

[0423] [Quantitative determination of residual chlorine content in resin (precursor) by combustion ion chromatography] 50 mg of the sample (precursor) was placed on a sample board, and after measuring the weight, measurements were carried out by combustion ion chromatography under the following conditions. Sample combustion temperature: 900℃ (inlet) / 1000℃ (outlet) Absorption solution conditions: Approximately 0.01% H2O2 aq. + 2 ppm KH2PO4 aq. (internal standard) Absorbed liquid volume: 5mL Column: Dionex IonPac AS22 Eluent: 4.5mmol / L Na2CO3+ 1.4mmol / L NaHCO3 Flow rate: 1.2mL / min Column temperature: 35℃ Amount of absorbent solution injected: 100uL Concentration correction: Volume check The measurement was carried out twice, and the amount of chlorine element in each sample was quantified, and the average value was used.

[0424] The amount of chloride ions in the precursor is shown in Table 1.

[0425] The content of elemental sulfur in the precursor was measured as follows.

[0426] [Quantitative determination of sulfur element in resin (precursor) by combustion ion chromatography] 50 mg of the sample (precursor) was placed on a sample board, and after measuring the weight, measurements were carried out by combustion ion chromatography under the following conditions. Sample combustion temperature: 900℃ (inlet) / 1000℃ (outlet) Absorption solution conditions: Approximately 0.01% H2O2 aq. + 2 ppm KH2PO4 aq. (internal standard) Absorbed liquid volume: 5mL Column: Dionex IonPac AS22 Eluent: 4.5mmol / L Na2CO3+ 1.4mmol / L NaHCO3 Flow rate: 1.2mL / min Column temperature: 35℃ Amount of absorbent solution injected: 100uL Concentration correction: Volume check The measurement was carried out twice, and the amount of elemental sulfur in each sample was quantified, and the average value was used.

[0427] The amount of sulfur element in the precursor is shown in Table 1.

[0428] [Table 1]

[0429] The ion exchange resins in Table 1 are as follows: R-1: MB-1 (amphoteric ion exchange resin (Organo Corporation)) R-2: AMBERJET TM UP6040 (anion exchange resin (manufactured by Organo Corporation)) R-3: Amberist TM B20-HG·DRY (anion exchange resin (manufactured by Organo Corporation)) R-4: Amberlite IRA96SB (anion exchange resin (manufactured by Organo Corporation))

[0430] <Examples and Comparative Examples> The components (precursor and other components) shown in Table 2 below were mixed to obtain each resin composition. The other components were used in the amounts (% by mass) shown in Table 2 below. Table 2 below lists the resin content (% by mass) and the content (% by mass) of other components relative to the total solid content of each resin composition. In Table 2, the content (% by mass) of each component relative to the total solid content of each resin composition is listed as "%." The solid content of each resin composition is 35% by mass. The "ratio" of the solvent is the mass ratio (mass %) of each solvent to the total amount of solvent. The resulting resin composition was filtered under pressure using a polytetrafluoroethylene filter having a pore width of 20.0 μm. In the table, a "-" in the "Precursor" column indicates that the corresponding compound was not used in the synthesis of the resin. Also, a "-" in the column for each component other than the precursor indicates that the resin composition does not contain the corresponding component.

[0431] [Table 2]

[0432] Details of each component listed in the above table are as follows:

[0433] <Polymerizable compound> The polymerizable compounds used are shown below.

[0434] [ka]

[0435] <Polymerization initiator> The polymerization initiators used are shown below. C-1: IRGACURE OXE 01 (BASF) C-2: IRGACURE OXE 02 (BASF)

[0436] <Base generator> The base generators used are shown below.

[0437] [ka]

[0438] <Migration inhibitor> The migration inhibitors used are shown below.

[0439] [ka]

[0440] <Metal adhesion improver> The metal adhesion improvers used are shown below.

[0441] [ka]

[0442] <Polymerization inhibitor> The polymerization inhibitors used are shown below.

[0443] [ka]

[0444] <Solvent> As the solvent, for example, the following solvents can be used, and in the examples, the solvents selected from the following solvents were used. DMSO: dimethyl sulfoxide GBL: gamma-butyrolactone NMP: N-methylpyrrolidone

[0445] <Evaluation> The evaluation was carried out as follows, and the results are shown in Table 2 above.

[0446] [Method for producing a reliability evaluation board] The resin compositions and comparative compositions prepared in each example and comparative example were each applied by spin coating to the surface of a TEG (test elementary group) substrate SIPOS-TEG SI06 manufactured by Waltz Corporation, and dried at 100°C for 300 seconds. The film thickness was adjusted so that the resulting cured product would have a thickness of 10 μm. Then, a photomask for TEG substrate evaluation was placed on the substrate, and 400 mJ / cm 2After exposure, the substrate was developed using cyclopentanone and rinsed with PGMEA, and then heated to 230°C for 180 minutes at a heating rate of 5°C / min in a N2 atmosphere in a Koyo Thermo Systems clean oven CLH-2 to prepare a reliability evaluation substrate.

[0447] [PCT Exam] In each example and comparative example, a PCT test was performed using the reliability evaluation board described above, using a HAST device PC-422R8D manufactured by Hirayama Manufacturing Co., Ltd., under conditions of 121°C, 100% RH (relative humidity), and 250 hours. After the test, the board was observed with an optical microscope, and visually inspected for the presence of foreign matter or wiring corrosion.

[0448] [Measurement of breaking elongation] <Evaluation> The resin compositions and comparative compositions prepared in each of the Examples and Comparative Examples were each applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer on which the resin composition layer was coated was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer with a uniform thickness of 20 µm on the silicon wafer. A photomask for evaluating strip samples was placed on the resin composition layer on the silicon wafer, and a photomask of 400 mJ / cm was applied. 2 The resulting resin composition layer on the silicon wafer was developed using cyclopentanone and rinsed with PGMEA. It was then heated to 230°C for 180 minutes at a heating rate of 5°C / min in a N2 atmosphere in a Koyo Thermo Systems CLH-2 clean oven to obtain a cured film. The cured product was immersed in a 3 mass % hydrofluoric acid solution, and the cured product was peeled off from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare test pieces with a width of 3 mm and a length of 30 mm. The resulting test pieces were measured for longitudinal elongation at break in accordance with JIS-K6251 using a tensile tester (Tensilon) at a crosshead speed of 300 mm / min under an environment of 25°C and 65% RH (relative humidity). Each evaluation was performed five times, and the arithmetic mean value of the elongation at break (elongation at break) was used as an index value. The index values ​​were evaluated according to the following evaluation criteria, and the evaluation results are shown in the "elongation at break" column in the table. It can be said that the larger the index value, the better the film strength (elongation at break) of the obtained cured film. (Evaluation criteria) A: The above index value was 70% or higher. B: The above index value was 60% or more and less than 70%. C: The above index value was 50% or more and less than 60%. D: The above index value was less than 50%.

[0449] From the above results, it was found that the examples of the present invention can provide a resin composition capable of forming a film having excellent breaking elongation and excellent PCT properties. Furthermore, it has been found that the examples of the present invention can provide a method for producing a polyamide precursor or a polyamideimide precursor that can be suitably applied to the above-mentioned resin composition.

Claims

1. a step of reacting a dicarboxylic acid compound represented by the following general formula (1) or (2) with a chlorinating agent not containing a sulfur element to obtain a dicarboxylic acid chloride represented by the following general formula (1)' or (2'): reacting the dicarboxylic acid chloride with a diamine; treating with an ion exchange resin; A method for producing a polyimide precursor or a polyamideimide precursor, comprising the steps of: 【Chemical 1】 (In general formulas (1) and (2), X １ represents a tetravalent organic group, Y １ represents a trivalent organic group, Z １ ~Z ３ are each independently an oxygen atom or —NR ｚ represents -, and R １ ~R ３ each independently represents a hydrogen atom or a monovalent organic group; R １ and R ２ At least one of R is a group having an ethylenically unsaturated bond, ３ is a group having an ethylenically unsaturated bond. ｚ represents a hydrogen atom or a monovalent organic group, R ｚ is R １ , R ２ , or R ３ may be bonded to form a ring.) 【Chemistry 2】 (In the general formulas (1)' and (2)', X １ , Y １ , Z １ , Z ２ , Z ３ , R １ , R ２ , and R ３ represents X in general formulas (1) and (2). １ , Y １ , Z １ , Z ２ , Z ３ , R １ , R ２ , and R ３ (Similar to the above.)

2. 2. The method for producing a polyimide precursor or a polyamideimide precursor according to claim 1, wherein the sulfur-free chlorinating agent is at least one selected from the group consisting of oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, and phenylphosphonic dichloride.

3. R in the general formulae (1), (1)′, (2), and (2′) １ , R ２ , and R ３ and each independently represent a group represented by the following formula (3): 【Chemistry 3】 (In formula (3), A represents a (q+1)-valent organic group, and R ４ ~R ６ each independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, q represents an integer of 1 to 4, and * represents a bonding site to another structure.

4. -Z in the general formula (1) and (1)′ １ -R １ and -Z ２ -R ２ 2. The method for producing a polyimide precursor or a polyamideimide precursor according to claim 1, wherein one of the groups represented by the formula (1) is a group having an ethylenically unsaturated bond, and the other is a group represented by the formula (4): 【Chemistry 4】 (In formula (4), Z ４ and Z ５ Each independently represents a monovalent organic group, and * represents a bonding site to another structure. ４ and Z ５ may be bonded to form a ring.)

5. The method for producing a polyimide precursor or a polyamideimide precursor according to claim 4, wherein the group represented by formula (4) is a group represented by the following formula (5): 【Chemistry 5】 In formula (5), Cy represents a nitrogen-containing heterocycle or aromatic ring, and * represents a bonding site to another structure.

6. 2. The method for producing a polyimide precursor or a polyamideimide precursor according to claim 1, wherein the content of elemental sulfur contained in the polyimide precursor or the polyamideimide precursor is less than 0.5% by mass based on the total mass of the polyimide precursor or the polyamideimide precursor.

7. 2. The method for producing a polyimide precursor or a polyamideimide precursor according to claim 1, wherein the weight average molecular weight of the polyimide precursor or the polyamideimide precursor is 5,000 to 50,000.

8. (1) A polyimide precursor or a polyamideimide precursor produced by the method according to any one of claims 1 to 7. (2) Solvent (3) Polymerization initiator A method for producing a curable resin composition, comprising mixing

9. (1) A polyimide precursor or a polyamideimide precursor produced by the method according to any one of claims 1 to 7. (2) Solvent (3) Polymerization initiator A curable resin composition comprising:

10. A polyimide precursor or a polyamideimide precursor having a repeating unit represented by the following general formula (11) or (12): the content of elemental sulfur contained in the polyimide precursor or polyamideimide precursor is less than 5 ppm based on the total mass of the polyimide precursor or polyamideimide precursor; the content of chloride ions contained in the polyimide precursor or polyamideimide precursor is less than 3 ppm based on the total mass of the polyimide precursor or polyamideimide precursor; Polyimide precursor or polyamideimide precursor. 【Chemistry 6】 In general formula (11) and general formula (12), R １１５ represents a tetravalent organic group, R １１７ represents a trivalent organic group, A １ ~A ３ are each independently an oxygen atom or —NR ｚ１ represents -, and R １１１ , R １１６ each independently represents a divalent organic group; R １１３ , R １１４ , and R １１８ each independently represents a hydrogen atom or a monovalent organic group; R ｚ１ represents a hydrogen atom or a monovalent organic group. R １１３ and R １１４ At least one of R is a group having an ethylenically unsaturated bond, １１８ is a group having an ethylenically unsaturated bond. ｚ１ represents a hydrogen atom or a monovalent organic group, R ｚ１ is R １１３ , R １１４ , or R １１８ may be bonded to form a ring.)

Images