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

Abstract

Provided are a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device, the resin composition containing: at least one resin selected from among polyimides and precursors thereof, the resin having a ring structure having 5 or more ring elements in a side chain; a polymerization initiator; and a polymerizable compound.

Description

Technical Field

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

[0002] Nowadays, in various fields, technologies for producing resin materials from resin compositions containing resins are being utilized.

[0003] For example, polyimide is used in various applications due to its excellent heat resistance and insulation properties. The above-mentioned applications are not particularly limited. If a semiconductor device for mounting is used as an example, it can be used as an insulating film, a sealing material, or a protective film. In addition, it can also be used as a base film, a cover film, etc. of a flexible substrate.

[0004] For example, in the above-mentioned applications, polyimide is used in the form of a resin composition containing polyimide or a polyimide precursor.

[0005] Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, subjected to exposure, development, heating, etc., to form a cured product on the substrate.

[0006] The polyimide precursor is cyclized by, for example, heating, and becomes a polyimide in a cured product.

[0007] The resin composition can be applied by a known coating method, etc., and therefore can be said to have excellent adaptability in manufacturing, for example, the applied resin composition has a high degree of freedom in designing the shape, size, application position, etc. during application. In addition to the high performance of polyimide, etc., this excellent adaptability in manufacturing has led to increasing expectations for the development of industrial applications of the resin composition.

[0008] For example, Patent Document 1 describes a curable resin composition comprising: at least one resin having a polyalkyleneoxy group and a polymerizable group and selected from polyimide and a polyimide precursor; a polymerization initiator; a polymerizable compound; and a solvent.

[0009] Patent Document 2 describes a curable resin composition containing a resin having a repeating unit as a specific structure and a solvent.

[0010] Previous technical literature

[0011] Patent Literature

[0012] Patent Document 1: International Publication No. 2020 / 255859

[0013] Patent Document 2: International Publication No. 2021 / 039782 Summary of the invention

[0014] Technical issues to be solved by the invention

[0015] A cured product containing polyimide is required to have a lower dielectric constant from the viewpoint of suppressing transmission loss and the like.

[0016] The object of the present invention is to provide a resin composition that can obtain a cured product with a low dielectric constant, a cured product formed by curing the above resin composition, a laminate containing the above cured product, a method for manufacturing the above cured product, a method for manufacturing the above laminate, a method for manufacturing a semiconductor device including the method for manufacturing the above cured product, and a semiconductor device containing the above cured product.

[0017] Means for solving technical problems

[0018] Hereinafter, examples of representative embodiments of the present invention will be described.

[0019] <1> A resin composition comprising:

[0020] At least one resin selected from polyimide and its precursor, wherein the resin has a ring structure with 5 or more ring members on the side chain;

[0021] a polymerization initiator; and

[0022] Polymeric compounds.

[0023] <2> A resin composition comprising:

[0024] At least one resin selected from polyimide and its precursor, the resin having a structure represented by the following formula (A-1);

[0025] a polymerization initiator; and

[0026] Polymeric compounds.

[0027] [Chemical formula 1]

[0028]

[0029] In formula (A-1), L A1 represents a single bond or an m+1-valent linking group, Cy each independently represents a ring structure having 5 or more ring members and optionally having a substituent, m represents an integer of 1 or more, and * represents a bonding site to an atom contained in the main chain of the resin.

[0030] <3> according to <1> or <2> The resin composition, wherein

[0031] The above resin further has a polymerizable group.

[0032] <4> according to <3> The resin composition, wherein

[0033] The polymerizable group value of the above resin is 0.2 to 5 mmol / g.

[0034] <5> according to <1> to <4> The resin composition described in any one of the preceding claims, wherein

[0035] When a film-like cured product having a film thickness of 10 μm is formed using the resin composition, the transmittance of the cured product at a wavelength of 365 nm is 15% or more.

[0036] <6> according to <1> to <5> The resin composition described in any one of the preceding claims, wherein

[0037] The above resin contains a repeating unit represented by the following formula (1-1).

[0038] [Chemical formula 2]

[0039]

[0040] In formula (1-1), X 1 represents an organic group having 4 or more carbon atoms, Y 1 represents an organic group with 4 or more carbon atoms, R 1 Each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or greater.

[0041] [Chemical formula 3]

[0042]

[0043] In formula (R-1), L 1 represents a2+1 valent connecting group, Z 1 represents an aromatic group or a cyclic aliphatic group, A 1 represents a polymerizable group, a1 represents 0 or more, and Z 1 a2 represents an integer greater than or equal to 1, and * represents the integer corresponding to X in formula (1-1). 1 or Y 1 bonding part.

[0044] <7> according to <6> The resin composition, wherein

[0045] A in the formula (R-1) contained in the formula (1-1) 1 At least one of them is a vinyl group, a (meth)acryloyloxy group, a vinyl ether group, an allyl group, an epoxy group, or a group containing these.

[0046] <8> according to <7> The resin composition, wherein

[0047] A in formula (R-1) in formula (1-1) 1 At least one of them is a vinyl group or a vinyl ether group.

[0048] <9> according to <6> to <8> The resin composition described in any one of the preceding claims, wherein

[0049] X in formula (1-1) 1 and Y 1 Each includes a structure in which two or more hydrogen atoms are removed from a structure represented by any of the following formulae (V-1) to (V-4).

[0050] [Chemical formula 4]

[0051]

[0052] In formula (V-2), R X1 are each independently a hydrogen atom, an alkyl group or a halogenated alkyl group.

[0053] In formula (V-3), R X2 and R X3 Each independently represents a hydrogen atom or a substituent, R X2 With R X3 They may be bonded to form a ring structure.

[0054] <10> according to <6> to <9> The resin composition described in any one of the preceding claims, wherein

[0055] In the above formula (R-1), L 1 It is a group represented by the following formula (L-1).

[0056] [Chemical formula 5]

[0057]

[0058] In formula (L-1), L x represents an a2+1 valent linking group, a2 represents an integer greater than 1, and * represents the same as X in formula (1-1) 1 or Y 1 The bonding site of Z in formula (R-1) is represented by #. 1 bonding part.

[0059] <11> A resin composition comprising:

[0060] At least one resin selected from polyimide and its precursor, the resin containing at least one of the repeating units represented by the following formula (2-1) and the following formula (3-1);

[0061] a polymerization initiator; and

[0062] Polymeric compounds.

[0063] [Chemical formula 6]

[0064]

[0065] In formula (2-1), X 2 represents an organic group having 4 or more carbon atoms, Y 2 represents an organic group having 4 or more carbon atoms, Y 2 Does not contain ester bonds, R 2 Each independently represents a group represented by the following formula (R-2), and n represents an integer of 1 or greater.

[0066] In formula (3-1), X 3 represents an organic group having 4 or more carbon atoms, Y 3 represents an organic group having 4 or more carbon atoms, Y 3 Contains no ester bond, A 3 and A 4 Each independently represents an oxygen atom or -NR N -, R 3 and R 4 Each independently represents a hydrogen atom or a monovalent organic group, R 2 Each independently represents a group represented by the following formula (R-2), and n represents an integer of 1 or greater.

[0067] [Chemical formula 7]

[0068]

[0069] In formula (R-2), L 2 represents a b2+1 valent connecting group, Z 2 Indicates a b1+1 valent organic group, A 2 represents a polymerizable group, b1 represents 1 or more, and Z 2 b2 represents an integer greater than or equal to 1, and * represents the same integer as Y of formula (2-1). 2 Or Y in formula (3-1) 3 The number of ester bonds contained in the formula (R-2) is 1 or 0.

[0070] <12> according to <11> The resin composition, wherein

[0071] The above resin is a resin having a ring structure having 5 or more ring members in a side chain.

[0072] <13> according to <11> or <12> The resin composition, wherein

[0073] The polymerizable group value of the above resin is 0.2 to 5 mmol / g.

[0074] <14> according to <11> to <13> The resin composition described in any one of the preceding claims, wherein

[0075] When a film-like cured product having a film thickness of 10 μm is formed using the resin composition, the transmittance of the cured product at a wavelength of 365 nm is 15% or more.

[0076] <15> according to <11> to <14> The resin composition described in any one of the preceding claims, wherein

[0077] A in the formula (R-2) contained in the formula (2-1) 2 At least one of them is a vinyl group, a (meth)acryloyloxy group, a vinyl ether group, an allyl group, an epoxy group or a group containing these, and A in the formula (R-2) contained in the formula (3-1) 2 At least one of them is a vinyl group, a (meth)acryloyloxy group, a vinyl ether group, an allyl group, an epoxy group or a group containing these, and X in formula (2-1) 2 and Y 2 Each of the structures represented by any of the following formulae (V-1) to (V-4) contains a structure obtained by removing two or more hydrogen atoms, and X in formula (3-1) 3 and Y 3 Each includes a structure in which two or more hydrogen atoms are removed from a structure represented by any of the following formulae (V-1) to (V-4).

[0078] [Chemical formula 8]

[0079]

[0080] In formula (V-2), R X1 are each independently a hydrogen atom, an alkyl group or a halogenated alkyl group.

[0081] In formula (V-3), R X2 and R X3 Each independently represents a hydrogen atom or a substituent, R X2 With R X3 They may be bonded to form a ring structure.

[0082] <16> According to <11> to <15> The resin composition described in any one of the preceding claims, wherein

[0083] In the above formula (R-2), L 2 is a group represented by the following formula (L-2), wherein A in the formula (R-2) 2 It is a vinyl group or a vinyl ether group.

[0084] [Chemical formula 9]

[0085]

[0086] In formula (L-2), L X represents a b2+1 valent linking group, b2 represents an integer greater than 1, and * represents the same as X in formula (2-1) 2 or Y 2 Or X in formula (3-1) 3 or Y 3 The bonding site of Z in formula (R-2) is represented by #. 2 bonding part.

[0087] <17> According to <1> to <16> The resin composition described in any one of the preceding claims, wherein

[0088] The above-mentioned polymerization initiator is a photoacid generator.

[0089] <18> According to <1> to <17> The resin composition described in any one of the above contains two or more polymerization initiators as the polymerization initiator.

[0090] <19> according to <1> to <18> The resin composition described in any one of the above contains a photopolymerization initiator and a thermal polymerization initiator or a photoradical polymerization initiator and a photoacid generator as the polymerization initiator.

[0091] <20> according to <1> to <19> The resin composition described above further comprises an azole compound and a silane coupling agent.

[0092] <21> according to <1> to <20> The resin composition described in any one of the above is used for forming an interlayer insulating film for a redistribution layer.

[0093] <22> A solidified material, which is solidified <1> to <21> The resin composition described in any one of the above.

[0094] <23> A laminate comprising two or more layers of <22> The layer composed of the cured product includes a metal layer between any of the layers composed of the cured product.

[0095] <24> A method for producing a solidified product, comprising: <1> to <21> A film forming step of applying any one of the resin compositions to a substrate to form a film.

[0096] <25> according to <24> The method for producing a cured product comprises an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern.

[0097] <26> according to <24> or <25> The method for producing the cured product comprises a heating step of heating the film at 50 to 450°C.

[0098] <27> A method for manufacturing a laminate, comprising: <24> to <26> The method for producing a cured product according to any one of the above.

[0099] <28> A method for manufacturing a semiconductor device, comprising: <24> to <26> The method for producing a cured product according to any one of the above.

[0100] <29> A semiconductor device comprising <22> The solidified material.

[0101] Effects of the Invention

[0102] According to the present invention, there can be provided a resin composition capable of obtaining a cured product having a low dielectric constant, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product. DETAILED DESCRIPTION

[0103] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0104] In the present specification, a numerical range expressed using the symbol “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0105] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process can be achieved.

[0106] In the marking of groups (atomic groups) in this specification, the marking not marked with substituted and unsubstituted includes groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0107] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include active light or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, and electron beams.

[0108] In this specification, “(meth)acrylate” means both or either “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either “acrylic acid” and “methacrylic acid”, and “(meth)acryloyl” means both or either “acryloyl” and “methacryloyl”.

[0109] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0110] In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In addition, in this specification, the solid content concentration is the mass percentage of other components excluding the solvent relative to the total mass of the composition.

[0111] In this specification, as long as there is no special instructions, weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) method, defined as polystyrene conversion value. In this specification, for example, using HLC-8220GPC (TOSOH CORPORATION system), protective column HZ-L, TSKgel Super HZM-M, TSKgel SuperHZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (more than TOSOH CORPORATION system) are connected in series and used as column, thus weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained. As long as there is no special instructions, these molecular weights are measured using THF (tetrahydrofuran) as eluent. However, in the case of low solubility, in the case where THF is not suitable as eluent, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, a UV ray (ultraviolet ray) detector with a wavelength of 254 nm was used for detection in GPC measurement.

[0112] In this specification, when the positional relationship of each layer constituting the laminate is recorded as "up" or "down", as long as there are other layers on the upper side or lower side of the layer that becomes the benchmark in the multilayer concerned. That is, a third layer or element can be further sandwiched between the layer that becomes the benchmark and the above-mentioned other layers, and the layer that becomes the benchmark does not need to contact the above-mentioned other layers. Unless otherwise specified, the direction of the substrate stacking layer is referred to as "up", or when there is a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the setting of this up and down direction is for the convenience of explaining this specification, and in actual mode, the "up" direction in this specification is also likely to be different from the vertical upward direction.

[0113] In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to the component as each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component.

[0114] In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0115] In the present specification, a combination of preferred embodiments is a more preferred embodiment.

[0116] (Resin composition)

[0117] The resin composition involved in the first aspect of the present invention (hereinafter also simply referred to as "first resin composition") contains: at least one resin selected from polyimide and its precursor, wherein the resin has a ring structure with 5 or more ring members in the side chain; a polymerization initiator; and a polymerizable compound.

[0118] The resin composition according to the second aspect of the present invention (hereinafter also simply referred to as “second resin composition”) contains: at least one resin selected from polyimide and its precursor, the resin containing a structure represented by formula (A-1); a polymerization initiator; and a polymerizable compound.

[0119] The resin composition involved in the third embodiment of the present invention (hereinafter also referred to as the "third resin composition") contains: at least one resin selected from polyimide and its precursor, wherein the resin contains at least one of the repeating units represented by formula (2-1) and formula (3-1); a polymerization initiator; and a polymerizable compound.

[0120] Hereinafter, the first resin composition, the second resin composition, and the third resin composition are also simply referred to as “resin composition”.

[0121] Hereinafter, the resin which is at least one resin selected from polyimide and its precursor contained in the first resin composition and has a ring structure having 5 or more ring members in a side chain is also referred to as a “first specific resin”.

[0122] Hereinafter, the resin which is at least one resin selected from polyimide and a precursor thereof and which is contained in the second resin composition and has a structure represented by formula (A-1) is also referred to as a “second specific resin”.

[0123] Hereinafter, the at least one resin selected from polyimide and its precursor contained in the third resin composition and containing at least one of the repeating units represented by formula (2-1) and formula (3-1) is also referred to as a "third specific resin".

[0124] Hereinafter, when simply described as "specific resin", it means all of the first specific resin, the second specific resin, and the third specific resin.

[0125] The resin composition of the present invention is preferably used to form a photosensitive film (subject to exposure and development), and is preferably used to form a film (subject to exposure and development using a developer containing an organic solvent).

[0126] The resin composition of the present invention can be used to form, for example, an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.

[0127] In particular, it is also one of the preferred aspects of the present invention that the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer.

[0128] Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative tone development.

[0129] In the present invention, among exposure and development, negative-tone development refers to development in which non-exposed areas are removed by development, and positive-tone development refers to development in which exposed areas are removed by development.

[0130] As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product to be described later, and the developer and the development method described in the development step can be used.

[0131] According to the resin composition of the present invention, a cured product having a low dielectric constant can be obtained.

[0132] The mechanism by which the above effects are obtained is not clear, but is presumed as follows.

[0133] The resin (first specific resin) contained in the resin composition according to the first embodiment of the present invention has a ring structure having 5 or more ring members in the side chain. It is believed that such a ring structure has a low polarizability, so that the ratio of polar groups contained in the resin can be reduced, and the dielectric constant of the obtained cured product can be reduced.

[0134] The resin (second specific resin) contained in the resin composition according to the second embodiment of the present invention contains a ring structure having 5 or more ring members in the structure represented by formula (A-1). It is believed that such a ring structure has a low polarizability, so that the ratio of polar groups contained in the resin can be reduced, and the dielectric constant of the obtained cured product can be reduced.

[0135] In the resin according to the third aspect of the present invention, R 2 The number of ester bonds contained in is 0 or 1. It is considered that by limiting the number of such structures with high polarizability, the dielectric constant of the obtained cured product is reduced.

[0136] However, Patent Documents 1 and 2 do not describe a resin composition containing a specific resin.

[0137] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0138] <Specific resin>

[0139] The first resin composition contains at least one resin selected from polyimide and a precursor thereof, and is a resin (first specific resin) having a ring structure having 5 or more ring members in a side chain.

[0140] In the present invention, the main chain of a resin refers to the longest bond chain in the resin molecule. When the main chain contains a ring structure, the atoms contained in the ring structure as ring members are the atoms contained in the main chain.

[0141] In the present invention, the side chain of the resin refers to a molecular chain bonded to the main chain, and the molecular chain may or may not have a repeating unit. That is, the molecular chain may or may not contain a repeating structure. In addition, the molecular chain is a molecular chain composed of more than 6 atoms, preferably a molecular chain composed of more than 10 atoms, and more preferably a molecular chain composed of more than 15 atoms. The upper limit of the number of atoms contained in the molecular chain is not particularly limited, for example, preferably less than 1,000, more preferably less than 500.

[0142] The side chain in the first specific resin is preferably bonded to a carbon atom contained in the main chain, and when the side chain is represented by R, the side chain R is preferably bonded to the carbon atom C of the main chain in the form of CR. That is, the bond to the main chain in one side chain is preferably only one.

[0143] The ring structure having 5 or more ring members in the first specific resin is preferably a ring structure having 5 to 20 ring members, and more preferably a ring structure having 5 to 12 ring members.

[0144] The ring structure having 5 or more ring members in the first specific resin may be an aromatic ring or an aliphatic ring, and is preferably an aromatic ring or an aliphatic hydrocarbon ring.

[0145] The aromatic ring may be any of an aromatic hydrocarbon ring and a heteroaromatic ring, and is preferably a heteroaromatic ring containing an aromatic hydrocarbon ring or a nitrogen atom as a ring member.

[0146] The aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and still more preferably a benzene ring.

[0147] Examples of the heteroaromatic ring include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, a pyridine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an indazole ring, a benzimidazole ring, and a purine ring.

[0148] Examples of the aliphatic ring include an aliphatic hydrocarbon ring having 5 to 20 carbon atoms, a pyrrolidine ring, a pyrroline ring, a pyrazolidine ring, an imidazole ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a piperazine ring, a tetrahydropyran ring, a dioxane ring, and a morpholine ring.

[0149] Among these, as the ring structure having 5 or more ring members, a benzene ring, a cyclohexane ring, or an adamantane ring is preferred.

[0150] The ring structure having 5 or more ring members may substitute a hydrogen atom. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, and a polymerizable group described below.

[0151] The content of the ring structure having 5 or more ring members in the first specific resin is preferably 0.01 to 5.0 mmol / g, more preferably 0.1 to 4.0 mmol / g, and even more preferably 0.5 to 2.5 mmol / g based on 1 g of the first specific resin.

[0152] The second resin composition contains at least one resin selected from polyimide and a precursor thereof, and contains a resin (second specific resin) having a structure represented by the following formula (A-1).

[0153] [Chemical formula 10]

[0154]

[0155] In formula (A-1), L A1 represents a single bond or an m+1-valent linking group, Cy each independently represents a ring structure having 5 or more ring members and optionally having a substituent, m represents an integer of 1 or more, and * represents a bonding site to an atom contained in the main chain of the resin.

[0156] In formula (A-1), L A1 It is preferably an m+1 valent linking group. A1 The preferred embodiment is the same as L in the formula (R-1) described later. 1 The preferred method is the same.

[0157] In formula (A-1), a preferred embodiment of Cy is the same as a preferred embodiment of the ring structure having 5 or more ring members in the first specific resin.

[0158] Furthermore, Cy is also preferably directly bonded to a polymerizable group described below. In the present invention, a certain structure A is directly bonded to another structure B means that the structure A and the structure B are bonded without a linking group.

[0159] In formula (A-1), * represents a bonding site to an atom contained in the main chain of the resin, preferably a bonding site to a carbon atom contained in the main chain. The carbon atom is preferably a tertiary carbon atom or a quaternary carbon atom.

[0160] In the structure represented by formula (A-1), it is preferably not included in the main chain.

[0161] Furthermore, it is also a preferred embodiment of the present invention that the structure represented by formula (A-1) is a structure represented by formula (R-1) described later.

[0162] The content of the structure represented by the formula (A-1) in the second specific resin is preferably 0.01 to 5.0 mmol / g, more preferably 0.1 to 4.0 mmol / g, and further preferably 0.5 to 2.5 mmol / g based on 1 g of the second specific resin.

[0163] The first specific resin and the second specific resin preferably have a polymerizable group.

[0164] The polymerizable group may be a cationically polymerizable group, and is preferably a radically polymerizable group.

[0165] Examples of the polymerizable group include an epoxy group, an oxetanyl group, an alkoxymethyl group, an acyloxymethyl group, a methylol group, a blocked isocyanate group, and a group containing an ethylenically unsaturated bond. An ethylenically unsaturated bond-containing group is preferred.

[0166] The group containing an ethylenically unsaturated bond is preferably a radical polymerizable group.

[0167] Furthermore, as the group containing an ethylenically unsaturated bond, vinyl, vinyl ether, allyl, isoallyl, 2-methylallyl, (meth) acrylamide, (meth) acryloxy, etc. can be listed, and vinyl or vinyl ether is preferred in terms of low polarity and lowering the dielectric constant of the obtained cured product. Among them, the above-mentioned vinyl is also preferably directly bonded to the ring structure with the above-mentioned ring member number of 5 or more. Specifically, the above-mentioned aromatic ring structure with the above-mentioned ring member number of 5 or more can be listed, and it is preferred that the above-mentioned aromatic ring structure is directly bonded to the above-mentioned vinyl.

[0168] The polymerizable group value in the specific resin (the total molar amount of the polymerizable groups per 1 g of the specific resin) is preferably 0.1 to 10 mmol / g, and more preferably 0.2 to 5 mmol / g.

[0169] The first specific resin and the second specific resin contain repeating units preferably represented by formula (1-1):

[0170] [Chemical formula 11]

[0171]

[0172] In formula (1-1), X 1 represents an organic group having 4 or more carbon atoms, Y 1 represents an organic group with 4 or more carbon atoms, R 1 Each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or greater.

[0173] [Chemical formula 12]

[0174]

[0175] In formula (R-1), L 1 represents a2+1 valent connecting group, Z 1 represents an aromatic group or a cyclic aliphatic group, A 1 represents a polymerizable group, a1 represents 0 or more, and Z 1 a2 represents an integer greater than or equal to 1, and * represents the integer corresponding to X in formula (1-1). 1 or Y 1 bonding part.

[0176] -R 1 -

[0177] R 1 Each independently represents the structure represented by formula (R-1).

[0178] In formula (R-1), L 1 It represents a2+1 valent connecting group.

[0179] L 1 Preferred is a group represented by the following formula (L-1).

[0180] [Chemical formula 13]

[0181]

[0182] In formula (L-1), L x a2 represents a 1-valent linking group, a2 represents an integer greater than 1, and * represents the same as X in formula (1-1). 1 or Y 1 The bonding site of Z in formula (R-1) is represented by #. 1 bonding part.

[0183] Lx An alkylene group is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, an alkylene group having 1 to 4 carbon atoms is further preferred, and a methylene group is particularly preferred.

[0184] Preferred aspects of a2 in formula (L-1) are the same as preferred aspects of a2 in formula (R-1).

[0185] -Z 1 -

[0186] Z in formula (R-1) 1 represents an aromatic group or a cyclic aliphatic group. Preferred embodiments of these groups are the same as preferred embodiments of the ring structure having 5 or more ring members in the first specific resin.

[0187] -A 1 -

[0188] A in formula (R-1) 1 represents a polymerizable group, and preferred aspects of the polymerizable group are the same as preferred aspects of the polymerizable group in the first specific resin and the second specific resin described above.

[0189] Among them, A in formula (R-1) contained in formula (1-1) 1 At least one of them is preferably a vinyl group, a (meth)acryloyloxy group, a vinyl ether group, an allyl group, an epoxy group or a group containing these, and more preferably a vinyl group or a vinyl ether group.

[0190] -a1, a2-

[0191] In formula (R-1), a1 is preferably an integer of 0 to 2, and more preferably 0 or 1. Furthermore, an embodiment in which a1 is 1 or 2 is also one of the preferred embodiments of the present invention.

[0192] In the formula (R-1), a2 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0193] Furthermore, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0194] -X 1 -

[0195] In formula (1-1), X 1 It is preferably a structure in which two or more hydrogen atoms are removed from a structure represented by any of the following formulae (V-1) to (V-4).

[0196] [Chemical formula 14]

[0197]

[0198] In formula (V-2), RX1 are each independently a hydrogen atom, an alkyl group or a halogenated alkyl group.

[0199] In formula (V-3), R X2 and R X3 Each independently represents a hydrogen atom or a substituent, R X2 With R X3 They may be bonded to form a ring structure.

[0200] In formula (V-2), R X1 Preferably, they are independently alkyl or halogenated alkyl, more preferably alkyl having 1 to 4 carbon atoms or halogenated alkyl having 1 to 4 carbon atoms, and further preferably methyl or trifluoromethyl. Halogenated alkyl refers to a group in which at least one of the hydrogen atoms of the alkyl group is substituted by a halogen atom. As the halogen atom, F or Cl is preferred, and F is more preferred.

[0201] In formula (V-3), R X2 and R X3 Preferably, they are each independently a hydrogen atom.

[0202] In R 1 With R 2 When the two are bonded to form a ring structure, R X2 With R X3 The structure formed by bonding is preferably a single bond, -O- or -CR 2 -, more preferably -0- or -CR 2 -, more preferably -0-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.

[0203] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), X 1 Preferably, it is a group represented by the following formula (V-1-1): In the following formula, * represents the same group as X in formula (1-1). 1 The bonding sites of the four carbonyl groups bonded are as follows: n1 represents an integer of 0 to 5, and is preferably an integer of 1 to 5. In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a hydroxyl group or a hydrocarbon group. In addition, when m in the above formula (1-1) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (1-1). 1 replace.

[0204] [Chemical formula 15]

[0205]

[0206] In X 1In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), it is preferably composed of X 1 The group represented by the following formula (V-2-1) or formula (V-2-2) is preferably a group represented by formula (V-2-2) in terms of reducing the amine value in the resin. In this specification, the bond crossing the edge of the ring structure refers to a bond that replaces any of the hydrogen atoms in the ring structure. In the following formula, L X1 represents a single bond or -O-, and * represents the X in formula (1-1) 1 The bonding sites of the four carbonyl groups bonded thereto. The definition and preferred embodiment of RX1 are as described above. In addition, the hydrogen atoms in these structures may be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when m in the above formula (1-1) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (1-1). 1 replace.

[0207] [Chemical formula 16]

[0208]

[0209] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), X 1 The group represented by the following formula (V-3-1) or formula (V-3-2) is preferred. In terms of lowering the dielectric constant, the group represented by formula (V-3-2) is preferred. In the following formula, * represents the same as X in formula (1-1). 1 The bonding sites of the four carbonyl groups bonded to the carbonyl groups. X2 and R X3 The definition and preferred embodiment of are as described above. Furthermore, the hydrogen atoms in these structures may be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups. Furthermore, when m in the above formula (1-1) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (1-1). 1 replace.

[0210] [Chemical formula 17]

[0211]

[0212] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), X 1 Preferably, it is a group represented by the following formula (V-4-1): In the following formula, * represents the same group as X in formula (1-1). 1The bonding sites of the four carbonyl groups bonded, and n1 represents an integer of 0 to 5. In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a hydroxyl group or a hydrocarbon group. In addition, when m in the above formula (1-1) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (1-1). 1 replace.

[0213] [Chemical formula 18]

[0214]

[0215] In addition, X 1 It can be obtained from R in the formula (4) described later. 132 The group represented by is obtained by removing m hydrogen atoms.

[0216] And, X 1 It is preferred that the structure does not contain an imide structure.

[0217] In the present invention, the imide structure is a structure represented by -C(=O)N(-*)C(=O)-. * represents a bonding site to another structure.

[0218] And, X 1 It is preferred that the structure does not contain a urethane bond, a urea bond, or an amide bond.

[0219] In the present invention, the carbamate bond is composed of *-OC(=O)-NR N -* indicates the bond, R N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site to a carbon atom. N It is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.

[0220] In the present invention, the urea bond is composed of *-NR N -C(=O)-NR N -* indicates the bond, R N R and R each independently represent a hydrogen atom or a monovalent organic group, and * each represents a bonding site to a carbon atom. N The preferred manner is as described above.

[0221] In the present invention, the amide bond is composed of *-NR N -C(=O)-* represents a bond, R N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site to a carbon atom. N The preferred manner is as described above.

[0222] In addition, X 1 It is preferred that no ester bond is contained in the structure.

[0223] In the present invention, the ester bond is a bond represented by *-OC(=O)-*.

[0224] Among these, X 1 It is preferred that the polyol contains no imide structure, no urethane bond, no urea bond, and no amide bond, and it is preferred that the polyol contains no imide structure, no urethane bond, no urea bond, no amide bond, and no ester bond.

[0225] -Y 1 -

[0226] In formula (1-1), Y 1 It preferably contains a structure in which two or more hydrogen atoms are removed from the structure represented by any of the above formulae (V-1) to (V-4).

[0227] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), Y 1 Preferably, it is a group obtained by removing n hydrogen atoms from a group represented by the following formula (V-1-2). In the following formula, * represents the same group as Y in formula (1-1). 1 The bonding site of the two nitrogen atoms bonded, n1 represents an integer of 1 to 5. n of the hydrogen atoms in the following structure are substituted by R1 in formula (1-1). The meaning of n is the same as the meaning of n in formula (1-1). In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a hydroxyl group or a hydrocarbon group.

[0228] [Chemical formula 19]

[0229]

[0230] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), Y 1 The group represented by the following formula (V-2-3) or formula (V-2-4) is preferred, and the group represented by formula (V-2-4) is preferred from the viewpoint of lowering the dielectric constant. X1 represents a single bond or -O-, and * represents the same as Y in formula (1-1) 1 The bonding site of the two nitrogen atoms bonded. X1 The preferred embodiment is as described above. The n hydrogen atoms in the following structure are represented by R in formula (1-1) 1 The meaning of n is the same as that of n in formula (1-1). In addition, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0231] [Chemical formula 20]

[0232]

[0233] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), Y 1 The group represented by the following formula (V-3-3) or formula (V-3-4) is preferred. In terms of lowering the dielectric constant, the group represented by formula (V-3-3) is preferred. 1 The bonding site of the two nitrogen atoms bonded. X2 and R X3 The preferred embodiment is as described above. The n hydrogen atoms in the following structure are represented by R in formula (1-1) 1 The meaning of n is the same as that of n in formula (1-1). In addition, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0234] [Chemical formula 21]

[0235]

[0236] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), Y 1 Preferably, it is a group represented by the following formula (V-4-2). In the following formula, * represents the same as Y in formula (1-1). 1 The bonding site of the two nitrogen atoms bonded, n1 represents an integer of 0 to 5. Furthermore, the embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. The number of hydrogen atoms n in the following structure is represented by R in formula (1-1): 1 The meaning of n is the same as that of n in formula (1-1). In addition, the hydrogen atoms in the following structure may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0237] [Chemical formula 22]

[0238]

[0239] In addition, Y 1 It can be obtained from R in the formula (4) described later. 131 The group represented by is obtained by removing n hydrogen atoms.

[0240] And, Y 1 It is preferred that the structure does not contain an imide structure.

[0241] And, Y 1It is preferred that the structure does not contain a urethane bond, a urea bond, or an amide bond.

[0242] In addition, Y 1 It is preferred that no ester bond is contained in the structure.

[0243] Among these, Y 1 It is preferred that the polyol contains no imide structure, no urethane bond, no urea bond, and no amide bond, and it is preferred that the polyol contains no imide structure, no urethane bond, no urea bond, no amide bond, and no ester bond.

[0244] Among these, X in formula (1-1) 1 and Y 1 Preferably, the structure is one in which two or more hydrogen atoms are removed from the structure represented by any of the above formulae (V-1) to (V-4).

[0245] In formula (1-1), m is preferably an integer of 0 to 2, and more preferably 0 or 1. Furthermore, an embodiment in which m is 0 is also one of the preferred embodiments of the present invention.

[0246] In formula (1-1), n ​​is preferably 1 or 2, and more preferably 2.

[0247] It is also preferred that the first specific resin and the second specific resin contain a repeating unit represented by formula (1-2).

[0248] [Chemical formula 23]

[0249]

[0250] In formula (1-2), A 1 and A 2 Each independently represents an oxygen atom or -NR z -, X 1 represents an organic group having 4 or more carbon atoms, Y 1 represents an organic group with 4 or more carbon atoms, R 1 Each independently represents a structure represented by the following formula (R-1), R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, Rz represents a hydrogen atom or a monovalent organic group, m represents an integer of 0 to 4, and n represents an integer of 1 or greater.

[0251] [Chemical formula 24]

[0252]

[0253] In formula (R-1), L 1 represents a2+1 valent connecting group, Z 1 represents an aromatic group or a cyclic aliphatic group, A 1represents a polymerizable group, a1 represents 0 or more, and Z 1 a2 represents an integer greater than or equal to 1, and * represents the integer corresponding to X in formula (1-2). 1 or Y 1 bonding part.

[0254] X in formula (1-2) 1 , Y 1 , R 1 The preferred embodiments of n and m are the same as those of X in the above formula (1-1). 1 , Y 1 , R 1 The preferred modes for , n and m are the same.

[0255] A in formula (1-2) 1 , A 2 , R 113 and R 114 The preferred embodiment is the same as A in the formula (2) described later. 1 , A 2 , R 113 and R 114 The preferred method is the same.

[0256] The first specific resin and the second specific resin may contain a repeating unit represented by formula (2).

[0257] The repeating unit corresponding to the repeating unit represented by the formula (1-2) is set not to correspond to the repeating unit represented by the formula (2).

[0258] [Chemical formula 25]

[0259]

[0260] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NR z -, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group.

[0261] A in formula (2) 1 and A 2 Each independently represents an oxygen atom or -NR z , preferably an oxygen atom.

[0262] R z represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.

[0263] R in formula (2) 111 Represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group. Preferably, it is 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. More preferably, it is a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group in the ring of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. As R in formula (2) 111 Examples of the group represented by -Ar- and -Ar-L-Ar- can be listed, and the group represented by -Ar-L-Ar- is preferred. However, Ar is independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges are as described above.

[0264] R 111 It is preferably derived from a diamine. Examples of the diamine include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. The diamine may be used alone or in combination of two or more.

[0265] Specifically, R 111 It is a diamine containing a straight or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, preferably 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 hydrocarbon group in the chain of the straight or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group of the ring member of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. As examples of the group containing an aromatic group, the following groups can be cited.

[0266] [Chemical formula 26]

[0267]

[0268] In the formula, A is a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO- or a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S- or -SO2-, further preferably -CH2-, -0-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0269] In the formula, * indicates the bonding site with other structures.

[0270] Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane;

[0271] 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;

[0272] Examples include those selected from the group consisting of m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'- or 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)hexafluoropropane, propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis( 4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)-10-hydroanthracene (4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, ethoguanamine, 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, diaminotrifluorotoluene, 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-trifluoromethyl) At least one diamine selected from the group consisting of 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine and 4,4'-diaminoquaternaryl.

[0273] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0274] Furthermore, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 can also be preferably used.

[0275] And, R 111 It may be a group containing a structure formed by removing two or more hydrogen atoms from a structure represented by any of the above formulae (V-1) to (V-4) and having no structure similar to the above R 1 The group at the bonding site.

[0276] From the viewpoint of the flexibility of the obtained organic film, R 111 Preferably, it is represented by -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted by fluorine atoms, -O-, -C0-, -S-, -SO2- 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 that may be substituted by fluorine atoms, -O-, -C0-, -S- or -SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.

[0277] And, R 111It is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any of the above formulae (V-1) to (V-4), and preferably has no structure similar to that of R 1 The group of the bonding site. 1 In addition to the bonding site of 1 The preferred embodiment of the group having a structure in which two or more hydrogen atoms are removed from the structure represented by any of the formulae (V-1) to (V-4) is the same.

[0278] Furthermore, from the perspective of i-ray transmittance, R 111 Preferred is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred.

[0279] Formula (51)

[0280] [Chemical formula 27]

[0281]

[0282] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2).

[0283] As 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).

[0284] [Chemical formula 28]

[0285]

[0286] In formula (61), R 58 and R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2).

[0287] Examples of the diamine that imparts the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

[0288] R in formula (2) 115 The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).

[0289] In formula (5) or (6), * each independently represents a bonding site with another structure.

[0290] [Chemical formula 29]

[0291]

[0292] In formula (5), R 112 It is a single bond or a divalent connecting group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO2-, further preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0293] About R 115 Specifically, the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride can be cited. 115 In the corresponding structure, the first specific resin or the second specific resin may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types of tetracarboxylic dianhydride residues.

[0294] It is preferable that tetracarboxylic dianhydride is represented by the following formula (0).

[0295] [Chemical formula 30]

[0296]

[0297] In formula (0), R 115 represents a tetravalent organic group. 115 The meaning of is the same as R in formula (2) 115 The meanings are the same, and the preferred ranges are also the same.

[0298] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane tetracarboxylic dianhydride, anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 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 alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0299] Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be cited as preferred examples.

[0300] And, R 115 It is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any of the above formulae (V-1) to (V-4), and preferably has no structure similar to that of R 1 The group of the bonding site. 1 In addition to the bonding site of 1 The preferred embodiment of the group having a structure in which two or more hydrogen atoms are removed from the structure represented by any of the formulae (V-1) to (V-4) contained therein is the same.

[0301] In formula (2), R 111 and R 115 At least one of R may have an OH group. 111 , the residues of bisaminophenol derivatives can be mentioned.

[0302] R in formula (2) 113 and R114 Each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkyleneoxy group. 113 and R 114 At least one of them preferably contains a polymerizable group, and more preferably both contain a polymerizable group. 113 and R 114 At least one of the first specific resin or the second specific resin also preferably contains more than two polymerizable groups. As a polymerizable group, it is a group that can be cross-linked by the action of heat, free radicals, etc., preferably a free radical polymerizable group. As a specific example of a polymerizable group, a group with an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetane group, a benzoxazolyl group, a blocked isocyanate group, and an amino group can be cited. As the free radical polymerizable group possessed by the first specific resin or the second specific resin, it is preferably a group with an ethylenically unsaturated bond.

[0303] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III). Preferably, the group represented by the following formula (III) is mentioned.

[0304] [Chemical formula 31]

[0305]

[0306] In formula (III), R 200 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0307] In formula (III), * represents a bonding site with other structures.

[0308] In formula (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group or a polyalkyleneoxy group.

[0309] R 201 Preferred examples include alkylene groups such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkyleneoxy groups, alkylene groups such as vinyl and propenyl, more preferably -CH2CH(OH)CH2-, cyclohexyl, and polyalkyleneoxy groups, and further preferably alkylene groups such as vinyl and propenyl or polyalkyleneoxy groups.

[0310] 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 plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.

[0311] When the polyalkyleneoxy group includes a plurality of 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, an arrangement having an alternating pattern, or the like.

[0312] The number of carbon atoms of the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0313] Furthermore, the above-mentioned alkylene group may have a substituent, and preferred substituents include an alkyl group, an aryl group, a halogen atom, and the like.

[0314] Furthermore, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.

[0315] As the polyalkyleneoxy group, from the aspects of solvent solubility and solvent resistance, preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and further preferably a polyethyleneoxy group. In the group in which a plurality of ethyleneoxy groups and a plurality of 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 an alternating pattern. The preferred form of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

[0316] In formula (2), R 113 In the case of a hydrogen atom or R 114 When it is a hydrogen atom, the first specific resin or the second specific resin may form a salt pair with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

[0317] In formula (2), R 113 and R 114 At least one of them may be a polar 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 hydroxyl group or a carboxyl group, and is preferably an acetal group, a ketal group, a silicon group, a silicon ether group, a tertiary alkyl ester group, etc., and is more preferably an acetal group or a ketal group from the perspective of exposure sensitivity.

[0318] Specific examples of the acid-decomposable group include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, trimethylsilyl ether, etc. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0319] The first specific resin and the second specific resin may contain a repeating unit represented by formula (4).

[0320] The repeating unit corresponding to the repeating unit represented by formula (1-1) is not assumed to correspond to the repeating unit represented by formula (4).

[0321] [Chemical formula 32]

[0322]

[0323] In formula (4), R 131 Represents a divalent organic group, R 132 It represents a tetravalent organic group.

[0324] R 131 The divalent organic group includes the following: 111 If the two are the same, the preferred range is also the same.

[0325] And, as R 131 , the diamine residue remaining after the amino group of the diamine is removed can be cited. As diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, R in formula (2) of the polyimide precursor can be cited. 111 Example.

[0326] From the viewpoint of more effectively suppressing the warping during calcination, R 131 A diamine residue having at least two alkylene glycol units in the main chain is more preferably a diamine residue containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule, and further preferably a diamine residue containing no aromatic ring but the above diamine.

[0327] Examples of the diamine containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (these are trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, and 1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, but are not limited to these.

[0328] R 132 The tetravalent organic group includes the following: 115 If the two are the same, the preferred range is also the same.

[0329] For example, as R 115 The four bonders of the exemplified tetravalent organic group are bonded to the four -C(=O)- moieties in the formula (4) to form a condensed ring.

[0330] R 132 Examples thereof include tetracarboxylic acid residues remaining after the anhydride groups are removed from tetracarboxylic dianhydride. Specific examples thereof include R in the formula (2) of the polyimide precursor. 115 From the perspective of the strength of the organic film, R 132 An aromatic diamine residue having 1 to 4 aromatic rings is preferred.

[0331] Also preferably in R 131 and R 132 More specifically, as R 131 As preferred examples, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) can be cited as R 132 As more preferred examples, the above-mentioned (DAA-1) to (DAA-5) can be cited.

[0332] The first specific resin and the second specific resin may contain a repeating unit represented by formula (3).

[0333] [Chemical formula 33]

[0334]

[0335] In formula (3), R 121Represents a divalent organic group, R 122 Represents a 4-valent organic group, R 123 and R 124 Each independently represents a hydrogen atom or a monovalent organic group.

[0336] In formula (3), R 123 and R 124 The meanings of are respectively the same as R in formula (2) 112 The meanings of are the same, and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.

[0337] In formula (3), R 121 represents a divalent organic group. As the divalent organic group, it is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, it is preferably a straight-chain aliphatic group. R 121 A dicarboxylic acid residue is preferred. The dicarboxylic acid residue may be used alone or in combination of two or more.

[0338] The dicarboxylic acid residue is preferably an aliphatic group-containing dicarboxylic acid residue or an aromatic group-containing dicarboxylic acid residue, and more preferably an aromatic group-containing dicarboxylic acid residue.

[0339] As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably a linear) aliphatic group is preferred, and a dicarboxylic acid composed of a linear or branched (preferably a linear) aliphatic group and two -COOH groups is more preferred. The number of carbon atoms in the linear or branched (preferably a linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.

[0340] Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetrafluorohexane. Methyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid) and dicarboxylic acid represented by the following formula, etc.

[0341] [Chemical formula 34]

[0342]

[0343] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0344] As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting only of a group having an aromatic group and two -COOH groups are more preferred.

[0345] [Chemical formula 35]

[0346]

[0347] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * independently represents a bonding site with other structures.

[0348] Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and phthalic acid.

[0349] In formula (3), R 122 The tetravalent organic group has the same meaning as R in the above formula (2). 115 The meanings are the same, and the preferred ranges are also the same.

[0350] R 122 The group derived from a bisaminophenol derivative is preferred. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4- bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bis-aminophenols can be used alone or in combination.

[0351] Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

[0352] [Chemical formula 36]

[0353]

[0354] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, * and # represent the bonding sites with other structures respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. And R 122 The structure represented by the above formula is also preferred. 122 In the case of the structure represented by the above formula, it is preferred that any two of the four * and # are the same as R in formula (3). 122 The bonding site of the nitrogen atom to which the bond is attached and the other two are R in formula (3) 122 The bonding site of the oxygen atom to which the bonding is bonded is preferably 2 * which is the same as R in formula (3) 122 The bonding site of the oxygen atom to which the bond is attached and the two # are the same as R in formula (3) 122 The bonding site of the nitrogen atom to which it is bonded, or the two * are R in formula (3) 122 The bonding site of the nitrogen atom to which it is bonded and the two # are the same as R in formula (3) 122The bonding site of the oxygen atom to which the bond is attached is more preferably 2 * which is the same as R in formula (3) 122 The bonding site of the oxygen atom to which the bond is attached and the two # are the same as R in formula (3) 122 The bonding site of the bonded nitrogen atom.

[0355] The bisaminophenol derivative is also preferably a compound represented by formula (As).

[0356] [Chemical formula 37]

[0357]

[0358] In formula (As), R1 is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond or an organic group selected from the group of the following formula (A-sc). R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, which may be the same or different. R3 is any one of a hydrogen atom, a straight-chain or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, which may be the same or different.

[0359] [Chemical formula 38]

[0360]

[0361] In the organic group selected from the group represented by formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by formula (As).

[0362] In formula (As), it is particularly preferred that R3 ortho to the phenolic hydroxyl group has a substituent because this brings the carbonyl carbon of the amide bond and the hydroxyl group closer together, thereby further improving the effect of high cyclization rate during curing at low temperatures.

[0363] In the formula (As), when R2 is an alkyl group and R3 is an alkyl group, it is preferable because high transparency to i-rays and a high cyclization rate can be maintained during curing at a low temperature.

[0364] In formula (As), R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group associated with R1 include a linear or branched alkyl group having 1 to 8 carbon atoms, among which -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred in terms of maintaining high transparency to i-rays and high cyclization rate when cured at low temperatures and obtaining a specific resin having a good balance of sufficient solubility in solvents.

[0365] As a method for producing the bisaminophenol derivative represented by formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506, and the contents of these are incorporated herein.

[0366] Specific examples of the structure of the bisaminophenol derivative represented by formula (As) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, the contents of which are incorporated herein. Specific examples of the structure of the bisaminophenol derivative represented by formula (As) are not limited to these.

[0367] From the viewpoint of being able to suppress the occurrence of warpage due to ring closure, it is preferred that the first specific resin and the second specific resin contain a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0368] [Chemical formula 39]

[0369]

[0370] In formula (SL), Z has structure a and structure b, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. Regarding the mole % of the Z part, structure a is 5 to 95 mole %, structure b is 95 to 5 mole %, and a+b is 100 mole %.

[0371] In formula (SL), preferred examples of Z include R in structure b. 5s and R 6s The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the specific resin after dehydration ring closure can be more effectively reduced, and the effect of suppressing warping and the effect of improving solvent solubility can be achieved.

[0372] When a diamine residue represented by the formula (SL) is included as another type of repeating unit, it is also preferred to further include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride as a repeating unit. Examples of such a tetracarboxylic acid residue include R in the formula (2): 115 Example.

[0373] The first specific resin and the second specific resin may contain a repeating unit represented by formula (3).

[0374] [Chemical formula 40]

[0375]

[0376] In formula (X), R 133 Represents a divalent organic group, R 134 It represents a tetravalent organic group.

[0377] In the case of having a polarity conversion group such as a polymerizable group or an acid-decomposable group, the polymerizable group or the acid-decomposable group may be located at R 133 and R 134 In at least one of them, as shown in the following formula (X-1) or formula (X-2), it may be located at the terminal of the specific resin.

[0378] Formula (X-1)

[0379] [Chemical formula 41]

[0380]

[0381] In formula (X-1), R 135 and R 136 At least one of them is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and when it is not a polarity conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups have the same meaning as that of formula (X).

[0382] Formula (X-2)

[0383] [Chemical formula 42]

[0384]

[0385] In formula (X-2), R 137 is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and the others are substituents. The meanings of the other groups are the same as those in formula (X).

[0386] The polarity conversion group such as the polymerizable group or the acid-decomposable group has the same meaning as the polymerizable group described in the polymerizable group of the polyimide precursor.

[0387] R 133 represents a divalent organic group. Examples of the divalent organic group include aliphatic groups and aromatic groups. As specific examples, R in the formula (3) of the polybenzoxazole precursor may be 121 Examples, preferably examples with R121 same.

[0388] R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include R in the formula (3) of the polybenzoxazole precursor: 122 Examples, preferably examples with R 122 same.

[0389] For example, as R 122 The four bonders of the exemplified tetravalent organic group are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. 134 In the case of the following organic groups, the following structures are formed. In the following structures, * represents a bonding site to a nitrogen atom or an oxygen atom in formula (X).

[0390] [Chemical formula 43]

[0391]

[0392] When the first specific resin or the second specific resin is a polyimide, the content of the repeating unit represented by formula (1-1) relative to the total mass of the first specific resin or the second specific resin is preferably 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass.

[0393] Furthermore, the first specific resin or the second specific resin may contain two or more repeating units represented by formula (1-1) having different structures. In this case, the total amount is preferably within the above range.

[0394] When the first specific resin or the second specific resin is a polyimide, the total content of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (4) relative to the total mass of the first specific resin or the second specific resin is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass.

[0395] Furthermore, when the first specific resin or the second specific resin contains a repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) having different structures. In this case, the total amount is preferably within the above range.

[0396] When the first specific resin or the second specific resin is a polyimide precursor, the content of the repeating unit represented by formula (1-2) relative to the total mass of the first specific resin or the second specific resin is preferably 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass.

[0397] Furthermore, the first specific resin or the second specific resin may contain two or more repeating units represented by formula (1-2) having different structures. In this case, the total amount is preferably within the above range.

[0398] When the first specific resin or the second specific resin is a polyimide precursor, the total content of the repeating unit represented by formula (1-2) and the repeating unit represented by formula (2) relative to the total mass of the first specific resin or the second specific resin is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass.

[0399] Furthermore, when the first specific resin or the second specific resin contains a repeating unit represented by formula (2), it may contain two or more repeating units represented by formula (2) having different structures. In this case, the total amount is preferably within the above range.

[0400] The third resin composition contains at least one resin selected from polyimide and a precursor thereof and contains at least one of the repeating units represented by the following formula (2-1) and formula (3-1) (third specific resin).

[0401] [Chemical formula 44]

[0402]

[0403] In formula (2-1), X 2 represents an organic group having 4 or more carbon atoms, Y 2 represents an organic group having 4 or more carbon atoms, Y 2 Does not contain ester bonds, R 2 Each independently represents a group represented by the following formula (R-2), and n represents an integer of 1 or greater.

[0404] In formula (3-1), X 3 represents an organic group having 4 or more carbon atoms, Y 3 represents an organic group having 4 or more carbon atoms, Y 3 Contains no ester bond, A 3 and A 4Each independently represents an oxygen atom or -NR N -, R 3 and R 4 Each independently represents a hydrogen atom or a monovalent organic group, R 2 Each independently represents a group represented by the following formula (R-2), and n represents an integer of 1 or greater.

[0405] [Chemical formula 45]

[0406]

[0407] In formula (R-2), L 2 represents a b2+1 valent connecting group, Z 2 Indicates a b1+1 valent organic group, A 2 represents a polymerizable group, b1 represents 1 or more, and Z 2 b2 represents an integer greater than or equal to 1, and * represents the same integer as Y of formula (2-1). 2 Or Y in formula (3-1) 3 The number of ester bonds contained in the formula (R-2) is 1 or 0.

[0408] X in formula (2-1) 2 , Y 2 The preferred embodiment of n is the same as X in formula (1-1) 1 , Y 1 The preferred manner of n is the same.

[0409] L in formula (R-2) 2 , A 2 The preferred embodiments of b1 and b2 are the same as L in formula (R-1): 1 , A 1 , a1 and a2 are preferably the same.

[0410] Furthermore, the number of ester bonds contained in formula (R-2) is 1 or 0, and 0 is also one of the preferred aspects of the present invention.

[0411] In formula (R-2), Z 2 It is preferably a group containing a ring structure, and more preferably a group obtained by removing b1+1 hydrogen atoms from a ring structure.

[0412] Z 2 Preferred aspects of the ring structure in are the same as preferred aspects of the ring structure having 5 or more ring members in the first specific resin.

[0413] And, in Z 2 When Z is a group formed by removing b1+1 hydrogen atoms from a ring structure, 2Preferably, Z is an aromatic group or a cyclic aliphatic group. 2 The preferred embodiment is the same as Z in the above formula (R-1) 1 The preferred method is the same.

[0414] In addition, Z 2 It can be a hydrocarbon group, or a hydrocarbon group and a group selected from -O-, -CO-, -S-, -SO2-, and -NR N -A group represented by a combination of at least one structure. N The preferred manner is as described above.

[0415] In formula (R-2), L 2 Preferably, it is a group represented by the following formula (L-2). 2 is a group represented by the following formula (L-2), wherein A in the formula (R-2) 2 More preferred is a vinyl group or a vinyl ether group.

[0416] [Chemical formula 46]

[0417]

[0418] In formula (L-2), L x represents a b2+1 valent linking group, b2 represents an integer greater than 1, and * represents the same as X in formula (2-1) 2 or Y 2 Or X in formula (3-1) 3 or Y 2 The bonding site of Z in formula (R-2) is represented by #. 2 bonding part.

[0419] In formula (L-2), L X The preferred embodiment is the same as L in the above formula (L-1) X The preferred method is the same.

[0420] In the formula (L-2), b2 has the same meaning as b2 in the formula (R-2), and preferred aspects are also the same.

[0421] Among these, A in the formula (R-2) contained in the formula (2-1) 2 At least one of them is a vinyl group, a (meth)acryloyloxy group, a vinyl ether group, an allyl group, an epoxy group or a group containing these, and A in the formula (R-2) contained in the formula (3-1) 2 At least one of them is a vinyl group, a (meth)acryloyloxy group, a vinyl ether group, an allyl group, an epoxy group or a group containing these, and X in formula (2-1) 2 and Y 2Each of the structures represented by any of the following formulae (V-1) to (V-4) contains a structure obtained by removing two or more hydrogen atoms, and X in formula (3-1) 3 and Y 3 Preferably, the structure is one in which two or more hydrogen atoms are removed from the structure represented by any of the following formulae (V-1) to (V-4).

[0422] Furthermore, the third specific resin may contain a repeating unit represented by the above formula (2). However, in this case, the repeating unit represented by the formula (2) does not contain a repeating unit represented by the formula (3-1).

[0423] Furthermore, the third specific resin may contain a repeating unit represented by the above formula (4). However, in this case, the repeating unit represented by the formula (4) does not contain a repeating unit represented by the formula (4-1).

[0424] When the third specific resin is a polyimide, the content of the repeating unit represented by formula (2-1) relative to the total mass of the third specific resin is preferably 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass.

[0425] Furthermore, the third specific resin may contain two or more repeating units represented by formula (2-1) having different structures. In this case, the total amount is preferably within the above range.

[0426] When the third specific resin is a polyimide, the total content of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (4) relative to the total mass of the third specific resin is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass.

[0427] Furthermore, when the third specific resin contains a repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) having different structures. In this case, the total amount is preferably within the above range.

[0428] When the third specific resin is a polyimide precursor, the content of the repeating unit represented by formula (1-2) relative to the total mass of the third specific resin is preferably 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass.

[0429] Furthermore, the third specific resin may contain two or more repeating units represented by formula (1-2) having different structures. In this case, the total amount is preferably within the above range.

[0430] When the third specific resin is a polyimide precursor, the total content of the repeating unit represented by formula (1-2) and the repeating unit represented by formula (2) relative to the total mass of the third specific resin is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass.

[0431] Furthermore, when the third specific resin contains a repeating unit represented by formula (2), it may contain two or more repeating units represented by formula (2) having different structures. In this case, the total amount is preferably within the above range.

[0432] When the specific resin is a polyimide, the weight average molecular weight (Mw) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 10,000 to 40,000. By setting the weight average molecular weight to 3,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight average molecular weight is particularly preferably 5,000 or more.

[0433] The number average molecular weight (Mn) of the polyimide is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and further preferably 5,000 to 20,000.

[0434] The molecular weight dispersion of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, but is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0435] When the resin composition contains multiple polyimides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyimide precursor are within the above ranges. The weight average molecular weight, number average molecular weight and dispersion degree calculated using the multiple polyimides as one resin are also preferably within the above ranges.

[0436] When the specific resin is a polyimide precursor, the weight average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000.

[0437] The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0438] In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[0439] When the resin composition contains multiple polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyimide precursor are within the above ranges. In addition, the weight average molecular weight, number average molecular weight and dispersion degree calculated using the multiple polyimide precursors as one resin are also preferably within the above ranges, respectively.

[0440] When the specific resin is polyimide, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the perspective of film strength, insulation, etc. of the obtained organic film. The upper limit of the imidization rate is not particularly limited as long as it is 100% or less.

[0441] Furthermore, when the specific resin is polyimide, the content of the imide structure in the specific resin is preferably 3 mmol / g or less, and more preferably 2.5 mmol / g or less. The lower limit of the content is not particularly limited, and can be, for example, 0.5 mmol / g or more.

[0442] When the specific resin is a polyimide precursor, the imidization rate (also referred to as "ring closure rate") of the polyimide precursor is preferably less than 70%, more preferably 50% or less, further preferably 20% or less, and particularly preferably 10% or less, from the perspective of film strength, insulation, etc. of the obtained organic film. The lower limit of the imidization rate is not particularly limited as long as it is 0% or less.

[0443] The imidization ratio can be measured, for example, by the following method.

[0444] The infrared absorption spectrum of the specific resin was measured, and the absorption peak at 1377 cm-1 derived from the imide structure was determined. -1 Next, after the specific resin was heat treated at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P1 at 1377 cm -1 The imidization ratio of the specific resin can be determined from the following formula using the obtained peak intensities P1 and P2.

[0445] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0446] [Method for producing specific resin]

[0447] For example, the specific resin can be obtained by the following methods: a method of reacting tetracarboxylic dianhydride with diamine at low temperature; a method of reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamic acid, and esterifying with a condensing agent or an alkylating agent; a method of obtaining a diester by tetracarboxylic dianhydride and alcohol and then reacting the diester in the presence of diamine and a condensing agent; and a method of obtaining a diester by tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting the remaining dicarboxylic acid with diamine, etc. Among the above-mentioned production methods, a method of obtaining a diester by tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting the remaining dicarboxylic acid with diamine is more preferred.

[0448] Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N′-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0449] Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate and the like.

[0450] Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.

[0451] Furthermore, when a polyimide is to be obtained as a specific resin, the following methods can be used for synthesis: a method of completely imidizing the resin obtained by the above method using a known imidization reaction method; a method of stopping the imidization reaction midway and introducing a part of the imide structure; and a method of introducing a part of the imide structure by mixing a completely imidized polymer with the polyimide precursor. Furthermore, other known methods for synthesizing polyimides can also be applied.

[0452] In the method for producing a specific resin, it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds.

[0453] The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.

[0454] In the method for producing a specific resin, it is preferred to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.

[0455] The basic compound can be appropriately determined depending on the starting material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0456] -Capping agent-

[0457] In the manufacturing method of a specific resin, in order to further improve storage stability, it is preferred to block the carboxylic anhydride, anhydride derivative or amino group remaining at the resin end of the specific resin. When blocking the carboxylic anhydride and anhydride derivative remaining at the resin end, as an end-capping agent, monoalcohol, phenol, thiol, thiophenol, monoamine, etc. can be listed. From the perspective of reactivity and film stability, it is more preferred to use monoalcohol, phenols, and monoamines. As the preferred compound of monoalcohol, methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, primary alcohols such as furfuryl alcohol, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, secondary alcohols such as tertiary ... Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy ...6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-carboxy- The terminal groups of the present invention include 2-amino-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and a variety of different terminal groups can be introduced by reacting a variety of end-capping agents.

[0458] In addition, when the amino group at the end of the resin is blocked, it can be blocked with a compound having a functional group that can react with the amino group. The preferred end-capping agent for the amino group is preferably carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic anhydride, sulfonic acid carboxylic anhydride, etc., and more preferably carboxylic anhydride and carboxylic acid chloride. As the preferred compound of carboxylic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. can be listed. In addition, as the preferred compound of carboxylic acid chloride, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc. can be listed.

[0459] -Solid Precipitation-

[0460] In the manufacture method of specific resin, solid precipitation process can be included. Specifically, after filtering the water absorption byproduct of the dehydration condensation agent coexisting in the reaction solution as required, in poor solvents such as water, aliphatic lower alcohol or its mixed solution, the obtained polymer component is dropped and the polymer component is precipitated, so that it can be precipitated with solid and dried to obtain specific resin. In order to improve the degree of purification, operations such as redissolution, reprecipitation, precipitation, drying can be repeated to the specific resin. In addition, the process of using ion exchange resin to remove ionic impurities can also be included.

[0461] [Specific example]

[0462] Specific examples of the specific resin include polyimides (SP-1) to (SP-15) and a polyimide precursor (P-1) in Examples described below, but the present invention is not limited thereto.

[0463] 〔content〕

[0464] 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, further preferably 40% by mass or more, and further preferably 50% by mass or more relative to the total solid content of the resin composition. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 95% by mass or less relative to the total solid content of the resin composition.

[0465] The resin composition of the present invention may contain only one specific resin or two or more specific resins. When containing two or more specific resins, the total amount is preferably within the above range.

[0466] The resin composition of the present invention also preferably contains at least two types of resins.

[0467] Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, may contain two or more specific resins, and preferably contains two or more specific resins.

[0468] When the resin composition of the present invention contains two or more specific resins, it is preferred that the resin composition contain two or more polyimide precursors having different structures derived from dianhydride, for example.

[0469] <Other resins>

[0470] The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins").

[0471] As other resins, other polyimide precursors different from the specific resin, other polyimides different from the specific resin, polybenzoxazole precursors, polybenzoxazole, aromatic polyether, polyamideimide precursor, polyamideimide, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, (meth) acrylic resin, (meth) acrylic amide resin, urethane resin, butyral resin, styrene resin, polyether resin, polyester resin, etc. can be listed.

[0472] Examples of other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, and polyamideimides include compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355. The above descriptions are incorporated into the present specification.

[0473] The aromatic polyether is not particularly limited, but polyphenylene ether is preferred.

[0474] The polyphenylene ether preferably contains a repeating unit represented by the following formula (PE).

[0475] [Chemical formula 47]

[0476]

[0477] In formula (PE), R E1 represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amino group which may have a substituent, a nitro group, and a carboxyl group.

[0478] Furthermore, the polyphenylene ether is also preferably a compound having a polymerizable group.

[0479] The polymerizable group is preferably an epoxy group, an oxetanyl group, an oxazolyl group, a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, a blocked isocyanate group, or a group having an ethylenically unsaturated bond, and more preferably a group having an ethylenically unsaturated bond.

[0480] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, and the like. Preferably, it is a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group, more preferably a vinylphenyl group or a (meth)acryloyloxy group, and still more preferably a (meth)acryloyloxy group.

[0481] When the polyphenylene ether is a compound having a polymerizable group, the position of the polymerizable group is not particularly limited, and for example, a structure in which the polymerizable group is introduced at the terminal of the main chain is preferred.

[0482] The polyphenylene ether may contain other repeating units, but the content of the other repeating units is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the polyphenylene ether.

[0483] The number average molecular weight of the polyphenylene ether is not particularly limited, but is preferably 500 to 50,000.

[0484] The lower limit of the number average molecular weight is preferably 800 or more, more preferably 1000 or more, and further preferably 1500 or more.

[0485] The upper limit of the number average molecular weight is preferably 30,000 or less, more preferably 20,000 or less, and further preferably 10,000 or less.

[0486] Specific examples of polyphenylene ether (PPE) include, for example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), copolymers of 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.), polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenyls or bisphenols, and polyphenylene ethers having a linear or branched structure obtained by heating poly(2,6-dimethyl-1,4-phenylene ether) and a phenolic compound such as bisphenols or trisphenols in a toluene solvent in the presence of an organic peroxide and subjecting the resulting mixture to a redistribution reaction, but the present invention is not limited thereto.

[0487] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more, relative to the total solid content of the resin composition.

[0488] The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0489] As a preferred embodiment of the resin composition of the present invention, it is also possible to set the content of other resins to be low. In the above embodiment, relative to the total solid content of the resin composition, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient.

[0490] The resin composition of the present invention may contain only one other resin or two or more other resins. When containing two or more other resins, the total amount is preferably within the above range.

[0491] <Polymerizable Compound>

[0492] The resin composition of the present invention contains a polymerizable compound.

[0493] In particular, from the viewpoint of lowering the dielectric constant, the polymerizable compound preferably contains a compound having a ClogP value of 3.0 or more, and more preferably contains a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms.

[0494] In this specification, the ClogP value of a compound is subject to the following definition.

[0495] The determination of octanol-water partition coefficient (logP value) can generally be implemented by the flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000). In addition, the octanol-water partition coefficient (logP value) can also be estimated by a computational chemical method or an empirical method instead of actual determination. As a calculation method, it is known to use Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989)), Broto's fragmentation method (Eur. J. Med. Chem. -Ch im. Theor., 19, 71 (1984)) etc. In the present invention, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is used.

[0496] The ClogP value refers to the value of the common logarithm logP of the partition coefficient P between 1-octanol and water obtained by calculation. The method or software used for calculating the ClogP value can be known, but unless otherwise specified, the ClogP program of the system PCModels assembled in Daylight Chemical Information Systems is used in the present invention.

[0497] The ClogP value is preferably 4.0 or more, more preferably 6.0 or more.

[0498] In addition, the upper limit of the ClogP value is not particularly limited, but is preferably 15.0 or less.

[0499] The aromatic ring structure may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic hydrocarbon ring, more preferably a benzene ring, and preferably a condensed ring such as a fluorene ring from the viewpoint of reducing the dielectric constant.

[0500] The aliphatic ring structure having 6 or more carbon atoms is preferably an aliphatic ring structure having 6 to 30 carbon atoms, and more preferably an aliphatic ring structure having 6 to 20 carbon atoms.

[0501] Examples of the aliphatic ring structure having 6 or more carbon atoms include monocyclic rings such as cyclohexane rings, dicyclopentane rings, tricyclic rings [5.2.1.0 2,6 ] a heterocyclic ring such as a decane ring, preferably a heterocyclic ring.

[0502] The polymerizable compound having a ClogP value of 3.0 or more (especially, a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms) is preferably a compound containing a group having an ethylenically unsaturated bond, and more preferably a compound containing two or more groups having an ethylenically unsaturated bond. In addition, a compound containing two groups having an ethylenically unsaturated bond is also preferred.

[0503] Furthermore, the polymerizable compound having a ClogP value of 3.0 or more (particularly, a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms) is preferably a compound corresponding to the radical crosslinking agent described below.

[0504] Specific examples of the polymerizable compound having a ClogP value of 3.0 or more include the following compounds, but are not limited thereto.

[0505] [Chemical formula 48]

[0506]

[0507] Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

[0508] 〔Free radical crosslinking agent〕

[0509] The resin composition of the present invention preferably contains a radical crosslinking agent.

[0510] The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenically unsaturated bond is preferred. As the above-mentioned group containing an ethylenically unsaturated bond, vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, (meth)acrylamide, etc. can be listed.

[0511] Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and a (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0512] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

[0513] 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 still more preferably a compound having 2 to 6 ethylenically unsaturated bonds.

[0514] The resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds, also from the viewpoint of the film strength of the obtained pattern (cured product).

[0515] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0516] As a specific example of a free radical crosslinking agent, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, and thiols and monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reactions of monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. In addition, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred, and substitution reactions of unsaturated carboxylic acid esters or amides with dissociable substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Furthermore, as another example, the above unsaturated carboxylic acid can be replaced with a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, and allyl ether. As a specific example, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, which are incorporated into this specification.

[0517] The radical crosslinking agent is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples of the compound having a boiling point of 100° C. or higher under normal pressure include compounds described in paragraph 0203 of International Publication No. 2021 / 112189, etc. This content is incorporated into this specification.

[0518] Preferred radical crosslinking agents other than those described above include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189, and the like. The contents are incorporated into the present specification.

[0519] As the radical crosslinking agent, dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.)), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) and these (meth)acryloyl groups are preferably bonded via an ethylene glycol residue or a propylene glycol residue. These oligomer types can also be used.

[0520] Commercially available products of the radical crosslinking agent include, for example, tetrafunctional acrylate SR-494 having four vinyloxy chains, bifunctional methacrylate SR-209, 231, 239 having four vinyloxy chains (all manufactured by Sartomer Company, Inc.), hexafunctional acrylate DPCA-60 having six pentyloxy chains, trifunctional acrylate TPA-330 having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (all manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (all manufactured by Nippon Kayaku Co., Ltd.), and NK ESTER 4G. Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0521] As the radical crosslinking agent, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. As the radical crosslinking agent, compounds having an amino structure or a thioether structure in the molecule described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 01-105238 can also be used.

[0522] The free radical crosslinking agent may be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free 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 free radical crosslinking agent in which the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group. Particularly preferred are the following compounds: in the free radical crosslinking agent in which the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. As commercially available products, for example, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD. can be cited.

[0523] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and more preferably 1 to 100 mgKOH / g. As long as the acid value of the radical crosslinking agent is within the above range, the workability in production and the developability are excellent. In addition, the polymerizability is good. The above acid value is measured according to the description of JIS K 0070:1992.

[0524] From the viewpoint of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate as the resin composition.

[0525] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate can be used. Ester, 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 adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds. Two or more of these can be used in combination as needed.

[0526] For example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain with a formula weight of about 200.

[0527] From the aspect of suppressing the warping of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as a radical crosslinking agent. As a monofunctional radical crosslinking agent, 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-hydroxymethyl (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono(meth) acrylate, mono(meth) acrylate polypropylene glycol (meth) acrylate derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether, etc. can be preferably used. As a monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, it is also preferred to have a boiling point of more than 100°C at normal pressure.

[0528] Examples of the bifunctional or higher-functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0529] When a free radical crosslinking agent is contained, the content of the free radical crosslinking agent is preferably more than 0% by mass and less than 60% by mass relative to the total solid content of the resin composition. The lower limit is more preferably more than 5% by mass. The upper limit is more preferably less than 50% by mass, and further preferably less than 30% by mass.

[0530] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used in combination, the total amount thereof is preferably within the above range.

[0531] 〔Other cross-linking agents〕

[0532] The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.

[0533] The other crosslinking agent refers to a crosslinking agent other than the above-mentioned free radical crosslinking agent, and is preferably a compound having a plurality of groups in the molecule that promote the reaction (form a covalent bond with other compounds in the composition or their reaction products) by the photosensitization of the above-mentioned photoacid generator or photobase generator, and more preferably a compound having a plurality of groups in the molecule that promote the reaction (form a covalent bond with other compounds in the composition or their reaction products) by the action of an acid or a base.

[0534] The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

[0535] As other crosslinking agents, compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355 can be mentioned. The above description is incorporated into the present specification.

[0536] 〔Polymerization initiator〕

[0537] The resin composition of the present invention contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, and it is particularly preferred to contain a photopolymerization initiator.

[0538] The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that acts on a photoexcited sensitizer and generates active free radicals.

[0539] The photoradical polymerization initiator preferably contains at least one photopolymerization initiator having a photopolymerization activity of at least about 50 L·mol in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). -1 cm -1The molar absorption coefficient of a compound can be measured by a known method, for example, by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), preferably using ethyl acetate as a solvent, at a concentration of 0.01 g / L.

[0540] As a photo-radical polymerization initiator, known compounds can be used arbitrarily. For example, 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, hexaarylbisimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For these details, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and the content is incorporated into this specification. In addition, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, Japanese Patent Publication No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313 can be listed, and these contents are incorporated into this specification.

[0541] Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0542] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents are incorporated into this specification.

[0543] As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF) can be used.

[0544] As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0545] As the aminoacetophenone-based initiator, the acylphosphine oxide-based initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be preferably used. The contents are incorporated into the present specification.

[0546] As the photo-radical polymerization initiator, an oxime compound can be more preferably cited. By using an oxime compound, the exposure latitude can be more effectively improved. Oxime compounds have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator, so they are particularly preferred.

[0547] Specific examples of oxime compounds include compounds described in Japanese Unexamined Patent Publication No. 2001-233842, compounds described in Japanese Unexamined Patent Publication No. 2000-080068, compounds described in Japanese Unexamined Patent Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. The compounds described in Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Publication No. 2004-534797, the compounds described in Japanese Patent Publication No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, the compounds described in International Publication No. 2013 / 167515, etc., are incorporated into the present specification.

[0548] Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferred to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0549] [Chemical formula 49]

[0550]

[0551] Commercially available products of 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-A-2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by DaitoChemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, oxime compounds of the following structures can also be used.

[0552] [Chemical formula 50]

[0553]

[0554] As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring, an oxime compound having a carbazole ring and having at least one benzene ring as a naphthalene ring skeleton, or an oxime compound having a fluorine atom described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189 can be used.

[0555] Furthermore, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a substituent having a hydroxyl group bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359 can also be used. These contents are incorporated into this specification.

[0556] As the photopolymerization initiator, an aromatic ring group Ar having an electron-withdrawing group introduced into the aromatic ring can also be used. OX1 As the aromatic ring group Ar OX1The electron withdrawing group possessed may include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, cyano, preferably acyl and nitro, and from the reason of the class of film with excellent light resistance, acyl is more preferred, and benzoyl is further preferred. Benzoyl may have a substituent. As a substituent, preferably a halogen atom, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclic oxygen group, alkenyl, alkyl sulfhydryl, aryl sulfhydryl, acyl or amino, more preferably alkyl, alkoxy, aryl, aryloxy, heterocyclic oxygen group, alkyl sulfhydryl, aryl sulfhydryl or amino, more preferably alkoxy, alkyl sulfhydryl or amino.

[0557] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by the formula (OX1) and a compound represented by the formula (OX2), and is more preferably a compound represented by the formula (OX2).

[0558] [Chemical formula 51]

[0559]

[0560] 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 alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphonyl group, a carbamoyl group or a sulfonamide group,

[0561] R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group,

[0562] R X3 ~R X14 Each independently represents a hydrogen atom or a substituent.

[0563] However, R X10 ~R X14 At least one of them is an electron withdrawing group.

[0564] In the above formula, R X12 is an electron-withdrawing group, R X10 , R X11 , R X13 , R X14 Preferred is a hydrogen atom.

[0565] Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, and the contents are incorporated into the present specification.

[0566] Particularly preferred oxime compounds include oxime compounds having specific substituents disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having a thioaryl group disclosed in Japanese Patent Application Laid-Open No. 2009-191061, and the like, and the contents thereof are incorporated into the present specification.

[0567] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole 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.

[0568] Furthermore, the photoradical polymerization initiator is more preferably a trihalomethyl triazine compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, and is at least one compound selected from the group consisting of a trihalomethyl triazine compound, an α-amino ketone compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, and a benzophenone compound, and is further preferably a metallocene compound or an oxime compound.

[0569] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, and the contents are incorporated into the present specification.

[0570] As the photo-radical polymerization initiator, a photo-radical polymerization initiator of difunctional or trifunctional or more can be used. By using this photo-radical polymerization initiator, more than two free radicals are produced from one molecule of the photo-radical polymerization initiator, so good sensitivity can be obtained. And, when using a compound of asymmetric structure, crystallinity decreases and the solubility in solvents etc. is improved, and becomes difficult to separate out over time, thereby being able to improve the stability over time of resin combination. Specific examples of the bifunctional or trifunctional or higher-functional photoradical polymerization initiator include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, compounds (E) described in JP-A-2013-522445, and compounds described in JP-A-2013-522445. The photoinitiator (G), Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Publication No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc., the contents of which are incorporated into this specification.

[0571] When the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and further preferably 1.0 to 10% by mass relative to the total solid content of the resin composition. The photopolymerization initiator may contain only one or more. When containing more than two photopolymerization initiators, the total amount is preferably within the above range.

[0572] In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, heating in an oven, a hot plate, or the like may further promote crosslinking by the photopolymerization initiator.

[0573] 〔Sensitizer〕

[0574] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with a thermal free radical polymerization initiator, a photo free radical polymerization initiator, etc., and generates electron transfer, energy transfer, heat generation, etc. As a result, the thermal free radical polymerization initiator and the photo free radical polymerization initiator induce chemical changes and decompose, and generate free radicals, acids or bases.

[0575] As sensitizers that can be used, compounds such as benzophenone, Michler'sketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole methylene azo, xanthene, phthalocyanine, benzopyran, and indigo can be used.

[0576] Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzylidenedihydroindanone, and p-dimethylaminobenzylidenedihydroindanone. ketone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene)benzothiazole, 2-(p-dimethylaminophenyl vinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7 -Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, diethylaminobenzene Isoamyl formate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like.

[0577] Also, other sensitizing pigments may be used.

[0578] For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification.

[0579] 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 further preferably 0.5 to 10 mass % relative to the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0580] 〔Chain transfer agent〕

[0581] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a group of compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH and GeH in the molecule, dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthate compounds having thiocarbonylthio groups for RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, etc. can be used. These can generate free radicals by supplying hydrogen to low-activity free radicals, or can generate free radicals by deprotonating after oxidation. In particular, thiol compounds can be preferably used.

[0582] Furthermore, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used, and the contents are incorporated into the present specification.

[0583] When the resin composition has 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 further 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 only one or more. When there are two or more chain transfer agents, it is preferred that the total is within the above range.

[0584] Furthermore, the polymerization initiator is preferably a photoacid generator. As the photoacid generator, a photoacid generator that generates radicals is preferred.

[0585] Specifically, a compound that absorbs light to decompose to generate radicals and that extracts hydrogen from a solvent or the acid generator itself to generate an acid is preferred.

[0586] Examples of the photoacid generator include quinonediazide compounds, oximesulfonate compounds, organic halogenated compounds, organic boronic acid chlorine compounds, disulfone compounds, and onium salts, and onium salts are preferred.

[0587] Examples of the onium salt include diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts.

[0588] Furthermore, the onium salt is a salt of a cation having an onium structure and an anion, and the cation and the anion may or may not be bonded via a covalent bond.

[0589] That is, the onium salt may be an intramolecular salt having a cationic portion and an anionic portion in the same molecular structure, or an intermolecular salt in which cationic molecules and anionic molecules as different molecules are ionically bonded, preferably an intermolecular salt. Furthermore, in the composition of the present invention, the cationic portion or cationic molecule and the anionic portion or anionic molecule may be bonded by ionic bonds or may be dissociated.

[0590] [Sulfonium salt]

[0591] In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion.

[0592] -Sulfonium cation-

[0593] The sulfonium cation is preferably a tertiary sulfonium cation, and more preferably a triarylsulfonium cation.

[0594] Furthermore, the sulfonium cation is preferably a cation represented by the following formula (103).

[0595] [Chemical formula 52]

[0596]

[0597] In formula (103), R 8 ~R 10 Each independently represents a hydrocarbon group.

[0598] R 8 ~R 10 Preferably, each is independently an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0599] R 8 ~R 10 It may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among these, as a substituent, it is preferred to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0600] R 8 ~R 10The groups may be the same or different, but are preferably the same in terms of synthetic suitability.

[0601] -Anions-

[0602] The anion is not particularly limited and may be selected in consideration of the acid to be generated, but B(C6F5)4 - 、BF4 - Boron anions, (Rf) N PF 6-n PF3(C2F5) 3- PF6 - Phosphorus anions, SbF6 - Antimony anions, other carboxylic acid anions, sulfonic acid anions, etc.

[0603] 〔Iodized salt〕

[0604] In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned sulfonium salt, and preferred embodiments are also the same.

[0605] -Ion cation-

[0606] The iodonium cation is preferably a diaryliodonium cation.

[0607] Furthermore, the iodonium cation is preferably a cation represented by the following formula (104).

[0608] [Chemical formula 53]

[0609]

[0610] In formula (104), R 11 and R 12 Each independently represents a hydrocarbon group.

[0611] R 11 and R 12 Preferably, each is independently an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0612] R 11 and R 12 It may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among these, as a substituent, it is preferred to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0613] R 11 and R 12 The groups may be the same or different, but are preferably the same in terms of synthetic suitability.

[0614] 〔Phosphonium salt〕

[0615] In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned sulfonium salt, and preferred embodiments are also the same.

[0616] -Phosphonium cation-

[0617] As the phosphonium cation, a fourth phosphonium cation is preferred, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.

[0618] Furthermore, the phosphonium cation is preferably a cation represented by the following formula (105).

[0619] [Chemical formula 54]

[0620]

[0621] In formula (105), R 13 ~R 16 Each independently represents a hydrogen atom or a hydrocarbon group.

[0622] R 13 ~R 16 Preferably, each is independently an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0623] R 13 ~R 16 It may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among these, as a substituent, it is preferred to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0624] R 13 ~R 16 The groups may be the same or different, but are preferably the same in terms of synthetic suitability.

[0625] The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, further preferably 0.5 to 10% by mass, further preferably 0.5 to 3% by mass, further preferably 0.5 to 1.2% by mass based on the total solid content of the resin composition.

[0626] The photoacid generator may be used alone or in combination of two or more. When two or more photoacid generators are used in combination, the total amount thereof is preferably within the above range.

[0627] Furthermore, in order to impart photosensitivity to a desired light source, it is also preferably used in combination with a sensitizer.

[0628] Furthermore, it is also one of the preferred embodiments of the present invention that the resin composition of the present invention contains two or more polymerization initiators as polymerization initiators.

[0629] Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0630] By containing a photopolymerization initiator and a thermal polymerization initiator described later, pattern formation by exposure can be performed, radical polymerization is easily performed during curing by a heating step described later, and chemical resistance is improved.

[0631] When a photopolymerization initiator and a thermal polymerization initiator described below are contained, the content of the thermal polymerization initiator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0632] By containing a photoradical polymerization initiator and a photoacid generator, performance such as resolution may be improved.

[0633] When a photopolymerization initiator and a photoacid generator are contained, the content of the photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, based on the total content of the photopolymerization initiator and the photoacid generator.

[0634] 〔Thermal polymerization initiator〕

[0635] As a thermal polymerization initiator, for example, a thermal free radical polymerization initiator can be cited. A thermal free radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the resin and the polymerizable compound can also be polymerized, thereby further improving the solvent resistance.

[0636] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.

[0637] When the resin composition contains a thermal polymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.5 to 15% by mass relative to the total solid content of the resin composition. The thermal polymerization initiator may contain only one or more than two. When containing more than two thermal polymerization initiators, the total amount is preferably within the above range.

[0638] <Alkali Generator>

[0639] The resin composition of the present invention may contain a base generator. The base generator refers to a compound that can generate a base through a physical action or a chemical action. Preferred base generators include thermal base generators and photobase generators.

[0640] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains an alkali generator. When the resin composition contains a thermal alkali generator, the cyclization reaction of the precursor can be promoted, for example, by heating, so that the mechanical properties and chemical resistance of the cured product are good, and the performance as an interlayer insulating film for a redistribution layer contained in a semiconductor package is improved.

[0641] 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.

[0642] The base generating agent is not particularly limited, and a known base generating agent can be used. Examples of known base generating agents 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, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimide compounds, and the like.

[0643] Specific examples of the nonionic base generator include compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355. The above description is incorporated into the present specification.

[0644] Examples of the base generating agent include the following compounds, but the base generating agent is not limited to these compounds.

[0645] [Chemical formula 55]

[0646]

[0647] The molecular weight of the nonionic base generating agent is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0648] Preferred compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0649] Specific examples of the ammonium salt include the following compounds, but are not limited to these.

[0650] [Chemical formula 56]

[0651]

[0652] Specific examples of the imide salt include the following compounds, but are not limited to these.

[0653] [Chemical formula 57]

[0654]

[0655] Furthermore, as the base generator, an amine in which the amino group is protected by a tert-butoxycarbonyl group is preferred from the viewpoints of storage stability and deprotection during sulfurization to generate a base.

[0656] Examples of the amine compound protected by a tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl] Benzyl alcohol, diethanolamine, diisopropanolamine, 3-hydroxypyrrolidine, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidine)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetrahydrotetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxoundecane, or an amino acid and a compound in which the amino group of the derivative is protected by a tert-butoxycarbonyl group, but the present invention is not limited thereto.

[0657] When the resin composition contains an alkali generator, the content of the alkali 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, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.

[0658] The base generating agent can be used alone or in combination. When two or more base generating agents are used, the total amount is preferably within the above range.

[0659] <Solvent>

[0660] The resin composition of the present invention preferably contains a solvent.

[0661] 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.

[0662] Examples of the 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, γ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.) Preferred esters include 2-alkoxy alkyl propionates (e.g., 2-alkoxy methyl propionate, 2-alkoxy ethyl propionate, 2-alkoxy propyl propionate, etc. (e.g., 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate), 2-alkoxy-2-methyl methyl propionate and 2-alkoxy-2-methyl ethyl propionate (e.g., 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0663] Preferred ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celulose acetate, ethyl celulose 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.

[0664] Examples of the ketones preferably include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0665] Examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene. Preferred cyclic hydrocarbons include these.

[0666] As the sulfoxides, for example, dimethyl sulfoxide can be mentioned as a preferred sulfoxide.

[0667] As amides, 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, N-acetylmorpholine and the like are listed as preferred amides.

[0668] As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are exemplified as preferred ureas.

[0669] Examples of the alcohol 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, methylbenzyl alcohol, n-pentanol, methylpentanol and diacetone alcohol.

[0670] Regarding the solvent, a mixture of two or more solvents is also preferred from the viewpoint of improving the properties of the coating surface.

[0671] In the present invention, it is preferred to use a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celulose 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, levulose ketone and dihydrolevulose ketone, or a mixed solvent consisting of two or more. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone in combination, dimethyl sulfoxide and γ-valerolactone in combination, 3-methoxy-N, N-dimethylpropionamide and γ-butyrolactone in combination, 3-methoxy-N, N-dimethylpropionamide and γ-butyrolactone in combination, or N-methyl-2-pyrrolidone and ethyl lactate in combination. One preferred embodiment of the present invention is to further add about 1 to 10% by mass of toluene relative to the total mass of the solvent to these solvents used in combination.

[0672] Especially, from the aspect of the storage stability of resin combination etc., the mode that comprises gamma-valerolactone as solvent is also one of preferred modes of the present invention.In this mode, the content of gamma-valerolactone relative to the gross mass of solvent is preferably more than 50 mass %, more preferably more than 60 mass %, further preferably more than 70 mass %.And, the upper limit of above-mentioned content is not particularly limited, can be 100 mass %.Above-mentioned content considers the solubility of the composition such as the specific resin contained in the resin combination etc. to determine.

[0673] Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferred that the solvent contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.

[0674] From the viewpoint of coating property, the content of solvent is preferably set to the amount of 5-80 mass % of the total solid content concentration of the resin composition of the present invention, more preferably set to the amount of 5-75 mass %, further preferably set to the amount of 10-70 mass %, and further preferably set to 20-70 mass %. About solvent content, as long as it is adjusted according to the desired thickness and coating method of the coating film. When containing more than two solvents, it is preferably within the above range in total.

[0675] <Metal Adhesion Improver>

[0676] The resin composition of the present invention preferably contains a metal adhesion improver from the aspect of improving adhesion to metal materials used in electrodes or wiring, etc. Examples of the metal adhesion improver include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, etc.

[0677] 〔Silane coupling agent〕

[0678] As a silane coupling agent, for example, the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Publication No. 2018-173573 can be cited, and these contents are incorporated into this specification. In addition, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358, it is also preferred to use two or more different silane coupling agents. The following compounds are also preferably used as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group. In addition, the following R can list the structure of the blocking agent derived from the blocked isocyanate group. As a blocking agent, it can be selected according to the detachment temperature, and alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, etc. can be listed. For example, from the aspect of setting the detachment temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available products of such a compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0679] [Chemical formula 58]

[0680]

[0681] Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl The invention also includes propyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-urea propyl trialkoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

[0682] Furthermore, as the silane coupling agent, an oligomer type compound having a plurality of alkoxysilyl groups can also be used.

[0683] Examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).

[0684] [Chemical formula 59]

[0685]

[0686] In formula (S-1), R S1 represents a monovalent organic group, R S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group, and n represents an integer of 0 to 2.

[0687] R S1 It is preferably a structure containing a polymerizable group. As a polymerizable group, a group with an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, an amino group, etc. can be listed. As a group with an ethylenically unsaturated bond, a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group with an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), a (methyl) acrylamide group, a (methyl) acryloxy group, etc. can be listed, preferably vinylphenyl, (methyl) acrylamide group or (methyl) acryloxy group, more preferably vinylphenyl or (methyl) acryloxy group, further preferably (methyl) acryloxy group.

[0688] R S2 It is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.

[0689] n represents an integer of 0 to 2, and is preferably 1.

[0690] However, the structures of the repeating units represented by the formula (S-1) contained in the oligomer type compound may be the same.

[0691] Among them, among the multiple repeating units represented by formula (S-1) contained in the oligomer type compound, n is preferably 1 or 2 in at least one, more preferably 1 or 2 in at least two, and even more preferably 1 in at least two.

[0692] As such an oligomer type compound, a commercially available product can be used, and examples of the commercially available product include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0693] 〔Aluminum-based adhesive additive〕

[0694] Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[0695] As other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used, and these contents are incorporated into the present specification.

[0696] 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 further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be only one or more. When using more than two kinds, it is preferred that the total is within the above range.

[0697] <Migration Inhibitor>

[0698] The resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0699] The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring, a 6H-pyran ring, a triazine ring), compounds having thioureas and sulfhydryl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0700] Among these, the resin composition of the present invention preferably contains an azole compound.

[0701] The azole compound is a compound containing an azole structure, and the azole structure refers to a 5-membered ring structure containing a nitrogen atom as a ring member, preferably a 5-membered ring structure containing two or more nitrogen atoms as ring members. Specifically, the azole structure can include an imidazole structure, a triazole structure, a tetrazole structure, etc. Such as benzimidazole, benzotriazole, etc., these structures can form polycyclic rings with other ring structures through condensation, etc.

[0702] Furthermore, as the compound having an azole structure, a compound in which a group represented by the following formula (R-1) or the following formula (R-2) is directly bonded to the azole structure is also preferred.

[0703] [Chemical formula 60]

[0704]

[0705] In formula (R-1), R 1 represents a monovalent organic group, and * represents a bonding site to the azole structure.

[0706] In formula (R-2), R 2 represents a hydrogen atom or a monovalent organic group, R 3 represents a monovalent organic group, and * represents a bonding site to the azole structure.

[0707] In formula (R-1), R 1 It is preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - is a group represented by a bond of at least one group in R. N As described above.

[0708] The hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these.

[0709] And, R 1 The total number of carbon atoms is preferably 1-30, preferably 2-25, more preferably 3-20.

[0710] R 1 The bonding site to the carbonyl group in formula (R-1) is preferably a hydrocarbon group or -NR N -.

[0711] In the formula (R-1), * represents a bonding site to the azole structure, and is preferably a bonding site to a carbon atom which is a ring member of the azole structure.

[0712] In formula (R-2), R 2 Preferred is a hydrogen atom.

[0713] In R 2 When R is a monovalent organic group, 2 It is preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - is a group represented by a bond of at least one group in R. N As described above.

[0714] The hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these.

[0715] And, in R 2 In the case of a monovalent organic group, the total number of carbon atoms is preferably 1 to 30, preferably 2 to 25, and more preferably 3 to 20.

[0716] In R 2 When R is a monovalent organic group, 2 The bonding site to the nitrogen atom in formula (R-2) is preferably a hydrocarbon group or -C(=0)-.

[0717] In formula (R-2), R 3 is a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - is a group represented by a bond of at least one group in R. N As described above.

[0718] The hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these.

[0719] And, in R 3 In the case of a monovalent organic group, the total number of carbon atoms is preferably 1 to 30, preferably 2 to 25, and more preferably 3 to 20.

[0720] R 3 The bonding site to the nitrogen atom in formula (R-2) is preferably a hydrocarbon group or -C(=O)-.

[0721] In the formula (R-2), * represents a bonding site to the azole structure, and is preferably a bonding site to a carbon atom which is a ring member of the azole structure.

[0722] As the migration inhibitor, an ion capture agent that captures anions such as halogen ions may also be used.

[0723] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015 / 199219, etc. can be used, and these contents are incorporated into this specification.

[0724] Specific examples of the migration inhibitor include the following compounds.

[0725] [Chemical formula 61]

[0726]

[0727] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass based on the total solid content of the resin composition.

[0728] The migration inhibitor may be one or two or more. When the migration inhibitor is two or more, the total amount thereof is preferably within the above range.

[0729] <Light absorber>

[0730] The resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at an exposure wavelength decreases due to exposure.

[0731] Whether a certain compound a contained in the resin composition corresponds to a light absorber (that is, whether the absorbance at the exposure wavelength decreases due to exposure) can be determined by the following method.

[0732] First, a solution of compound a having the same concentration as that contained in the resin composition is prepared, and the molar absorption coefficient (mol -1 ·L·cm-1, also known as "molar absorption coefficient 1". ). In order to reduce the influence of changes such as a decrease in the molar absorption coefficient of compound a, the above measurement is performed as early as possible. Regarding the solvent in the above solution, when the resin composition contains a solvent, the solvent is used, and when the resin composition does not contain a solvent, N-methyl-2-pyrrolidone is used.

[0733] Next, the solution of the compound a was irradiated with exposure light at an exposure dose of 500 mJ as a cumulative dose per mol of the compound a.

[0734] Then, the molar absorption coefficient (mol -1 ·L·cm -1 , also called the "molar absorption coefficient 2". ).

[0735] The attenuation rate (%) is calculated from the above-mentioned molar absorption coefficient 1 and molar absorption coefficient 2 according to the following formula. When the attenuation rate (%) is 5% or more, compound a is judged to be a compound whose absorbance at the exposure wavelength decreases due to exposure (i.e., a light absorber).

[0736] Attenuation rate (%) = 1-molar absorption coefficient 2 / molar absorption coefficient] × 100

[0737] The attenuation rate is preferably 10% or more, and more preferably 20% or more. The lower limit of the attenuation rate is not particularly limited, and may be 0% or more.

[0738] When the resin composition is used to form a photosensitive film, the wavelength of the exposure light may be a wavelength at which the photosensitive film can be exposed.

[0739] The wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition is sensitive. The photopolymerization initiator being sensitive to a certain wavelength means that polymerization initiating species are generated when the photopolymerization initiator is exposed to light at a certain wavelength.

[0740] As for the wavelength of the above-mentioned exposure light, in relation to the light source, there can be listed (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide wavelengths (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), (6) electron beams, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc.

[0741] The wavelength of the exposure light may be any wavelength to which the photopolymerization initiator is sensitive, and is preferably h-ray (wavelength 405 nm) or i-ray (wavelength 365 nm), more preferably i-ray (wavelength 365 nm).

[0742] The light absorber may be a compound that generates a radical polymerization initiating species upon exposure, but is preferably a compound that does not generate a radical polymerization initiating species upon exposure from the viewpoint of resolution and chemical resistance.

[0743] Whether the light absorber is a compound that generates a radical polymerization initiating species upon exposure can be determined by the following method.

[0744] A solution containing a light absorber and a radical crosslinking agent at the same concentration as that contained in the resin composition is prepared. When the resin composition contains a radical crosslinking agent, the radical crosslinking agent in the solution is used at the same concentration as that of the radical crosslinking agent contained in the resin composition. When the resin composition does not contain a radical crosslinking agent, methyl methacrylate is used at a concentration 5 times that of the light absorber.

[0745] Thereafter, exposure light was irradiated, and the accumulated exposure amount was set to 500 mJ.

[0746] After exposure, the polymerization of the polymerizable compound is determined by, for example, high performance liquid chromatography. When the ratio of the molar amount of the polymerized polymerizable compound to the total molar amount of the polymerizable compound is 10% or less, the light absorber is determined to be a compound that does not generate free radical polymerization initiating species due to exposure.

[0747] The above molar ratio is preferably 5% or less, and more preferably 3% or less. The lower limit of the above molar ratio is not particularly limited, and may be 0%.

[0748] When the resin composition is used to form a photosensitive film, the wavelength of the exposure light may be a wavelength at which the photosensitive film can be exposed.

[0749] Furthermore, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity.

[0750] As compounds that generate free radical polymerization initiating species upon exposure, the same compounds as the above-mentioned photo radical polymerization initiators can be cited. When the composition contains a photo radical polymerization initiator as a light absorber, the one with the lowest polymerization initiation ability of the generated free radical species is used as the light absorber, and the others are used as photopolymerization initiators.

[0751] Examples of the compound that does not generate radical polymerization initiating species by exposure include, in addition to photoacid generators and photobase generators, pigments whose absorption wavelength changes by exposure.

[0752] Among these, the light absorber is preferably a naphthoquinonediazide compound or a dye whose absorbance changes upon exposure to light, and more preferably a naphthoquinonediazide compound.

[0753] Furthermore, as the light absorber, for example, it is also conceivable to use a photoacid generator or a photobase generator in combination with a compound whose absorbance at the exposure wavelength decreases depending on pH.

[0754] 〔Naphthoquinone diazide compounds〕

[0755] Examples of the naphthoquinonediazide compound include compounds that generate indene carboxylic acid upon exposure and whose absorbance at the exposure wavelength decreases, and compounds having a 1,2-naphthoquinonediazide structure are preferred.

[0756] The naphthoquinonediazide compound is preferably a naphthoquinonediazidesulfonic acid ester of a hydroxy compound.

[0757] The hydroxy compound is preferably a compound represented by any one of the following formulas (H1) to (H6).

[0758] [Chemical formula 62]

[0759]

[0760] In formula (H1), R 1 and R 2 Each independently represents a monovalent organic group, R 3 and R 4 Each independently represents a hydrogen atom or a monovalent organic group; n1, n2, m1 and m2 each independently represent an integer of 0 to 5; and at least one of m1 and m2 represents an integer of 1 to 5.

[0761] In formula (H2), Z represents a tetravalent organic group, L 1 , L 2 , L 3 and L 4 Each independently represents a single bond or a divalent organic group, R 5 , R 6 , R 7 and R 8 Each independently represents a monovalent organic group, n3, n4, n5 and n6 each independently represent an integer of 0 to 3, m3, m4, m5 and m6 each independently represent an integer of 0 to 2, and at least one of m3, m4, m5 and m6 represents 1 or 2.

[0762] In formula (H3), R 9 and R 10 Each independently represents a hydrogen atom or a monovalent organic group, L 5 Each independently represents a divalent organic group, and n7 represents an integer of 3-8.

[0763] In formula (H4), L 6 Represents a divalent organic group, L 7 and L 8 Each independently represents a divalent organic group containing an aliphatic tertiary or quaternary carbon.

[0764] In formula (H5), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, L 9 , L 10 and L 11Each independently represents a single bond or a divalent organic group; m7, m8, m9, and m10 each independently represent an integer of 0 to 2; and at least one of m7, m8, m9, and m10 is 1 or 2.

[0765] In formula (H6), R 42 , R 43 , R 44 and R 45 Each independently represents a hydrogen atom or a monovalent organic group, R 46 and R 47 Each independently represents a monovalent organic group, n16 and n17 each independently represent an integer of 0 to 4, m11 and m12 each independently represent an integer of 0 to 4, and at least one of m11 and m12 is an integer of 1 to 4.

[0766] In formula (H1), R 1 and R 2 Each of R is preferably independently a monovalent organic group having 1 to 60 carbon atoms, and more preferably a monovalent organic group having 1 to 30 carbon atoms. 1 and R 2 The monovalent organic group in the ' includes a hydrocarbon group which may have a substituent, for example, an aromatic hydrocarbon group which may have a substituent such as a hydroxyl group, and the like.

[0767] In formula (H1), R 3 and R 4 Each of R is independently preferably a monovalent organic group having 1 to 60 carbon atoms, and more preferably a monovalent organic group having 1 to 30 carbon atoms. 3 and R 4 The monovalent organic group in the ' may be a hydrocarbon group which may have a substituent, for example, a hydrocarbon group which may have a substituent such as a hydroxyl group, etc.

[0768] In formula (H1), n1 and n2 are preferably 0 or 1, and more preferably 0, respectively and independently.

[0769] In formula (H1), it is preferred that both m1 and m2 are 1.

[0770] The compound represented by formula (H1) is preferably a compound represented by any one of formula (H1-1) to formula (H1-5).

[0771] [Chemical formula 63]

[0772]

[0773] In formula (H1-1), R 21 , R 22 and R 23Each independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a group represented by the following formula (R-1).

[0774] [Chemical formula 64]

[0775]

[0776] In formula (R-1), R 29 represents a hydrogen atom, an alkyl group or an alkoxy group, n13 represents an integer of 0 to 2, and * represents a bonding site with other structures.

[0777] In (H1-1), n8, n9 and n10 each independently represent an integer of 0 to 2, and preferably 0 or 1.

[0778] In formula (H1-2), R 24 represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. n14, n15, and n16 each independently represent an integer of 0 to 2. 30 represents a hydrogen atom or an alkyl group.

[0779] In formula (H1-3), R 25 , R 26 , R 27 and R 28 Preferably, each independently represents a monovalent organic group, a hydrogen atom, an alkyl group or a group represented by the above formula (R-1).

[0780] In formula (H1-3), n11, n12 and n13 each independently represent an integer of 0 to 2, and preferably 0 or 1.

[0781] The compound represented by the formula (H1-1) is preferably a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4).

[0782] The compound represented by the formula (H1-2) is preferably a compound represented by the following formula (H1-2-1) or (H1-2-2).

[0783] As the compound represented by the formula (H1-3), compounds represented by the following formulas (H1-3-1) to (H1-3-3) are preferred.

[0784] [Chemical formula 65]

[0785]

[0786] In formula (H2), Z is preferably a tetravalent group having 1 to 20 carbon atoms, and more preferably a group represented by any of the following formulae (Z-1) to (Z-4). In the following formulae (Z-1) to (Z-4), * represents a bonding site to another structure.

[0787] [Chemical formula 66]

[0788]

[0789] In formula (H2), L 1 , L 2 , L 3 and L 4 Preferably, they are each independently a single bond or a methylene group.

[0790] In formula (H2), R 5 , R 6 , R 7 and R 8 Preferably, each independently is an organic group having 1 to 30 carbon atoms.

[0791] In formula (H2), n3, n4, n5 and n6 are preferably integers of 0 to 2, more preferably 0 or 1, respectively and independently.

[0792] In formula (H2), m3, m4, m5 and m6 are preferably 1 or 2, more preferably 1, respectively and independently.

[0793] Examples of the compound represented by formula (H2) include compounds having the following structures.

[0794] [Chemical formula 67]

[0795]

[0796] In formula (H3), R 9 and R 10 Preferably, each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0797] In formula (H3), L 5 Preferably, each independently is a group represented by the following formula (L-1).

[0798] [Chemical formula 68]

[0799]

[0800] In formula (L-1), R 30 represents a monovalent organic group having 1 to 20 carbon atoms, n14 represents an integer of 1 to 5, and * represents a bonding site to other structures.

[0801] In formula (H3), n7 is preferably an integer of 4-6.

[0802] Examples of the compound represented by the formula (H3) include the following compounds. In the following formula, n each independently represents an integer of 0 to 9.

[0803] [Chemical formula 69]

[0804]

[0805] In formula (H4), L 6 Preferred is -C(CF3)2-, -S(=O)2- or -C(=O)-.

[0806] In formula (H4), L 7 and L 8 Preferably, each independently is a divalent organic group having 2 to 20 carbon atoms.

[0807] Examples of the compound represented by formula (H4) include the following compounds.

[0808] [Chemical formula 70]

[0809]

[0810] In formula (H5), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 Preferably, they are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group or an acyl group.

[0811] In formula (H5), L 9 , L 10 and L 11 Preferably, they are each independently a single bond, -O-, -S-, -S(=O)2-, -C(=O)-, -C(=O)O-, cyclopentylene, cyclohexylene, phenylene or a divalent organic group having 1 to 20 carbon atoms, and more preferably a group represented by any one of the following formulae (L-2) to (L-4).

[0812] [Chemical formula 71]

[0813]

[0814] In formula (L-2) to formula (L-4), R 31 and R 32Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R 34 , R 35 , R 36 and R 37 Each independently represents a hydrogen atom or an alkyl group, n15 is an integer from 1 to 5, and R 38 , R 39 , R 40 and R 41 Each independently represents a hydrogen atom or an alkyl group, and * represents a bonding site to other structures.

[0815] Examples of the compound represented by formula (H5) include the following compounds.

[0816] [Chemical formula 72]

[0817]

[0818] In formula (H6), R 42 , R 43 , R 44 and R 45 Preferably, each independently represents a hydrogen atom or a monovalent organic group, a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0819] In formula (H6), R 46 and R 47 Preferably, they are each independently an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group.

[0820] In formula (H6), n16 and n17 are preferably integers of 0 to 2, and more preferably 0 or 1, respectively and independently.

[0821] In formula (H6), n16 and n17 are preferably integers of 1 to 3, and more preferably 2 or 3, respectively and independently.

[0822] Examples of the compound represented by formula (H6) include the following compounds.

[0823] [Chemical formula 73]

[0824]

[0825] Examples of the hydroxy compound include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,4,6,3′,4′-pentahydroxybenzophenone, 2,3,4,2′,4′-pentahydroxybenzophenone, 2,3,4,2′,5′-pentahydroxybenzophenone, 2,4,6,3′,4′,5′-hexahydroxybenzophenone and 2,3,4,3′,4′,5′-hexahydroxybenzophenone;

[0826] Polyhydroxyphenyl alkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenylpentanone, 2,3,4-trihydroxyphenylhexanone,

[0827] Bis((poly)hydroxyphenyl)alkanes such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane-1, bis(2,3,4-trihydroxyphenyl)propane-1, nordihydroretic acid, 1,1-bis(4-hydroxyphenyl)cyclohexane,

[0828] Polyhydroxybenzoates such as propyl 3,4,5-trihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate,

[0829] Bis(2,3,4-trihydroxybenzoyl)methane, bis(3-acetyl-4,5,6-trihydroxyphenyl)methane, bis(2,3,4-trihydroxybenzoyl)benzene, bis(2,4,6-trihydroxybenzoyl)benzene and other bis(polyhydroxybenzoyl)alkanes or bis(polyhydroxybenzoyl)aryls,

[0830] Alkylene-bis(polyhydroxybenzoates) such as ethylene glycol-bis(3,5-dihydroxybenzoate) and ethylene glycol-bis(3,4,5-trihydroxybenzoate),

[0831] Polyhydroxybiphenyls such as 2,3,4-biphenyltriol, 3,4,5-biphenyltriol, 3,5,3′,5′-biphenyltetraol, 2,4,2′,4′-biphenyltetraol, 2,4,6,3′,5′-biphenylpentaol, 2,4,6,2′,4′,6′-biphenylhexanol, 2,3,4,2′,3′,4′-biphenylhexanol,

[0832] 4,4'-thiobis(1,3-dihydroxy)benzene and other bis(polyhydroxy)sulfides,

[0833] 2,2',4,4'-Tetrahydroxydiphenyl ether and other bis(polyhydroxyphenyl) ethers,

[0834] 2,2',4,4'-tetrahydroxydiphenyl sulfoxide and other bis(polyhydroxyphenyl) sulfoxides,

[0835] 2,2',4,4'-diphenyl sulfone and other bis(polyhydroxyphenyl) sulfones,

[0836] tris(4-hydroxyphenyl)methane, 4,4′,4"-trihydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',3",4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy-phenol, 4,4'-(3,4-diol-benzylidene)bis[2,6-dimethylphenol], 4,4'-[(2-hydroxy-phenyl)methylene]bis[2-cyclohexyl-5-methylphenol, 4,4',2",3",4"-pentahydroxy-3,5,3' , 5′-tetramethyltriphenylmethane, 2,3,4,2′,3′,4′-hexahydroxy-5,5′-diacetyltriphenylmethane, 2,3,4,2′,3′,4′,3″,4″-octahydroxy-5,5′-diacetyltriphenylmethane, 2,4,6,2′,4′,6′-hexahydroxy-5,5′-dipropionyltriphenylmethane and the like polyhydroxytriphenylethanes, 4,4′-(phenylmethylene)bisphenol, 4,4′-(1-phenyl-ethylene)bis[2-methylphenol], 4,4′,4″-ethylene-triphenol and the like,

[0837] Polyhydroxyspirobis-indanes such as 3,3,3′,3′-tetramethyl-1,1′-spirobis-indanes-5,6,5′,6′-tetraol, 3,3,3′,3′-tetramethyl-1,1′-spirobis-indanes-5,6,7,5′,6′,7′-hexanol, 3,3,3′,3′-tetramethyl-1,1′-spirobis-indanes-4,5,6,4′,5′,6′-hexanol, 3,3,3′,3′-tetramethyl-1,1′-spirobis-indanes-4,5,6,5′,6′,7′-hexanol, and polyhydroxyspirobis-indanes such as 2,4,4-trimethyl-2′,4′,7′-trihydroxyflavanes,

[0838] Polyhydroxyphthalide lactones such as 3,3-bis(3,4-dihydroxyphenyl)phthalide, 3,3-bis(2,3,4-trihydroxyphenyl)phthalide, 3′,4′,5′,6′-tetrahydroxybis[phthalide-3,9′-xanthen], flavonoid pigments such as morin, quercetin, and rutin,

[0839] α,α',α"-tris(4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-dimethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-diethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-di-n-propyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-di-n-propyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-di-n-butyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3-methyl- 4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α',α"-tri(3-methoxy-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α',α"-tri(2,4-dihydroxyphenyl) 1,3,5-triisopropylbenzene, 1,3,5-tri(3,5-dimethyl-4-hydroxyphenyl)benzene, 1,3,5-tri(5-methyl-2-hydroxyphenyl)benzene, 2,4,6-tri(3,5-dimethyl-4-hydroxyphenylthiomethyl)-mesitylene, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(4'-hydroxyphenyl)ethyl]-3-[ α,α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3',5'-dimethyl-4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(3",5"-dimethyl-4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(3'-methyl-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3"-methyl-4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3'-methoxy-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3"-methoxy-4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(2',4'-dihydroxyphenyl)ethyl]-4-[ polyhydroxy compounds described in Japanese Patent Application Laid-Open No. 4-253058, such as α',α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(2',4'-dihydroxyphenyl)ethyl]-3-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene, polyhydroxy compounds described in Japanese Patent Application Laid-Open No. 5-224410, such as α,α,α',α',α",α"-hexa-(4-hydroxyphenyl)-1,3,5-triethylbenzene, polyhydroxy compounds described in Japanese Patent Application Laid-Open No. 5-303200, EP-530148, such as 1,2,2,3-tetra(p-hydroxyphenyl)propane and 1,3,3,5-tetra(p-hydroxyphenyl)pentane,

[0840] p-Bis(2,3,4-trihydroxybenzoyl)benzene, p-Bis(2,4,6-trihydroxybenzoyl)benzene, m-Bis(2,3,4-trihydroxybenzoyl)benzene, m-Bis(2,4,6-trihydroxybenzoyl)benzene, p-Bis(2,5-dihydroxy-3-bromobenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-methylbenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-methoxybenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-nitrobenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5 -cyanobenzoyl)benzene, 1,3,5-tris(2,5-dihydroxybenzoyl)benzene, 1,3,5-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,3-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4,5-tetrakis(2,3,4-trihydroxybenzoyl)benzene, α,α'-bis(2,3,4-trihydroxybenzoyl)p-xylene, α,α',α'-tris(2,3,4-trihydroxybenzoyl)mesitylene,

[0841] 2,6-bis-(2-hydroxy-3,5-dimethylbenzyl)-p-cresol, 2,6-bis-(2-hydroxy-5′-methylbenzyl)-p-cresol, 2,6-bis-(2,4,6-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-3,5-dimethyl-phenol, 4,6-bis-(4-hydroxy-3,5-dimethylbenzyl)-galactol, 2,6-bis-(4 4,6-bis-(2,4,6-trihydroxybenzyl)-2,4-dimethylphenol, 4,6-bis-(2,3,4-trihydroxybenzyl)-2,5-dimethylphenol, 2,6-bis-(4-hydroxybenzyl)-p-cresol, 2,6-bis(4-hydroxybenzyl)-4-cyclohexylphenol, 2,6-bis(4-hydroxy-3-methylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-3,5 -dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-2,5-dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-3-methylbenzyl)-4-phenyl-phenol, 2,2′,6,6′-tetrakis[(4-hydroxyphenyl)methyl]-4,4′-methylenediphenol, 2,2′,6,6′-tetrakis[(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4′-methylenediphenol, 2,2′,6,6′-tetrakis[(4-hydroxy- 3-methylphenyl)methyl]-4,4′-methylenediphenol, 2,2′-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]6,6′-dimethyl-4,4′-methylenediphenol, 2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobis(1H-indene)-5,5′,6,6′,7,7′hexanol, bis(4-hydroxy-3,5-dimethylphenyl)methyl]-(4-hydroxy-3-methoxyphenyl)methane, and the like.

[0842] Furthermore, low-nuclear forms of phenolic resins such as novolac resins can also be used.

[0843] Examples of the naphthoquinonediazidesulfonic acid include 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, and these may be used in combination.

[0844] The method for producing the naphthoquinonediazidesulfonic acid ester of a hydroxy compound is not particularly limited, and it can be obtained, for example, by sulfonylation of naphthoquinonediazidesulfonic acid with chlorosulfonic acid or thionyl chloride and condensation reaction of the obtained naphthoquinonediazidesulfonyl chloride with a hydroxy compound.

[0845] For example, it can be obtained by reacting a hydroxy compound with a predetermined amount of naphthoquinonediazidesulfonyl chloride in a solvent such as dioxane, acetone or tetrahydrofuran in the presence of a basic catalyst such as triethylamine to carry out esterification, and washing and drying the obtained product.

[0846] The esterification rate of naphthoquinone diazide sulfonic acid ester is not particularly limited, but is preferably 10% or more, and more preferably 20% or more. The upper limit of the esterification rate is not particularly limited, and may be 100%.

[0847] The above esterification rate can be expressed as the ratio of esterified groups in the hydroxyl groups of the hydroxyl compound. 1 Confirmed by H-NMR etc.

[0848] Furthermore, as the light absorber, the compounds described in paragraphs 0088 to 0108 of JP-A-2019-206689 can also be used.

[0849] The content of the light absorber based on the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass.

[0850] In particular, in terms of improving adhesion to the substrate, the resin composition of the present invention further preferably contains the above-mentioned azole compound and the above-mentioned silane coupling agent. By containing these compounds, it is easy to maintain adhesion to the substrate even after the cured product is exposed under high temperature and high humidity conditions.

[0851] <Polymerization Inhibitor>

[0852] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0853] Specific examples of the polymerization inhibitor include compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. This content is incorporated into this specification.

[0854] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass based on the total solid content of the resin composition.

[0855] The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is used in combination of two or more, the total amount thereof is preferably within the above range.

[0856] <Other additives>

[0857] The resin composition of the present invention can also contain various additives as required, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, light acid generators, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliary agents (such as defoamers, flame retardants, etc.) within the scope of the effect of the present invention. By appropriately containing these components, properties such as film physical properties can be adjusted. About these components, for example, the records of the 0183rd paragraph after (the 0237th paragraph of the corresponding U.S. Patent Application Publication No. 2013 / 0034812 specification) of Japanese Patent Application Publication No. 2008-250074, the records of the 0101~0104, 0107~0109 paragraphs, etc., can be referenced to the Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated into this specification. When these additives are blended, it is preferred that the total content is set to less than 3% by mass of the solid content of the resin composition of the present invention.

[0858] 〔Inorganic particles〕

[0859] Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0860] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[0861] The above average particle size of the inorganic particles is a primary particle size and a volume average particle size. The volume average particle size can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (NIKKISO C0., LTD. system).

[0862] When the above measurement is difficult to perform, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.

[0863] 〔Organotitanium compounds〕

[0864] Since the resin composition contains the organic titanium compound, a resin layer having excellent chemical resistance can be formed even when the resin composition is cured at a low temperature.

[0865] Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0866] Specific examples of the organic titanium compound are shown in the following I) to VII):

[0867] I) Titanium chelate compound: From the aspect of excellent storage stability of the resin composition and the good curing pattern that can be obtained, titanium chelate compound having two or more alkoxy groups is more preferred. Specific examples are diisopropyl bis(triethanolamine) titanium, di(n-butyl alcohol)bis(2,4-pentanedione) titanium, diisopropyl bis(2,4-pentanedione) titanium, diisopropyl bis(tetramethylheptanedione) titanium, diisopropyl bis(ethyl acetoacetate) titanium, etc.

[0868] 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-nonoxide), titanium tetra(n-propoxide), titanium tetrastearylate, titanium tetra[bis{2,2-(allyloxymethyl)butoxide}], and the like.

[0869] III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[0870] IV) Monoalkoxy titanium compound: for example, tris(dioctyl phosphate)titanium isopropoxide, tris(dodecylphenyl sulfonate)titanium isopropoxide, and the like.

[0871] V) Titanium oxide compound: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), titanium phthalocyanine oxide, and the like.

[0872] VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

[0873] VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0874] Among them, as the organic titanium compound, from the viewpoint of exerting better chemical resistance, at least one compound selected from the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound is preferred. In particular, bis(ethyl acetoacetate)titanium diisopropylate, tetra(n-butoxide)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0875] When an organic titanium compound is contained, the content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when the content is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0876] As other additives, compounds described in paragraphs 0316 to 0358 of International Publication No. 2022 / 145355 can be mentioned. The above description is incorporated into the present specification.

[0877] <Characteristics of Resin Composition>

[0878] The viscosity of the resin composition of the present invention can be adjusted according to the solid content concentration of the resin composition. From the aspect of the coating film thickness, it is preferably 1,000 mm 2 / s~12,000mm 2 / s, more preferably 2,000mm 2 / s~10,000mm 2 / s, more preferably 2,500mm 2 / s~8,000mm 2 / s. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000 mm 2 / s or more, it is easy to apply the film thickness required as a redistribution insulating film. If it is 12,000 mm 2 / s or less, a coating film having an excellent coating surface shape can be obtained.

[0879] When a cured product having a film thickness of 10 μm is formed using the resin composition of the present invention, the transmittance of the cured product at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more.

[0880] The upper limit of the transmittance is not particularly limited and may be 100%.

[0881] The cured product can be obtained, for example, by applying the resin composition of the present invention to a silicon wafer, drying the wafer at 100° C. for 5 minutes, and heating the wafer at 500 mJ / cm 2 After the entire surface was exposed by i-rays at an exposure energy of , the temperature was increased at a rate of 10° C. / min in a nitrogen atmosphere, and heated at 230° C. for 180 minutes.

[0882] <Restrictions on substances contained in the resin composition>

[0883] 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 further preferably less than 1.0% by mass. When the water content is less than 2.0%, the storage stability of the resin composition is improved.

[0884] Examples of methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0885] From the perspective of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As metals, sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc. can be listed, but metals contained as complexes of organic compounds and metals are excluded. When containing multiple metals, it is preferred that the total of these metals is within the above range.

[0886] In addition, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following methods can be listed: selecting raw materials with a low metal content as raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the device with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.

[0887] Regarding the resin composition of the present invention, if the use as a semiconductor material is considered, from the aspect of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm. Among them, the content in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be listed. The total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is preferably within the above ranges, respectively.

[0888] As a method for adjusting the content of halogen atoms, preferably, an ion exchange treatment or the like is used.

[0889] As a storage container for the resin composition of the present invention, a conventionally known storage container can be used. As a storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the resin composition of the present invention, a multilayer bottle having an inner wall of the container composed of six kinds of six layers of resins or a bottle having a seven-layer structure composed of six kinds of resins is preferably used. As such a container, for example, a container described in Japanese Patent Publication No. 2015-123351 can be cited.

[0890] <Cured product of resin composition>

[0891] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0892] The cured product of the present invention is a cured product obtained by curing the resin composition.

[0893] The curing of the resin composition is preferably carried out by heating, and the heating temperature is more preferably 120°C to 400°C, further 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 a film, rod, spherical, granular, etc. can be selected according to the purpose. In the present invention, the cured product is preferably in the form of a film. Through the pattern processing of the resin composition, the shape of the cured product can also be selected according to the purpose of forming a protective film on the wall, forming a conductive through hole, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film composed of the cured product) is preferably 0.5μm or more and 150μm or less.

[0894] The shrinkage rate when curing the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less. The shrinkage rate refers to the percentage of volume change before and after curing of the resin composition, and can be calculated by the following formula.

[0895] Shrinkage rate [%] = 100-(volume after curing ÷ volume before curing) × 100

[0896] <Characteristics of Cured Product of Resin Composition>

[0897] 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. When it is 70% or more, the cured product may have excellent mechanical properties.

[0898] 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.

[0899] 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.

[0900] The transmittance of the cured product at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and further preferably 25% or more.

[0901] The upper limit of the transmittance is not particularly limited and may be 100%.

[0902] <Preparation of resin composition>

[0903] 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 performed by a conventionally known method.

[0904] Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing while rotating a pot.

[0905] The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0906] For the purpose of removing foreign matter such as dust or particles in the resin composition of the present invention, it is preferred to filter using a filter. Regarding the filter pore size, for example, it is preferably less than 5 μm, more preferably less than 1 μm, further preferably less than 0.5 μm, and further preferably less than 0.1 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. In the case where the material of the filter is polyethylene, HDPE (high-density polyethylene) is more preferably used. The filter can be pre-cleaned with an organic solvent. In the filtering process of the filter, a variety of filters can be connected in series or in parallel for use. In the case of using a variety of filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, the following method can be cited: a HDPE filter with a pore size of 1 μm is used as the first section, and a HDPE filter with a pore size of 0.2 μm is used as the second section, and the two are connected in series. In addition, various materials can be filtered multiple times. In the case of filtering multiple times, it can be a circulation filter. In addition, pressure filtration can be performed. When filtering is performed by pressurization, the pressure applied is, for example, preferably 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, further preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa.

[0907] In addition to filtering using a filter, impurity removal using an adsorbent may also be performed. Filter filtering and impurity removal using an adsorbent may also be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be cited.

[0908] After filtering with a filter, the resin composition filled in the bottle may be placed under reduced pressure for degassing.

[0909] (Method for producing cured product)

[0910] The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0911] The method for producing a cured product more preferably includes the film forming step, an exposure step of selectively exposing the film formed in the film forming step, and a developing step of developing the film exposed in the exposure step with a developer to form a pattern.

[0912] The method for producing a cured product includes the film forming step, the exposure step, the developing step, and preferably at least one of a heating step of heating the pattern obtained by the developing step and a post-development exposure step of exposing the pattern obtained by the developing step.

[0913] Furthermore, it is also preferable that the method for producing a cured product includes the above-mentioned film forming step and the step of heating the above-mentioned film.

[0914] Hereinafter, the details of each step will be described.

[0915] <Film Formation Step>

[0916] The resin composition of the present invention can be used in a film forming step of applying the composition to a substrate to form a film.

[0917] The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0918] 〔Base material〕

[0919] The type of substrate can be appropriately determined according to the purpose and is not particularly limited. As the substrate, there can be cited semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, deposited film, magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates (for example, any one of the substrates formed by metal and the substrates with a metal layer formed by plating, deposition, etc.), paper, SOG (Spin On Glass: Spin-on Glass), TFT (Thin Film Transistor) array substrate, molded substrate, plasma display panel (PDP) electrode plate, etc. The substrate is particularly preferably a semiconductor manufacturing substrate, more preferably a silicon substrate, a Cu substrate and a molded substrate.

[0920] On the surface of these substrates, a layer such as an adhesion layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided.

[0921] The shape of the substrate is not particularly limited, and may be circular or rectangular.

[0922] Regarding the size of the substrate, for example, if the substrate is circular, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm, and for example, if the substrate is rectangular, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm.

[0923] As the substrate, for example, a plate-shaped substrate (substrate) can be used, and preferably a panel-shaped substrate (substrate) is used.

[0924] When a film is formed by applying the resin composition to the surface of a resin layer (for example, a layer composed of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as a substrate.

[0925] As a method of applying the resin composition to the substrate, coating is preferred.

[0926] As the mechanism used, specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet can be cited. From the aspect of uniformity of film thickness, preferably spin coating, slit coating, spray coating or inkjet, from the aspect of uniformity of film thickness and productivity, more preferably spin coating and slit coating. According to the method used, the solid content concentration or coating conditions of the resin composition are adjusted, thereby a film of the desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, it is preferably spin coating or spray coating, inkjet, etc. If it is a rectangular substrate, it is preferably slit coating, spray coating, inkjet, etc. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.

[0927] Furthermore, a method of transferring a coating film formed on a temporary support body in advance by the above-mentioned imparting method to a substrate can also be applied.

[0928] As the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used.

[0929] Furthermore, a process of removing excess film at the edge of the substrate may be performed. Examples of such a process include edge bead rinse (EBR) and backside rinse.

[0930] A pre-wetting step may be adopted in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0931] <Drying process>

[0932] After the film forming step (layer forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent.

[0933] 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.

[0934] The drying step is preferably performed after the film forming step and before the exposure step.

[0935] The drying temperature of the film in the drying step is preferably 50 to 150° C., more preferably 70 to 130° C., and further preferably 90 to 110° C. Furthermore, the drying can be performed by reducing pressure. The drying time can be exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0936] <Exposure Process>

[0937] The film may be subjected to an exposure step of selectively exposing the film.

[0938] The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film forming step.

[0939] Selective exposure refers to exposing a portion of the film to light, and by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.

[0940] The exposure amount is not particularly limited as long as it can cure the resin composition of the present invention, and is preferably 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 , more preferably 200 to 8,000 mJ / cm 2 .

[0941] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0942] Regarding the exposure wavelength, in relation to the light source, there can be mentioned (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), wide wavelengths (three wavelengths of g, h, and i-rays), (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, (7) second harmonics of YAG lasers of 532 nm and third harmonics of 355 nm, etc. With regard to the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and exposure using i-rays is more preferred from the viewpoint of exposure sensitivity.

[0943] The exposure method is not particularly limited as long as at least a part of the film composed of the resin composition of the present invention is exposed, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0944] <Post-exposure heating process>

[0945] The film may be subjected to a step of heating after exposure (post-exposure heating step).

[0946] That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.

[0947] The post-exposure heating step can be performed after the exposure step and before the development step.

[0948] The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.

[0949] The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0950] The temperature increase rate in the post-exposure heating step is preferably 1 to 12° C. / min, more preferably 2 to 10° C. / min, and even more preferably 3 to 10° C. / min from the temperature at the start of heating to the maximum heating temperature.

[0951] Furthermore, the heating rate can be appropriately changed during the heating process.

[0952] The heating method in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.

[0953] Furthermore, during heating, it is also preferred to flow an inert gas such as nitrogen, helium, or argon in an environment with a low oxygen concentration.

[0954] <Development Process>

[0955] The film after exposure may be subjected to a developing step of developing with a developer to form a pattern.

[0956] That is, the method for producing a cured product of the present invention may include a developing step of developing the film exposed in the exposing step using a developing solution to form a pattern.

[0957] By performing development, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern.

[0958] Here, development in which the non-exposed portion of the film is removed by the development step is referred to as negative development, and development in which the exposed portion of the film is removed by the development step is referred to as positive development.

[0959] 〔Developer〕

[0960] As the developer used in the development step, a developer containing an alkaline aqueous solution or an organic solvent can be mentioned.

[0961] When the developer is an alkaline aqueous solution, examples of the alkaline compound that the alkaline aqueous solution may contain include inorganic bases, 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, tetrapropylamine hydroxide, tetrabutylamine hydroxide, tetrapentylamine hydroxide, tetrahexylamine hydroxide, tetraoctylamine hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferred is TMAH. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total amount of the developer.

[0962] When the developer contains an organic solvent, the compound described in paragraph 0387 of International Publication No. 2021 / 112189 can be used as the organic solvent. This content is incorporated into this specification. In addition, as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc. can also be preferably listed, and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can also be preferably listed.

[0963] Furthermore, when the developer contains an organic solvent, the organic solvent may be used alone or in a mixture of two or more. In the present invention, a developer containing at least one selected from cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is particularly preferred, a developer containing at least one selected from cyclopentanone, γ-butyrolactone and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0964] 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, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content may also be 100% by mass.

[0965] When the developer contains an organic solvent, the developer may further contain at least one of an alkaline compound and an alkali generator. When at least one of the alkaline compound and the alkali generator in the developer penetrates into the pattern, the performance of the pattern such as elongation at break may be improved.

[0966] As the basic compound, an organic base is preferred from the viewpoint of reliability when remaining in a film after curing (adhesion to a substrate when the cured product is further heated).

[0967] As the basic compound, a basic compound having an amino group is preferred, preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. In order to promote the imidization reaction, it is preferably a primary amine, a secondary amine, a tertiary amine or an ammonium salt, more preferably a secondary amine, a tertiary amine or an ammonium salt, further preferably a secondary amine or a tertiary amine, and especially preferably a tertiary amine.

[0968] The basic compound is preferably one that is unlikely to remain in the cured film (the obtained cured product) from the perspective of mechanical properties (elongation at break) of the cured product, and is preferably one whose remaining amount is unlikely to decrease due to vaporization or the like before heating from the perspective of promoting cyclization.

[0969] Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and further preferably 100°C to 230°C at normal pressure (101, 325 Pa).

[0970] The boiling point of the basic compound is higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent preferably contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.

[0971] For example, when the boiling point of the organic solvent is 100° C., the boiling point of the basic compound used is preferably 80° C. or higher, and more preferably 100° C. or higher.

[0972] The developer may contain only one kind of basic compound or two or more kinds thereof.

[0973] Specific examples of the basic compound 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, butylenediamine, 1,5-diaminopentane, N-methylhexylamine, N -methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, fine triamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamineethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propylenediamine, etc.

[0974] Preferred embodiments of the base generator are the same as those of the base generator contained in the above-mentioned composition. In particular, the base generator is preferably a thermal base generator.

[0975] When the developer contains at least one of an alkaline compound and an alkali generator, the content of the alkaline compound or the alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the developer. The lower limit of the above content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[0976] When the alkaline compound or the base generator is solid in an environment where the developer is used, the content of the alkaline compound or the base generator is preferably 70 to 100% by mass based on the total solid content of the developer.

[0977] The developer may contain only one or more of the alkaline compound and the alkali generator. When the alkaline compound and the alkali generator are two or more, the total amount thereof is preferably within the above range.

[0978] The developer may further contain other components.

[0979] As other components, a well-known surfactant, a well-known defoaming agent, etc. are mentioned, for example.

[0980] [Developer supply method]

[0981] As long as the desired pattern can be formed, the method of supplying the developer is not particularly limited, and there are the following methods: a method of immersing the substrate formed with a film in the developer, a method of using a nozzle to supply the developer to the film formed on the substrate by immersion development, or 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, a spray nozzle, and the like.

[0982] From the perspective of the permeability of the developer, the removability of the non-image area, and the efficiency in manufacturing, the method of supplying the developer using a straight nozzle or the method of continuously supplying the developer using a spray nozzle is preferred. From the perspective of the permeability of the developer to the image area, the method of supplying the developer using a spray nozzle is more preferred.

[0983] In addition, the following process can be adopted: after continuously supplying the developer with a straight nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a straight nozzle again, and the substrate is rotated to remove the developer from the substrate. This process can also be repeated multiple times.

[0984] Examples of a method for supplying the developer in the development step include a step of continuously supplying the developer to the substrate, a step of keeping the developer substantially stationary on the substrate, a step of vibrating the developer on the substrate using ultrasonic waves or the like, and a combination of these steps.

[0985] The development time is preferably 10 seconds to 10 minutes, and 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, and more preferably 18 to 30°C.

[0986] In the development step, the pattern may be cleaned (rinsed) with a rinse liquid after the processing with the developer. Alternatively, a method may be adopted in which the rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0987] 〔Rinsing fluid〕

[0988] When the developer is an alkaline aqueous solution, water can be used as the rinse liquid, for example. When the developer is a developer containing an organic solvent, 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.

[0989] Examples of the organic solvent in the case where the rinse solution contains an organic solvent include the same organic solvents as exemplified in the case where the developer contains an organic solvent.

[0990] The organic solvent contained in the rinse solution is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent having a lower solubility in the pattern than the organic solvent contained in the developer.

[0991] When the rinse liquid 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, PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, PGME, and even more preferably cyclohexanone and PGMEA.

[0992] When the rinse liquid contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more relative to the total mass of the rinse liquid. Furthermore, the organic solvent may be 100% by mass relative to the total mass of the rinse liquid.

[0993] The rinse solution may contain at least one of a basic compound and an alkali generator.

[0994] Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains at least one of an organic solvent, a basic compound, and an alkali generator is also one of the preferred embodiments of the present invention.

[0995] Examples of the alkaline compound and the alkaline generator contained in the rinse solution include the alkaline compounds and the compounds exemplified as the alkaline generator that may be contained in the developer containing an organic solvent, and preferred embodiments are also the same.

[0996] The basic compound and the base generating agent contained in the rinsing liquid may be selected in consideration of their solubility in the solvent in the rinsing liquid.

[0997] When the rinse liquid contains at least one of a basic compound and an alkali generator, the content of the basic compound or the alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the rinse liquid. The lower limit of the above content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[0998] When the basic compound or the base generator is solid in the environment where the rinse liquid is used, the content of the basic compound or the base generator is preferably 70 to 100% by mass based on the total solid content of the rinse liquid.

[0999] When the rinse liquid contains at least one of an alkaline compound and an alkali generator, the rinse liquid may contain only one alkaline compound and at least one of an alkali generator, or may contain at least two or more alkaline compounds and at least one of an alkali generator. When at least one of an alkaline compound and an alkali generator is two or more, it is preferred that the total amount thereof is within the above range.

[1000] The rinse solution may also contain other ingredients.

[1001] As other components, a well-known surfactant, a well-known defoaming agent, etc. are mentioned, for example.

[1002] [Method of supplying flushing fluid]

[1003] As long as the desired pattern can be formed, there is no particular limitation on the method for supplying the rinsing liquid, and the following methods are available: a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate through a liquid pile, a method of supplying the rinsing liquid to the substrate through spraying, and a method of continuously supplying the rinsing liquid to the substrate through a straight nozzle or the like.

[1004] From the perspective of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, it is preferred to use a method of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying using a spray nozzle. From the perspective of the permeability of the rinse liquid to the image area, it is more preferred to use a method of supplying using a spray nozzle. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.

[1005] That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle.

[1006] The method for supplying the rinsing liquid in the rinsing step may include a step of continuously supplying the rinsing liquid to the substrate, a step of maintaining the rinsing liquid in a substantially static state on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound or the like, and a combination of these steps.

[1007] 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.

[1008] In the development process, after processing with a developer or after cleaning the pattern with a rinse solution, a process of bringing the treatment solution into contact with the pattern may be included. In addition, a method of supplying the treatment solution before the developer or rinse solution in contact with the pattern is completely dried may also be adopted.

[1009] Examples of the treatment liquid include a treatment liquid containing at least one of water and an organic solvent and at least one of a basic compound and an alkali generator.

[1010] Preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator are the same as preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator used in the rinse liquid.

[1011] The method for supplying the processing liquid to the pattern can be the same method as the method for supplying the rinse liquid, and the preferred aspects are also the same.

[1012] The content of the basic compound or base generating agent in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment liquid. The lower limit of the content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[1013] Furthermore, when the basic compound or the base generating agent is solid in the environment where the treatment liquid is used, the content of the basic compound or the base generating agent is preferably 70 to 100% by mass based on the total solid content of the treatment liquid.

[1014] When the treatment liquid contains at least one of an alkaline compound and an alkali generator, the treatment liquid may contain only one alkaline compound and at least one of the alkali generators, or may contain two or more alkaline compounds and at least one of the alkali generators. When at least one of the alkaline compound and the alkali generator is two or more, it is preferred that the total amount thereof is within the above range.

[1015] <Heating process>

[1016] The pattern obtained by the development step (the pattern after the rinsing step when the rinsing step is performed) can be subjected to a heating step of heating the pattern obtained by the development.

[1017] 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.

[1018] Furthermore, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a development step or a film obtained by a film forming step.

[1019] In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as a polyimide.

[1020] Furthermore, crosslinking of unreacted crosslinking groups in the specific resin or the crosslinking agent other than the specific resin is also performed.

[1021] The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, further preferably 160 to 250°C, particularly preferably 160 to 230°C.

[1022] The heating step is preferably a step of accelerating the cyclization reaction of the polyimide precursor in the pattern by the action of a base generated by the base generating agent.

[1023] The heating in the heating process is preferably performed at a heating rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The heating rate is more preferably 2 to 10°C / min, and further preferably 3 to 10°C / min. By setting the heating rate to 1°C / min or more, productivity can be ensured and excessive volatilization of the acid or solvent can be prevented. By setting the heating rate to 12°C / min or less, the residual stress of the cured product can be relaxed.

[1024] In the case of an oven capable of rapid heating, the temperature is preferably increased at a rate of 1 to 8° C. / second from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7° C. / second, and even more preferably 3 to 6° C. / second.

[1025] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further 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 to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, it is preferably the temperature of the dried film (layer), for example, starting from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[1026] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[1027] In particular, when a multilayer laminate is formed, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, further preferably 100° C. or higher, and particularly preferably 120° C. or higher from the viewpoint of interlayer adhesion.

[1028] The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and further preferably 240°C or lower.

[1029] Heating can be performed in stages. As an example, the following process can be performed: heating from 25°C to 120°C at 3°C / min and maintaining at 120°C for 60 minutes, heating from 120°C to 180°C at 2°C / min and maintaining at 180°C for 120 minutes. In addition, as described in the specification of U.S. Patent No. 9159547, it is also preferred to treat while irradiating with ultraviolet rays. The properties of the film can be improved by this pretreatment process. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process can be set as a process of more than two stages, for example, the first stage pretreatment process can be performed in the range of 100 to 150°C, and then the second stage pretreatment process can be performed in the range of 150 to 200°C.

[1030] Furthermore, the heating may be followed by cooling, and the cooling rate at this time is preferably 1 to 5° C. / min.

[1031] The heating step is preferably performed in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[1032] The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[1033] <Exposure Step after Development>

[1034] The pattern obtained by the development step (the pattern after the rinse step when the rinse step is performed) may be subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.

[1035] 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 a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step.

[1036] In the post-development exposure step, for example, the cyclization reaction of the polyimide precursor and the like can be accelerated by the photosensitization of the photobase generator.

[1037] In the post-development exposure step, at least a portion of the pattern obtained in the development step may be exposed, and preferably the entire pattern is exposed.

[1038] The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm2 in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. 2 , more preferably 100 to 15,000 mJ / cm 2 .

[1039] The post-development exposure step can be performed, for example, using the light source in the above-mentioned exposure step, and preferably using broadband light.

[1040] <Metal Layer Formation Step>

[1041] The pattern obtained by the development step (preferably the pattern provided to at least one of the heating step and the post-development exposure step) can be provided to the metal layer forming step of forming a metal layer on the pattern.

[1042] 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 a pattern obtained by the developing step (preferably a pattern provided to at least one of the heating step and the post-development exposure step).

[1043] The metal layer is not particularly limited, and existing metals can be used. Examples thereof 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 further preferred.

[1044] The formation method of metal layer is not particularly limited, and existing method can be applied. For example, the method of recording in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical deposition method), CVD (chemical vapor deposition method), peeling (lift off), electroplating, electroless plating, etching, printing and combining these methods etc. can be considered. More specifically, the patterning method combining sputtering, photolithography and etching, the patterning method combining photolithography and electroplating can be enumerated. As the preferred mode of plating, the electroplating using copper sulfate plating solution or copper cyanide plating solution can be enumerated.

[1045] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest portion.

[1046] <Purpose>

[1047] As the fields to which the manufacturing method of the cured product of the present invention or the cured product can be applied, the insulating film of the electronic device, the interlayer insulating film for the redistribution layer, the stress buffer film, etc. can be listed. In addition, the sealing film, the substrate material (the base film or cover film of the flexible printed circuit board, the interlayer insulating film) or the case where a pattern is formed on the insulating film for the installation purpose of the above-mentioned type by etching can be listed. For these uses, for example, reference can be made to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaaki / Supervision, CMC Technical Library "Basics and Development of Polyimide Materials" issued in November 2011, Japan Polyimide Aromatic Polymer Research Association / Editor "Latest Polyimide Basics and Applications" NTS, August 2010, etc.

[1048] The method for producing a cured product of the present invention or the cured product of the present invention can also be used for the production of offset printing plates or screen printing plates, for etching of molded parts, and for the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

[1049] (Laminate and method for producing laminate)

[1050] The laminate of the present invention refers to a structure having a plurality of layers composed of the cured product of the present invention.

[1051] The laminate is a laminate including two or more layers composed of a cured product, and may be a laminate including three or more layers.

[1052] Among the two or more layers consisting of the above-mentioned cured product contained in the above-mentioned laminate, at least one layer is a layer consisting of the cured product of the present invention. From the viewpoint of suppressing the shrinkage of the cured product or the deformation of the cured product accompanying the above-mentioned shrinkage, all the layers consisting of the cured product contained in the above-mentioned laminate are also preferably layers consisting of the cured product of the present invention.

[1053] 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 a step of repeating the method for producing a cured product of the present invention a plurality of times.

[1054] The laminate of the present invention comprises two or more layers consisting of a cured product, and preferably comprises a metal layer between any of the layers consisting of the cured product. The metal layer is preferably formed by the metal layer forming step.

[1055] That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer composed of a cured product between performing the method for producing a cured product a plurality of times. A preferred embodiment of the metal layer forming step is as described above.

[1056] As the above-mentioned laminate, for example, a laminate having a layer structure in which at least three layers, namely, a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product, are sequentially stacked can be cited as a preferred laminate.

[1057] The layer consisting of the first cured product and the layer consisting of the second cured product are preferably layers consisting of the cured product of the present invention. The resin composition of the present invention for forming the layer consisting of the first cured product and the resin composition of the present invention for forming the layer consisting of the second cured product can be a composition having the same composition or a composition having different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

[1058] <Lamination process>

[1059] The method for producing a laminated body of the present invention preferably includes a lamination step.

[1060] The lamination process is a series of processes including performing at least one of (a) a film forming process (layer forming process), (b) an exposure process, (c) a developing process, (d) a heating process, and a post-development exposure process in sequence again on the surface of a pattern (resin layer) or a metal layer. However, it may be a method of repeating at least one of (a) a film forming process, (d) a heating process, and a post-development exposure process. Furthermore, (e) a metal layer forming process may be included after at least one of (d) a heating process and a post-development exposure process. Of course, the lamination process may further include the above-mentioned drying process, etc. as appropriate.

[1061] When the lamination process is further performed after the lamination process, a surface activation process may be further performed after the exposure process and after the heating process or after the metal layer forming process. As the surface activation process, plasma treatment is exemplified. The details of the surface activation process will be described later.

[1062] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.

[1063] For example, in the structure of resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, the resin layer is preferably configured with 2 to 20 layers, more preferably with 2 to 9 layers.

[1064] The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.

[1065] In the present invention, it is particularly preferred that after the metal layer is set, the cured product (resin layer) of the resin composition of the present invention is further formed to cover the above-mentioned metal layer. Specifically, the method of repeating the order of (a) film forming process, (b) exposure process, (c) developing process, (d) heating process and at least one of the post-exposure process, (e) metal layer forming process, or (a) film forming process, (d) heating process and at least one of the post-exposure process, (e) metal layer forming process can be cited. By alternately stacking the stacking process and the metal layer forming process of the resin composition layer (resin layer) of the present invention, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately stacked.

[1066] (Surface activation treatment process)

[1067] The method for producing a laminate of the present invention preferably includes a surface activation treatment step of performing surface activation treatment on at least a portion of the metal layer and the resin composition layer.

[1068] The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step may be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and after the resin composition layer is subjected to the surface activation treatment step.

[1069] The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and preferably on a portion or all of the region where the resin composition layer is formed on the surface of the metal layer. In this way, by performing a surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on the surface thereof can be improved.

[1070] The surface activation treatment is also preferably performed 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, the adhesion with the metal layer and the resin layer provided on the surface after the surface activation treatment can be improved. In particular, when the resin composition layer is cured, such as when negative development is performed, it is not easy to be damaged by the surface treatment, and the adhesion is easily improved.

[1071] The surface activation treatment can be performed by the method described in paragraph 0415 of International Publication No. 2021 / 112189, for example. This content is incorporated into this specification.

[1072] (Semiconductor device and method of manufacturing the same)

[1073] The present invention also discloses a semiconductor device comprising the cured product or the laminate of the present invention.

[1074] Furthermore, the present invention discloses a method for producing a semiconductor device including the method for producing a cured product or a method for producing a laminate according to the present invention.

[1075] As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated herein.

[1076] Example

[1077] Below, enumerate embodiment and the present invention is further specifically described.The material, usage amount, ratio, processing content, processing sequence etc. shown in the following embodiment can be appropriately changed as long as it does not depart from the gist of the present invention.Therefore, the scope of the present invention is not limited to the specific example shown below.As long as there is no special explanation, "part", "%" are mass references.

[1078] <Synthesis of Polyimide Precursor>

[1079] [Synthesis Example SP-1: Synthesis of polyimide (SP-1)]

[1080] 20.80 g (40 mmol) of 4,4'-(4,4'-isopropylidene diphenyloxy) diphthalic anhydride was dissolved in 70 g of N-methylpyrrolidone (NMP). Next, 9.08 g (35.2 mmol) of 4,4'-isopropylidene bis(2-aminophenol) was dissolved in 50 g of NMP and added dropwise at a temperature of 10°C to 25°C for 1 hour. After stirring at 25°C for 30 minutes, 10 g of toluene was added, and the mixture was reacted at 200°C for 4 hours while nitrogen was flowing, and then cooled to 25°C. Next, 15.3 g (100 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.66 g (12 mmol) of potassium iodide, and 0.08 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical were added, and the mixture was reacted at 95°C for 15 hours, then cooled to 25°C and diluted with 120 g of tetrahydrofuran. Next, the reaction solution was added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, and the mixture was stirred for 15 minutes, and then the polyimide resin was filtered. Next, the resin was re-slurried with 1 L of water and filtered, and then re-slurried with 1 L of methanol and filtered, and then dried at 40°C for 8 hours under reduced pressure. Next, the dried resin was dissolved in 250 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added and stirred for 4 hours. After filtering out the ion exchange resin, the polyimide resin was precipitated in 2 liters of methanol and stirred for 15 minutes. The polyimide resin was filtered to obtain the polyimide resin, and dried at 45°C under reduced pressure for 1 day to obtain a polyimide resin (SP-1). The weight average molecular weight of the obtained polyimide (SP-1) was 15,500, and the number average molecular weight was 7,000. Polyimide (SP-1) is a resin having a repeating unit represented by the following formula (SP-1). By 1 The structure of the repeating unit was confirmed by H-NMR spectroscopy.

[1081] [Chemical formula 74]

[1082]

[1083] [Synthesis Examples SP-2 to SP-5: Synthesis of polyimides (SP-2 to SP-5, SP-12)]

[1084] Polyimides (SP-2) to (SP-5) and (SP-12) were synthesized by the same method as that of polyimide (SP-1) except that the raw materials used were appropriately changed.

[1085] Polyimides (SP-2) to (SP-5) and (SP-12) are resins having repeating units represented by the following formulae (SP-2) to (SP-5) and (SP-12), respectively. 1The structure of each repeating unit was determined by H-NMR spectroscopy. In the following structures, the ratios are expressed as the molar ratio of each structure. The weight average molecular weight and number average molecular weight of these resins are shown in the following table.

[1086] [Chemical formula 75]

[1087]

[1088] [Chemical formula 76]

[1089]

[1090] [Table 1]

[1091] Weight average molecular weight Number average molecular weight SP-2 22，100 8，900 SP-3 50，100 19，100 SP-4 35.500 14.200 SP-5 20，700 8，800 SP-12 18.900 7，700

[1092] [Synthesis Example SP-6: Synthesis of polyimide (SP-6)]

[1093] 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidene diphenyloxy) diphthalic anhydride was dissolved in 120 g of N-methylpyrrolidone (NMP). Then, 9.94 g (24.2 mmol) of 4,4'-isopropylidene bis(2-aminophenol), 5.235 g (24.2 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl, and 0.629 g (5.764 mmol) of p-aminophenol were dissolved in 100 g of NMP, and added dropwise at a temperature of 10°C to 25°C for 1 hour. After stirring at 25°C for 30 minutes, 10 g of toluene was added, and the mixture was reacted at 200°C for 4 hours while nitrogen was flowing, and then cooled to 25°C. Next, 13.2 g (86.4 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.66 g (12 mmol) of potassium iodide, and 0.08 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical were added, and the mixture was reacted at 95°C for 15 hours, then cooled to 25°C and diluted with 200 g of tetrahydrofuran. Next, the reaction solution was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, and the mixture was stirred for 15 minutes, and then the polyimide resin was filtered. Next, the resin was re-slurried with 1 L of water and filtered, and then re-slurried with 1 L of methanol and filtered, and then dried at 40°C for 10 hours under reduced pressure. Next, the dried resin was dissolved in 250 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added and stirred for 4 hours. After filtering out the ion exchange resin, the polyimide resin was precipitated in 2 liters of methanol and stirred for 15 minutes. The polyimide resin was filtered to obtain the polyimide resin, and dried at 45°C under reduced pressure for 1 day to obtain a polyimide resin (SP-6). The weight average molecular weight of the obtained polyimide (SP-6) is 19,600, and the number average molecular weight is 7,700. Polyimide (SP-6) is a resin having a repeating unit represented by the following formula (SP-6). By 1 The structure of the repeating unit was confirmed by H-NMR spectroscopy. In the following structures, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[1094] [Chemical formula 77]

[1095]

[1096] [Synthesis Example SP-7 to Synthesis Example SP-11: Synthesis of polyimides (SP-7) to (SP-11), (SP-13) to (SP-15)]

[1097] Polyimides (SP-7) to (SP-11) and (SP-13) to (SP-15) were synthesized by the same method as that of polyimide (SP-6) except that the raw materials used were appropriately changed.

[1098] Polyimides (SP-7) to (SP-11) and (SP-13) to (SP-15) are resins having repeating units represented by the following formulae (SP-7) to (SP-11) and (SP-13) to (SP-15), respectively. 1 The structure of each repeating unit was confirmed by H-NMR spectrum. In the following structure, the subscript of the repeating unit indicates the molar ratio of each repeating unit. In the following structure, the subscript of the repeating unit indicates the molar ratio of each repeating unit.

[1099] In addition, the weight average molecular weight and number average molecular weight of these resins are described in the following table.

[1100] [Chemical formula 78]

[1101]

[1102] [Chemical formula 79]

[1103]

[1104] [Chemical formula 80]

[1105]

[1106] [Chemical formula 81]

[1107]

[1108] [Table 2]

[1109] Weight average molecular weight Number average molecular weight SP-7 15.700 7.130 SP-8 25.900 12.600 SP-9 45.600 17.500 SP-10 8.900 3.800 SP-11 10.600 4.200 SP-13 14.500 7.000 SP-14 20.500 8.800 SP-15 21.200 9.100

[1110] <Synthesis of Polyimide Precursor>

[1111] [Synthesis Example P-1: Synthesis of polyimide precursor P-1]

[1112] 19.90 g (38.1 mmol) of 4,4'-(4,4'-isopropylidene diphenyloxy) diphthalic anhydride, 17.80 g (77.8 mmol) of glycerol dimethacrylate, 0.05 g of hydroquinone, 13.40 g (169 mmol) of pyridine, and 70 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 5 hours to produce a diester of 4,4'-(4,4"-isopropylidene diphenyloxy) bis(phthalic anhydride) and glycerol dimethacrylate. Then, after the mixture was cooled to -10°C, 9.53 g (79.2 mmol) of thionyl chloride was added dropwise over 90 minutes, and stirred for 2 hours to obtain a white precipitate of pyridinium hydrochloride. Then, the mixture was cooled to -10°C, and 9.53 g (79.2 mmol) of thionyl chloride was added dropwise over 90 minutes, and stirred for 2 hours to obtain a white precipitate of pyridinium hydrochloride. , 13.47 g (32.8 mmol) of 4,4'-isopropylidenebis[(4-aminophenoxy)benzene] dissolved in 100 mL of NMP was added dropwise over 2 hours. Next, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was filtered and stirred again in 4 liters of water for 30 minutes and filtered again, and dried at 40°C for 2 days. Next, the dried resin was dissolved in 200 g of tetrahydrofuran, and an ion exchange resin (MB-1: ORGANO CORPORATION) and stirred for 6 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was filtered to obtain a polyimide precursor resin, which was dried at 45°C under reduced pressure for 2 days to obtain a polyimide precursor (P-1). The weight average molecular weight of the obtained polyimide precursor (P-1) is 28,500, and the number average molecular weight is 10,400. The polyimide precursor (P-1) is a resin having a repeating unit represented by the following formula (P-1). 1 The structure of the repeating unit was confirmed by H-NMR spectroscopy.

[1113] [Chemical formula 82]

[1114]

[1115] [Synthesis Example P-2: Synthesis of polyimide precursor (P-2)]

[1116] A polyimide precursor (P-2) was synthesized in the same manner as in Synthesis Example P-1 except that the raw materials used were appropriately changed. The polyimide precursor (P-2) is a resin having a repeating unit represented by the following formula (P-2). 1 The structure of the repeating unit was confirmed by H-NMR spectroscopy. In the following structures, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[1117] The weight average molecular weight (Mw) of the polyimide precursor (P-2) was measured to be 20,500, and the number average molecular weight (Mn) was 8,900.

[1118] [Chemical formula 83]

[1119]

[1120] [Synthesis Example A-1: ​​Synthesis of polyimide precursor (A-1) for comparative example]

[1121] In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 31.0 g (100 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 180.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 44.4 g (100 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride was added, and stirred at 40°C for 2 hours. Then, after adding 50 mL of toluene, nitrogen was charged at a flow rate of 200 ml / min, and the temperature was raised to 180°C and stirred for 6 hours, and then cooled to room temperature. Then, 130.0 g of N-methylpyrrolidone was added, and after dilution, polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2000 rpm for 30 minutes. The polyimide precursor resin was filtered off, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes and filtered again. Then, the obtained polyimide was dried at 40°C for 1 day under reduced pressure to obtain A-1. The weight average molecular weight (Mw) of A-1 was 30,100, and the number average molecular weight (Mn) was 14,500.

[1122] The polyimide precursor (A-1) is a resin having a repeating unit represented by the following formula (A-1). 1 The structure of the repeating unit was confirmed by H-NMR spectroscopy.

[1123] The polyimide precursor (A-1) for comparative examples does not correspond to a specific resin.

[1124] [Chemical formula 84]

[1125]

[1126] [Synthesis Example A-2: Synthesis of polyimide precursor (A-2)]

[1127] 77.5 g of 4,4'-oxydiphthalic anhydride (ODPA) and 73.5 g of 4,4'-biphenyl dicarboxylic anhydride were added to a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. 79.1 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the exothermic reaction was completed, the mixture was cooled to room temperature and left to stand for 16 hours.

[1128] Next, under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour. Thereafter, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was obtained by filtration, thereby obtaining a reaction solution.

[1129] The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate consisting of a crude polymer. The generated crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered and recovered and then vacuum dried to obtain a powdered comparative polyimide precursor (A-2). The weight average molecular weight (Mw) of the comparative polyimide precursor (A-2) was measured and the result was 22,600.

[1130] The comparative polyimide precursor (A-2) is a resin having a repeating unit represented by the following formula (A-2). 1 The structure of the repeating units was confirmed by H-NMR spectroscopy. The molar ratio of the repeating units was 1:1.

[1131] [Chemical formula 85]

[1132]

[1133] <Examples and Comparative Examples>

[1134] In each example, the components described in the following table were mixed to obtain each resin composition. In addition, in each comparative example, the components described in the following table were mixed to obtain each comparative composition.

[1135] Specifically, the content of each component described in the table is set to the amount (parts by mass) described in the "amount added" column of each column in the table.

[1136] The obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter having a pore width of 0.5 μm.

[1137] In the table, "-" indicates that the composition does not contain the corresponding component.

[1138]

[1139]

[1140] The details of each component described in the table are as follows.

[1141] 〔Resin〕

[1142] SP-1 to SP-15: Polyimides (SP-1) to (SP-15) synthesized in the above

[1143] ·P-1~P-2: The polyimide precursors (P-1)~(P-2) synthesized above

[1144] A-1 to A-2: the above-mentioned synthetic products (comparative examples)

[1145] 〔Polymerizable compounds〕

[1146] ·B-1 to B-2: polymerizable compounds having the following structures

[1147] [Chemical formula 86]

[1148]

[1149] ·B-3: SR-209 (manufactured by Sartomer Company, Inc.)

[1150] B-4: ADPH (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1151] · B-5: 1,6-bis(acryloyloxy)heptane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1152] B-6: Neopentyl glycidyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1153] ·B-7: BLEMMER PDBP (manufactured by NOF CORPORATION)

[1154] ·B-8: BLEMMER ADT-250 (manufactured by NOF CORPORATION)

[1155] ·B-9: SR-209 (manufactured by Sartomer Company, Inc.)

[1156] 〔Solvent〕

[1157] DMSO: dimethyl sulfoxide

[1158] ·GBL:Y-butyrolactone

[1159] ·NMP: N-methylpyrrolidone

[1160] γ-V: γ-valerolactone

[1161] In the table, "DMSO / GBL" and "DMSO / γ-V" indicate that DMSO and GBL were mixed at a mixing ratio (mass ratio) of DMSO:GBL = 80:20 and DMSO:γ-valerolactone = 80:20.

[1162] [Polymerization initiator (all trade names)]

[1163] OXE-01: IRGACURE OXE 01 (manufactured by BASF)

[1164] OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[1165] ·Irgacure 784: Irgacure 784 (manufactured by BASF)

[1166] ·CPI-310B (made by San-Apro Ltd.)

[1167] D-1: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1168] 〔Migration inhibitor〕

[1169] ·E-1 to E-7: Compounds of the following structures

[1170] [Chemical formula 87]

[1171]

[1172] 〔Metal Adhesion Improver〕

[1173] ·F-1 to F-3: Compounds of the following structures

[1174] [Chemical formula 88]

[1175]

[1176] F-4: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1177] F-5: KR-513 (manufactured by Shin-Etsu Chemica Co., Ltd.)

[1178] F-6: 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1179] F-7: tris[3-(trimethoxysilyl)propyl]isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1180] 〔Inhibitor〕

[1181] ·G-1: 1,4-Benzenequinone

[1182] ·G-2: 4-Methoxyphenol

[1183] ·G-3: 1,4-dihydroxybenzene

[1184] ·G-4: Compound having the following structure

[1185] [Chemical formula 89]

[1186]

[1187] ·G-5: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1188] ·G-6: 2,2,6,6-Tetramethylpiperidinyl 1-oxyl radical

[1189] 〔Alkali-generating agent〕

[1190] ·D-1 to D-3: Compounds of the following structures

[1191] [Chemical formula 90]

[1192]

[1193] <Evaluation>

[1194] 〔Evaluation of resolution〕

[1195] In each embodiment or comparative example, each resin composition or comparative composition was applied on a silicon substrate to form a coating film. Then, a heat treatment was performed using a hot plate at 100° C. for 240 seconds to form a resin composition layer with a film thickness of 15 μm. Then, a stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) was used at 100 to 1000 mJ / cm 2 And at 100mJ / cm 2 The exposure amount was changed, and i-rays (light with a wavelength of 365 nm) were irradiated to the resin composition layer through a Bayer pattern mask with a size of 15 μm square. Then, the silicon substrate with the exposed negative photosensitive resin composition layer was placed on a horizontal turntable of a rotary / spray developer (DW-30 type; manufactured by HEMITRONICS CO., Ltd.), and the developer described in the column of "Developing method (developer)" in the table was used to develop at 23°C for 30 seconds, and the unexposed part was removed by development, and the rinse solution (PGMEA) was used to rinse at 23°C for 60 seconds to form a pattern. The resolution of the resin composition or the comparative composition was evaluated by the following evaluation criteria. In addition, the case where the exposed width of the base substrate is 15 μm ± 3 μm is set to be able to resolve a pattern with a line width of 15 μm (a pattern of 15 μm square).

[1196] -Evaluation Criteria-

[1197] A: The difference between the maximum and minimum exposure doses that can analyze a pattern with a thickness of 15 μm and a line width of 15 μm is 900 mJ / cm 2 above.

[1198] B: The difference between the maximum and minimum exposure values ​​that can analyze a pattern with a thickness of 15 μm and a line width of 15 μm is 600 mJ / cm 2 Above and less than 900mJ / cm 2 .

[1199] C: The difference between the maximum and minimum exposure doses that can resolve a pattern with a thickness of 15 μm and a line width of 15 μm is 300 mJ / cm 2 Above and less than 600mJ / cm 2 .

[1200] D: The difference between the maximum and minimum exposure values ​​that can analyze a pattern with a thickness of 15 μm and a line width of 15 μm is less than 300 mJ / cm 2 .

[1201] [Evaluation of focus margin]

[1202] Each resin composition or comparative composition prepared in each embodiment and comparative example was applied to an 8-inch silicon wafer by spin coating to form a coating film. The silicon wafer to which the coating film was applied was dried on a hot plate at 100° C. for 5 minutes to form a uniform resin composition layer with a thickness of about 8 μm on the silicon wafer.

[1203] Using a mask having a circular pattern with a mask size of 5 μm in diameter, an i-ray stepper FPA-3030iWa (NA=0.16) (manufactured by Canon) was used to irradiate the sample at a rate of 200 mJ / cm 2 Up to 600mJ / cm 2 At 100mJ / cm 2 The energy is irradiated to the resin composition layer in a stepwise manner. At this time, for each exposure amount, the focus is moved toward the bottom of the film with the film surface as the reference, and the exposure is performed by moving 2 μm. After exposure, the wafer is placed on a horizontal turntable of a rotary / spray developer (DW-30 type; manufactured by CHEMITRONICS CO., Ltd.), and the developer described in the column of "Development Method (Developer)" in the table is used to develop at 23°C for 30 seconds, and the unexposed part is removed by development, and the rinse solution (PGMEA) is used to rinse at 23°C for 60 seconds to form a pattern.

[1204] The exposed resin composition layer (resin layer) was heated at a heating rate of 10°C / min in a nitrogen atmosphere and heated at the temperature described in the "Temperature" column of the "Curing Conditions" in the table for 180 minutes, thereby obtaining a pattern of the cured layer (resin layer) of the resin composition layer.

[1205] The pattern shape and pattern width of each obtained pattern were observed under an optical microscope to determine the focus margin. When the angle between the bottom surface and the side surface of the pattern was 80 to 100° and the pattern diameter was 4 to 6 μm, the pattern was determined to be formed.

[1206] The wider the focus margin (the larger the numerical value), the more preferable the focus margin property is.

[1207] -Evaluation Criteria-

[1208] A: The focus margin is 10 μm or more.

[1209] B: The focus margin is 7 μm or more and less than 10 μm.

[1210] C: The focus margin exceeds 4 μm and is less than 7 μm.

[1211] D: The focus margin is 4 μm or less.

[1212] 〔Evaluation of chemical resistance〕

[1213] Each resin composition or comparative composition prepared in each embodiment and comparative example was applied to a silicon wafer by spin coating, thereby forming a coating film. The silicon wafer to which the coating film was applied was dried on a hot plate at 100°C for 5 minutes, and a uniform resin composition layer with a thickness of about 15 μm was formed on the silicon wafer. The resin composition layer on the silicon wafer was spun at 500 mJ / cm using a stepper (Nikon NSR2005i9C). 2 The entire surface is exposed with an exposure energy of, the exposed resin composi...

Claims

1. A resin composition comprising: At least one resin selected from polyimide and its precursor, wherein the resin has a ring structure with 5 or more ring members on the side chain; a polymerization initiator; and Polymeric compounds.

2. A resin composition comprising: At least one resin selected from polyimide and its precursor, the resin having a structure represented by the following formula (A-1); a polymerization initiator; and Polymeric compounds, In formula (A-1), L A1 represents a single bond or an m+1-valent linking group, Cy each independently represents a ring structure having 5 or more ring members and optionally having a substituent, m represents an integer greater than 1, and * represents a bonding site to an atom contained in the main chain of the resin.

3. The resin composition according to claim 1 or 2, wherein The resin further has a polymerizable group.

4. The resin composition according to claim 3, wherein The polymerizable group value of the resin is 0.2 mmol / g to 5 mmol / g.

5. The resin composition according to claim 1 or 2, wherein When a film-like cured product having a film thickness of 10 μm is formed using the resin composition, the transmittance of the cured product at a wavelength of 365 nm is 15% or more.

6. The resin composition according to claim 1 or 2, wherein The resin contains a repeating unit represented by the following formula (1-1), In formula (1-1), X 1 represents an organic group having 4 or more carbon atoms, Y 1 represents an organic group with 4 or more carbon atoms, R 1 Each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more, In formula (R-1), L 1 represents a2+1 valent connecting group, Z 1 represents an aromatic group or a cyclic aliphatic group, A 1 represents a polymerizable group, a1 represents 0 or more, and Z 1 a2 represents an integer greater than or equal to 1, and * represents the integer corresponding to X in formula (1-1). 1 or Y 1 bonding part.

7. The resin composition according to claim 6, wherein A in the formula (R-1) contained in the formula (1-1) 1 At least one of them is a vinyl group, a (meth)acryloyloxy group, a vinyl ether group, an allyl group, an epoxy group, or a group containing these.

8. The resin composition according to claim 7, wherein A in formula (R-1) in formula (1-1) 1 At least one of them is a vinyl group or a vinyl ether group.

9. The resin composition according to claim 6, wherein X in formula (1-1) 1 and Y 1 Each of the following formulas (V-1) to (V-4) contains a structure in which two or more hydrogen atoms are removed from the structure represented by any of the following formulas (V-1) to (V-4), In formula (V-2), R X1 are independently a hydrogen atom, an alkyl group or a halogenated alkyl group, In formula (V-3), R X2 and R X3 Each independently represents a hydrogen atom or a substituent, R X2 With R X3 Optionally bond to form a ring structure.

10. The resin composition according to claim 6, wherein L in the formula (R-1) 1 is a group represented by the following formula (L-1), In formula (L-1), L x represents an a2+1 valent linking group, a2 represents an integer greater than 1, and * represents the same as X in formula (1-1) 1 or Y 1 The bonding site of Z in formula (R-1) is represented by #. 1 bonding part.

11. A resin composition comprising: At least one resin selected from polyimide and its precursor, the resin containing at least one of the repeating units represented by the following formula (2-1) and the following formula (3-1); a polymerization initiator; and Polymeric compounds, In formula (2-1), X 2 represents an organic group having 4 or more carbon atoms, Y 2 represents an organic group having 4 or more carbon atoms, Y 2 Does not contain ester bonds, R 2 Each independently represents a group represented by the following formula (R-2), n represents an integer greater than 1, In formula (3-1), X 3 represents an organic group having 4 or more carbon atoms, Y 3 represents an organic group having 4 or more carbon atoms, Y 3 Contains no ester bond, A 3 and A 4 Each independently represents an oxygen atom or -NR N -, R 3 and R 4 Each independently represents a hydrogen atom or a monovalent organic group, R 2 Each independently represents a group represented by the following formula (R-2), n represents an integer greater than 1, In formula (R-2), L 2 represents a b2+1 valent connecting group, Z 2 Indicates a b1+1 valent organic group, A 2 represents a polymerizable group, b1 represents 1 or more, and Z 2 b2 represents an integer greater than or equal to 1, and * represents the same integer as Y of formula (2-1). 2 Or Y in formula (3-1) 3 The number of ester bonds contained in the formula (R-2) is 1 or 0.

12. The resin composition according to claim 11, wherein The resin is a resin having a ring structure having 5 or more ring members in a side chain.

13. The resin composition according to claim 11, wherein The polymerizable group value of the resin is 0.2 mmol / g to 5 mmol / g.

14. The resin composition according to claim 11, wherein When a film-like cured product having a film thickness of 10 μm is formed using the resin composition, the transmittance of the cured product at a wavelength of 365 nm is 15% or more.

15. The resin composition according to claim 11, wherein A in the formula (R-2) contained in the formula (2-1) 2 At least one of them is a vinyl group, a (meth)acryloyloxy group, a vinyl ether group, an allyl group, an epoxy group or a group containing these, and A in the formula (R-2) contained in the formula (3-1) 2 At least one of them is a vinyl group, a (meth)acryloyloxy group, a vinyl ether group, an allyl group, an epoxy group or a group containing these, and X in formula (2-1) 2 and Y 2 Each of the structures represented by any of the following formulae (V-1) to (V-4) contains a structure obtained by removing two or more hydrogen atoms, and X in formula (3-1) 3 and Y 3 Each of the following formulas (V-1) to (V-4) contains a structure in which two or more hydrogen atoms are removed from the structure represented by any of the following formulas (V-1) to (V-4), In formula (V-2), R X1 are independently a hydrogen atom, an alkyl group or a halogenated alkyl group, In formula (V-3), R X2 and R X3 Each independently represents a hydrogen atom or a substituent, R X2 With R X3 Optionally bond to form a ring structure.

16. The resin composition according to claim 11, wherein L in the formula (R-2) 2 is a group represented by the following formula (L-2), wherein A in the formula (R-2) 2 is a vinyl group or a vinyl ether group, In formula (L-2), L x represents a b2+1 valent linking group, b2 represents an integer greater than 1, and * represents the same as X in formula (2-1) 2 or Y 2 Or X in formula (3-1) 3 or Y 3 The bonding site of Z in formula (R-2) is represented by #. 2 bonding part.

17. The resin composition according to any one of claims 1, 2, and 11 to 16, wherein The polymerization initiator is a photoacid generator. 18 . The resin composition according to claim 1 , 2 and any one of claims 11 to 16 , comprising two or more polymerization initiators as the polymerization initiator. 19 . The resin composition according to claim 1 , 2 and any one of claims 11 to 16 , comprising a photopolymerization initiator and a thermal polymerization initiator or a photoradical polymerization initiator and a photoacid generator as the polymerization initiator. 20 . The resin composition according to claim 1 , further comprising an azole compound and a silane coupling agent.

21. The resin composition according to any one of claims 1, 2, and 11 to 16, which is used for forming an interlayer insulating film for a redistribution layer.

22. A cured product obtained by curing the resin composition according to any one of claims 1, 2, and 11 to 16. 23 . A laminate comprising two or more layers consisting of the cured product according to claim 22 , wherein a metal layer is provided between any of the layers consisting of the cured product. 24 . A method for producing a cured product, comprising a film forming step of applying the resin composition according to claim 1 , 2 , and 11 to 16 to a substrate to form a film. 25 . The method for producing a cured product according to claim 24 , comprising an exposure step of selectively exposing the film to light and a development step of developing the film using a developer to form a pattern. 26 . The method for producing a cured product according to claim 24 , comprising a heating step of heating the film at 50° C. to 450° C.

27. A method for producing a laminate, comprising the method for producing a cured product according to claim 24.

28. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 24.

29. A semiconductor device comprising the cured product according to claim 22.

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