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

Abstract

A resin composition, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product. The resin composition contains: a heterocycle-containing polymer A-1 having a polymerizable group and an optionally protected amino group; a heterocycle-containing polymer A-2 having a polymerizable group and having a structure A in which two groups selected from the group consisting of a carboxylic acid ester group and an optionally protected carboxyl group are linked by a linking group having a linking chain length of 2-4; and a polymerization initiator.

Description

Technical Field

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

[0002] Today, resin materials made from resin compositions containing resins are used in various fields.

[0003] For example, heterocyclic polymers such as polyimide are suitable for a variety of applications due to their excellent heat resistance and insulation properties. These applications are not particularly limited; for example, when listing semiconductor devices for mounting, their use as insulating films, sealing materials, or protective films can be cited. Furthermore, they are also used as base films or coverlays for flexible substrates.

[0004] For example, in the above-described applications, heterocyclic polymers such as polyimide are used in the form of resin compositions comprising heterocyclic polymers.

[0005] By applying this resin composition to a substrate, for example, by coating, a photosensitive film is formed, and then, as needed, exposure, development, heating, etc., a cured product can be formed on the substrate.

[0006] The resin composition can be applied using known coating methods, thus exhibiting excellent manufacturing adaptability. For example, it offers a high degree of design freedom in terms of the shape, size, and application location of the resin composition. From the perspective of this excellent manufacturing adaptability, in addition to the high performance inherent in heterocyclic polymers such as polyimide, the industrial applications of the aforementioned resin composition are increasingly anticipated.

[0007] For example, Patent Document 1 describes a polyimide resin composition characterized by comprising a resin and a filler dispersed in the resin, wherein the resin comprises a polyimide resin having a dicarboxylic acid group or an anhydride group at both ends, and the filler has at least one inorganic compound selected from the group consisting of alumina, aluminum hydroxide, magnesium oxide, and magnesium hydroxide on its surface.

[0008] Previous technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2022-129993 Summary of the Invention

[0011] The technical problem to be solved by the invention

[0012] In recent years, the increasing importance of high-speed signal transmission in inter-chip wiring has led to the miniaturization of rewiring between chips. Consequently, there is a growing demand for higher resolution in cured photosensitive resin compositions used in applications such as pattern formation and insulation.

[0013] The purpose of this invention is to provide a resin composition that can produce a cured product with excellent resolution, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product.

[0014] means for solving technical problems

[0015] The following are examples of representative embodiments of the present invention.

[0016] <1> A resin composition comprising:

[0017] A-1 is a heterocyclic polymer containing polymerizable groups and protected amino groups;

[0018] A heterocyclic polymer A-2 having polymerizable groups and structure A, wherein structure A is a structure in which two groups selected from the group consisting of a carboxylic acid ester group and a protected carboxyl group are linked by a linking group with a chain length of 2 to 4; and

[0019] Polymerization initiator.

[0020] <2> The resin composition according to <1>, wherein,

[0021] The heterocyclic polymer A-2 described above contains groups represented by any of the following formulas (S-1) to (S-4).

[0022] [Chemical Formula 1]

[0023]

[0024] In equations (S-1) to (S-4), R S1 Represents -OH, -O - or -OR S2 R S2 Indicates a protecting group, Cy indicates an aliphatic ring structure, and L represents a protecting group. 1 This indicates a single bond or an aliphatic group with a chain length of 1 or 2, where n represents an integer of 1 or 2, and * indicates a bonding site with other structures.

[0025] <3> The resin composition according to <1> or <2>, wherein,

[0026] The heterocyclic polymer A-1 has two or more of the above-mentioned protected amino groups, and the heterocyclic polymer A-2 has two or more of the above-mentioned structure A.

[0027] <4> The resin composition according to any one of <1> to <3>, wherein,

[0028] The heterocyclic polymer A-1 mentioned above is a polyimide or a polybenzoxazole.

[0029] <5> The resin composition according to any one of <1> to <4>, wherein,

[0030] The heterocyclic polymer A-1 is a polyimide or a polybenzoxazole, and the heterocyclic polymer A-2 is a polyimide.

[0031] <6> The resin composition according to any one of <1> to <5>, wherein,

[0032] The above-mentioned protected amino groups are those of the following formula (R T The group represented by ).

[0033] [Chemical Formula 2]

[0034]

[0035] Formula (R) T In ), T 1 This represents an organic group with a monovalent valence.

[0036] <7> The resin composition according to any one of <1> to <6>, wherein,

[0037] The weight-average molecular weight of the heterocyclic polymer A-1 is less than 26,000, and the weight-average molecular weight of the heterocyclic polymer A-2 is less than 26,000.

[0038] <8> The resin composition according to any one of <1> to <7>, wherein,

[0039] The content of the heterocyclic polymer A-1 is 50 to 150 by mass relative to the content of the heterocyclic polymer A-2.

[0040] <9> The resin composition according to any one of <1> to <8> further comprises resin C, said resin C being a resin containing repeating units represented by the following formula (4-1) or the following formula (4-2) and not belonging to heterocyclic polymer A-1 and heterocyclic polymer A-2.

[0041] [Chemical Formula 3]

[0042]

[0043] In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each is an independent hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of them is a monovalent organic group having an olefinic unsaturated bond.

[0044] [Chemical Formula 4]

[0045]

[0046] In equation (4-2), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Let each independently represent the structure represented by the following formula (R-2), where n and m independently represent integers from 0 to 4, and n+m is 1 or higher.

[0047] [Chemical Formula 5]

[0048]

[0049] In equation (R-2), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an organic group with a valence of a1+1. 1 The terms represent vinyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, or epoxy, where a1 represents an integer greater than or equal to 1, a2 represents an integer greater than or equal to 1, and * represents X in formula (4-2). 1 Or Y 1 The bonding sites.

[0050] <10> A resin composition comprising:

[0051] Resin 1 comprising repeating units represented by the following formula (1-1);

[0052] Resin 2 comprising repeating units represented by formula (1-2) or formula (1-3) below; and

[0053] Polymerization initiator.

[0054] [Chemical Formula 6]

[0055]

[0056] In equation (1-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1W represents an organic group with 4 or more carbon atoms. 1 V represents an organic group with 4 or more carbon atoms. 1 R represents the organic group represented by the following formula (2-1). 1 Each of the above groups independently represents a group containing a polymerizable group, and n and m independently represent integers from 0 to 4, with n+m being 1 or higher.

[0057] In equation (1-2), X 2 Y represents an organic group with 4 or more carbon atoms. 2 W represents an organic group with 4 or more carbon atoms. 2 G represents an organic group with 4 or more carbon atoms. 1 and G 2 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. 2 Each of the above groups independently represents a group containing a polymerizable group, and n and m independently represent integers from 0 to 4, with n+m being 1 or higher.

[0058] In equation (1-3), X 3 Y represents an organic group with 4 or more carbon atoms. 3 W represents an organic group with 4 or more carbon atoms. 3 V represents a single bond or an organic group with 4 or more carbon atoms. 3 R represents the organic group represented by formula (3-1) or formula (3-2) below. 3 Each of the above groups independently represents a group containing a polymerizable group, and n and m independently represent integers from 0 to 4, with n+m being 1 or higher.

[0059] [Chemical Formula 7]

[0060]

[0061] In equation (2-1), Q 1 The symbol represents a hydrogen atom or a group represented by the following formula (2-2), and * represents the W in formula (1-1). 1 The bonding sites.

[0062] [Chemical Formula 8]

[0063]

[0064] In equation (2-2), T 1 The symbol represents a monovalent organic group, and * indicates the bonding site with the nitrogen atom in formula (2-1).

[0065] [Chemical Formula 9]

[0066]

[0067] In equation (3-1), R C1 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. C2 The substituent is represented by 'a', which represents an integer from 0 to 3, and '*' represents the substituent in equation (1-3). 3 The bonding sites.

[0068] In equation (3-2), R C1 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. C2 The substituent is represented by 'a', which represents an integer from 0 to 9, and '*' represents the substituent in equation (1-3). 3 The bonding sites.

[0069] <11> The resin composition according to <10>, wherein,

[0070] R in equation (1-1) above 1 R in equation (1-2) above 2 and R in the above equation (1-3) 3 Let (R-1) represent the structure described in the following equation.

[0071] [Chemical Formula 10]

[0072]

[0073] In equation (R-1), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an aromatic group or a cyclic aliphatic group. 1 Indicates a polymerizable group, a1 indicates 1 or more and Z 1 Integers below the largest substitution base, a2 represents integers above 1, and * represents X in equation (1-1). 1 Or Y 1 The bonding sites.

[0074] <12> The resin composition according to <11>, wherein,

[0075] In the above formula (R-1), A 1 At least one of them is vinyl.

[0076] <13> The resin composition according to <10>, wherein,

[0077] R in equation (1-1) above 1 R in equation (1-2) above 2 and R in the above equation (1-3) 3 It contains maleimide groups.

[0078] <14> The resin composition according to any one of <10> to <13>, wherein,

[0079] G in the above equation (1-2) 1 and G 2 R in the above formula (3-1) C1 And R in the above equation (3-2) C1 Both are -OH or -O - .

[0080] <15> The resin composition according to any one of <10> to <14>, wherein,

[0081] The weight-average molecular weight of resin 1 is below 26,000.

[0082] <16> The resin composition according to any one of <10> to <15>, wherein,

[0083] The weight-average molecular weight of resin 1 is below 16,000.

[0084] <17> The resin composition according to any one of <10> to <16>, further comprising resin C,

[0085] The resin C is a resin that contains repeating units represented by the following formula (4-1) or the following formula (4-2) and does not belong to resin 1 or resin 2.

[0086] [Chemical Formula 11]

[0087]

[0088] In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each is an independent hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of them is a monovalent organic group having an olefinic unsaturated bond.

[0089] [Chemical Formula 12]

[0090]

[0091] In equation (4-2), X 1Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Let each independently represent the structure represented by the following formula (R-2), where n and m independently represent integers from 0 to 4, and n+m is 1 or higher.

[0092] [Chemical Formula 13]

[0093]

[0094] In equation (R-2), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an organic group with a valence of a1+1. 1 The terms represent vinyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, or epoxy, where a1 represents an integer greater than or equal to 1, a2 represents an integer greater than or equal to 1, and * represents X in formula (4-2). 1 Or Y 1 The bonding sites.

[0095] <18> The resin composition according to any one of <10> to <17>, wherein,

[0096] The content of resin 1 is 50 to 150 by mass relative to the content of resin 2.

[0097] <19> The resin composition according to any one of <1> to <18> further comprises a polymerizable compound.

[0098] <20> The resin composition according to any one of <1> to <19> contains a solvent with a boiling point of 100 to 260°C.

[0099] <21> The resin composition according to <20>, wherein,

[0100] The content of the solvent with a boiling point of 100 to 260°C is 40% by mass or more relative to the total mass of the composition.

[0101] <22> The resin composition according to <20> contains two or more solvents with boiling points of 100 to 260°C.

[0102] <23> The resin composition according to any one of <1> to <22> is used to form an interlayer insulating film for a redistribution layer.

[0103] <24> A cured product formed by curing any one of the resin compositions <1> to <23>.

[0104] <25> A laminate comprising two or more layers formed of the cured material described in <24>, wherein a metal layer is included between any of the layers formed of the cured material.

[0105] <26> A method for manufacturing a cured material, comprising:

[0106] In the film forming process, the resin composition described in any one of <1> to <23> is applied to a substrate to form a film.

[0107] <27> The method for manufacturing the cured product according to <26> includes:

[0108] The exposure process selectively exposes the film to light; and the development process develops the film using a developing solution to form a pattern.

[0109] <28> The method for manufacturing a cured product according to <26> or <27> includes:

[0110] The heating process involves heating the membrane at 50–450°C.

[0111] <29> A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in any one of <26> to <28>.

[0112] <30> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in any one of <26> to <28>.

[0113] <31> A semiconductor device comprising the cured material described in <24>.

[0114] Invention Effects

[0115] According to the present invention, a resin composition that can obtain a cured product with excellent resolution is provided, 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 are provided. Attached Figure Description

[0116] Figure 1 This is a schematic cross-sectional view of a silicon wafer with copper wiring formed on which a solidified material has been formed. Detailed Implementation

[0117] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown.

[0118] In this specification, the numerical range indicated by the symbol “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0119] 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 expected function of the process can be achieved.

[0120] In this specification, the descriptions of groups (atomic groups) without indicating whether they are substituted or unsubstituted include both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0121] In this instruction manual, unless otherwise specified, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used in exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation.

[0122] In this specification, "(meth)acrylate" means either "acrylate" or "methacrylate", "(meth)acrylic acid" means either "acrylic acid" or "methacrylic acid", and "(meth)acryloyl" means either "acryloyl" or "methacryloyl".

[0123] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0124] In this specification, total solids content refers to the total mass of the components after removing the solvent from all components of the composition. Furthermore, in this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0125] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined using gel permeation chromatography (GPC) and are defined as polystyrene equivalents. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8420 GPC (manufactured by TOSOH CORPORATION) and connecting two guard columns, TSK SuperAW-H, TSK SuperAWM-H, and TSK SuperAWM-H (two such columns), in series. Unless otherwise specified, these molecular weights are determined using a lithium bromide (10 mmol / g) NMP (N-methyl-2-pyrrolidone) solution as the eluent. Furthermore, unless otherwise specified, a 275 nm UV (ultraviolet) detector is used in the GPC determination.

[0126] In this specification, when referring to the positional relationship of the layers constituting the laminate, "upper" or "lower" simply means that there are other layers above or below the reference layer among the layers of interest. That is, a third layer or element may be further inserted between the reference layer and the other layers, without the reference layer needing to be in contact with the other layers. Unless otherwise specified, the direction of the stacked layers relative to the substrate is referred to as "upper," or, when a resin composition layer is present, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction as "lower." Furthermore, this vertical direction is provided for convenience in this specification; in practice, the "upper" direction in this specification may differ from the vertical direction.

[0127] In this specification, unless otherwise specified, each component in the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to that component.

[0128] Unless otherwise specified, the temperature in this manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH.

[0129] In this specification, the preferred combination of methods is a more preferred method.

[0130] (Resin composition)

[0131] The resin composition according to the first aspect of the present invention (hereinafter also simply referred to as the "first resin composition") comprises: a heterocyclic polymer A-1 having polymerizable groups and having a protected amino group; a heterocyclic polymer A-2 having polymerizable groups and having a structure A, wherein the structure A is a structure in which two groups selected from the group consisting of a carboxylic acid ester group and a protected carboxyl group are linked by a linking group with a chain length of 2 to 4; and a polymerization initiator.

[0132] The resin composition according to the second aspect of the present invention (hereinafter also simply referred to as the "second resin composition") comprises: a resin 1 containing repeating units represented by formula (1-1); a resin 2 containing repeating units represented by formula (1-2) or formula (1-3); and a polymerization initiator.

[0133] Hereinafter, the first resin composition and the second resin composition will also be collectively referred to as "resin compositions".

[0134] Hereinafter, heterocyclic polymer A-1, heterocyclic polymer A-2, resin 1 and resin 2 will be collectively referred to as "specific resins".

[0135] The resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and more preferably to form a film for exposure and development using a developer containing an organic solvent.

[0136] The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for rewiring layers.

[0137] In particular, using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer is also one of the preferred embodiments of the present invention.

[0138] Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative development.

[0139] In this invention, negative development refers to the development of non-exposed areas by developing during exposure and development, while positive development refers to the development of exposed areas by developing.

[0140] As the above-described exposure method, developer, and development method, for example, the exposure method described in the exposure step, the developer described in the development step, and the development method described in the following description of the method for manufacturing a cured object can be used.

[0141] The resin composition according to the present invention can yield cured products with excellent resolution.

[0142] The mechanism by which the above effects are achieved is not yet clear, but the following is a speculation.

[0143] Through in-depth investigation, the inventors discovered that by using a composition containing two heterocyclic polymers, A-1 and A-2 (the first resin composition) or a composition containing two resins, 1 and 2 (the second resin composition), a cured product with excellent resolution can be obtained.

[0144] Here, when the first resin composition is patterned by exposure and development and then cured by heat, during curing, the amino groups in the heterocyclic polymer A-1 (amino groups present in the heterocyclic polymer A-1 or amino groups generated from protected amino groups during curing, etc.) and the structure A or deprotected structure A in the heterocyclic polymer A-2 react to form a long heterocyclic polymer.

[0145] In the second resin composition, a long heterocyclic polymer is also formed due to the reaction between the amino groups in resin 1 and the carboxyl groups in resin 2 during curing.

[0146] Here, compared to using a composition containing long heterocyclic polymers from the outset, even when the molecular weight of the final obtained resin is set to the same level, as in the resin composition of the present invention, the molecular weight of each resin in the composition is smaller. It is presumed that, as a result, the photosensitive film obtained from the resin composition exhibits excellent removability from the developing solution, thus yielding a cured product with excellent resolution. Furthermore, it is believed that because each of these resins has polymerizable groups, the crosslinking density of the image region increases, making it easier for differences in the removability of the image region and non-image region from the developing solution to arise.

[0147] Furthermore, it is believed that, as described above, the molecular weight of each resin can be reduced, so even when a photosensitive film is formed on a substrate with unevenness, the film's fluidity is excellent during heating, thus improving the flatness of the photosensitive film.

[0148] Moreover, it is believed that long heterocyclic polymers can eventually be obtained, thus producing cured films with excellent mechanical and physical properties such as elongation at break and low coefficient of thermal expansion.

[0149] In addition, long heterocyclic polymers that are usually difficult to dissolve in solvents and therefore difficult to use as resin compositions or that are usually difficult to be removed by developers can be generated in the cured product, thus enabling further improvement of the mechanical and physical properties of the film and suppression of the coefficient of thermal expansion.

[0150] Here, Patent Document 1 does not describe a resin composition containing a specific resin in the above combination.

[0151] The components contained in the resin composition of the present invention will be described in detail below.

[0152] <Specific Resins>

[0153] The first resin composition of the present invention comprises: a heterocyclic polymer A-1 having a polymerizable group and a protected amino group; and a heterocyclic polymer A-2 having a polymerizable group and a structure A, wherein the structure A is a structure in which two groups selected from the group consisting of carboxylic acid ester groups or protected carboxyl groups are linked by a linking group with a chain length of 2 to 4.

[0154] It is believed that by including structure A in heterocyclic polymer A-2, it is possible to form an imide structure with the amino group present or generated at the end of heterocyclic polymer A-1, thereby improving mechanical properties such as insulation and elongation at break, as well as chemical resistance.

[0155] Hereinafter, the amino groups present in the heterocyclic polymer A-1 and the protected amino groups will be collectively referred to as specific substituents A-1.

[0156] Hereinafter, the group consisting of two groups selected from the group consisting of a carboxylic acid ester group and a protected carboxyl group in heterocyclic polymer A-2, linked by a linking group with a chain length of 2 to 4, i.e., structure A, is also called specific substituent A-2.

[0157] [Heterocyclic polymer A-1]

[0158] The first resin composition comprises a heterocyclic polymer A-1.

[0159] The heterocyclic polymer A-1 is preferably polyimide or polybenzoxazole, more preferably polyimide.

[0160] Furthermore, the heterocyclic polymer A-1 is preferably a polyimide or a polybenzoxazole and the heterocyclic polymer A-2 is a polyimide, more preferably the heterocyclic polymer A-1 is a polyimide and the heterocyclic polymer A-2 is a polyimide.

[0161] In this invention, polyimide refers to a resin having repeating units containing an imide structure within its molecular chain, preferably a resin having repeating units containing an imide ring structure within its molecular chain.

[0162] Furthermore, when the polyimide is a linear resin, the polyimide is preferably a resin having repeating units containing an imide structure in the main chain, and more preferably a resin having repeating units containing an imide ring structure in the main chain.

[0163] In this invention, "main chain" refers to the longest bonded chain in the resin molecule, and "side chain" refers to the bonded chain other than the main chain.

[0164] In this invention, the imide structure refers to the structure represented by *-C(=O)N(-*)C(=O)-*, where * represents the bonding site with other structures, preferably the bonding site with a carbon atom, and more preferably the bonding site with a quaternary carbon atom.

[0165] In this invention, the imide ring structure refers to a ring structure in which all two carbon atoms and the nitrogen atom in the above-mentioned imide structure are used as ring-forming atoms. The imide ring structure is preferably a 5-membered ring.

[0166] In this invention, polybenzoxazole refers to a resin having repeating units containing a benzoxazole structure within its molecular chain.

[0167] Furthermore, when polybenzoxazole is a linear resin, polybenzoxazole is preferably a resin having repeating units containing a benzoxazole structure in the main chain.

[0168] In this invention, the benzoxazole structure refers to the structure represented by the following formula (PBO-1).

[0169] [Chemical Formula 14]

[0170]

[0171] In formula (PBO-1), * indicates the bonding site with other structures.

[0172] -polymeric groups-

[0173] Heterocyclic polymer A-1 has polymerizable groups.

[0174] Examples of polymerizable groups include groups with olefinic unsaturated bonds, epoxy groups, oxocyclobutyl groups, benzoxazolyl groups, etc., with groups having olefinic unsaturated bonds being preferred.

[0175] Examples of groups containing olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0176] Among these, (meth)acryloyl, (meth)acrylamido, vinylphenyl, or maleimide are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity. Furthermore, vinylphenyl or maleimide is preferred from the viewpoint of reducing dielectric loss tangent.

[0177] The content of polymerizable groups (polymerizable group value) relative to the total mass of the heterocyclic polymer A-1 is preferably 0.2 to 5.0 mmol / g, more preferably 0.25 to 4.0 mmol / g, and even more preferably 0.3 to 3.0 mmol / g. In this specification, the polymerizable group value in the resin is calculated as the number of polymerizable groups in one molecule of the resin divided by the number average molecular weight of the resin.

[0178] -Specific substituent A-1-

[0179] Regarding the amino group that serves as the specific substituent A-1, it can be either an unsubstituted amino group (-NH2) or a protected amino group (-N(R)2, where R represents a hydrogen atom or an organic group, and one of the two Rs is an organic group. Furthermore, R is preferably a hydrocarbon group.), but it is more preferably an unsubstituted amino group.

[0180] Furthermore, the protected amino group is preferably a group that generates an amino group through light, heat, acid or alkali.

[0181] The following method can be used to confirm whether the group that is a specific substituent A-1 is a group that generates an amino group through light.

[0182] Under conditions of 1 atmosphere pressure, 25°C, and an exposure illuminance of 25 W / cm² 2 Under specific conditions, a 1% (w / w) N-methylpyrrolidone solution of a particular resin was irradiated with light of wavelength 190–800 nm for 60 seconds, and then... 1 Methods such as H-NMR were used to confirm whether amino groups were produced.

[0183] When the group that is the specific substituent A-1 is a group that generates an amino group by heat, it is preferably a group that generates an amino group by heat at 180°C, more preferably a group that generates an amino group by heat at 200°C, and even more preferably a group that generates an amino group by heat at 230°C.

[0184] The heating time for producing alkali is preferably 180 minutes, more preferably 120 minutes, and even more preferably 60 minutes.

[0185] The following method can be used to confirm whether a group that is a specific substituent A-1 is a group that produces an amino group by heating at a certain temperature X℃ for a certain time Y hours.

[0186] A 1% (w / w) N-methylpyrrolidone solution of a specific resin was exposed to heating at X °C for Y hours, and then... 1 Methods such as H-NMR can be used to confirm whether amino groups have been generated.

[0187] The following method can be used to confirm whether the group that is a specific substituent A-1 is a group that generates an amino group through an acid.

[0188] In a 1% by mass N-methylpyrrolidone solution of a specific resin, 1% by mass methanesulfonic acid relative to the solid content of the resin was added, and the solution was allowed to stand at 25°C for 60 minutes. Then, the solution was analyzed by... 1 Methods such as H-NMR can be used to confirm whether amino groups have been generated.

[0189] The following method can be used to confirm whether the group that is a specific substituent A-1 is a group that generates an amino group through a base.

[0190] In a 1% N-methylpyrrolidone solution of a specific resin, a 10% (by mass) methanol solution of tetrabutylammonium hydroxide (relative to 1% by mass of the resin solids) was added, and the mixture was allowed to stand at 25°C for 60 minutes. Then, the reaction proceeded by... 1 Methods such as H-NMR can be used to confirm whether amino groups have been generated.

[0191] The protected amino group, which is a specific substituent A-1, is preferably of the following formula (R T The group represented by ).

[0192] [Chemical Formula 15]

[0193]

[0194] Formula (R) T In ), T 1 This represents an organic group with a monovalent valence.

[0195] Formula (R) T In ), T 1 Preferably, it is an alkyl group or a cyclically substituted alkyl group, more preferably a tertiary alkyl group or a cyclically substituted methyl group, and even more preferably tert-butyl or 9-fluorenylmethyl.

[0196] The specific substituent A-1 may be present at the end of the side chain of the heterocyclic polymer A-1, but is preferably present at the end of the main chain.

[0197] The content of the specific substituent A-1 in the heterocyclic polymer A-1 is not particularly limited, but is preferably 0.01 to 2 mmol / g, more preferably 0.05 to 1 mmol / g, and even more preferably 0.015 to 0.75 mmol / g.

[0198] The number of specific substituents A-1 in the heterocyclic polymer A-1 is preferably 2 to 10 per molecule, more preferably 2 to 4, and even more preferably 2.

[0199] -The repeating unit represented by equation (1-1)-

[0200] The heterocyclic polymer A-1 preferably contains repeating units represented by the following formula (1-1).

[0201] [Chemical Formula 16]

[0202]

[0203] In equation (1-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 W represents an organic group with 4 or more carbon atoms. 1 V represents an organic group with 4 or more carbon atoms. 1 R represents the organic group represented by the following formula (2-1). 1 Each of the above groups independently represents a group containing a polymerizable group, and n and m independently represent integers from 0 to 4, with n+m being 1 or higher.

[0204] -X 1 -

[0205] X 1 The carbon number is 4 or more, preferably 4 to 50, and more preferably 4 to 40.

[0206] In equation (1-1), X 1 Preferably, it represents an organic group that includes a structure formed by removing two or more hydrogen atoms from the structure represented by any of the following formulas (V-1) to (V-4).

[0207] The chemical resistance and flatness of the cured material are improved by adding an organic group to the structure formed by removing two or more hydrogen atoms from the structure represented by any of the formulas (V-1) to (V-4).

[0208] Furthermore, by using organic groups containing structures formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-4), effects such as suppressing the generation of developing residues, reducing the dielectric constant of the cured product, and decreasing the coefficient of thermal expansion can be obtained.

[0209] [Chemical Formula 17]

[0210]

[0211] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0212] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0213] In equation (V-2), R X1Preferably, each component is an alkyl or a haloalkyl group, more preferably an alkyl or a haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted with a halogen atom. The halogen atom is preferably F or Cl, more preferably F.

[0214] In equation (V-3), R X2 and R X3 Preferably, each atom is a hydrogen atom.

[0215] When R X2 With R X3 When bonded to form a ring structure, R X2 With R X3 The structure formed by bonding is preferably a single bond, -O- or -C(R)2, more preferably -O- or -C(R)2-, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, alkyl or aryl, and even more preferably a hydrogen atom.

[0216] When X 1 When X is a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), 1 Preferably, it is a group represented by the following formula (V-1-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups, n1, represent an integer from 0 to 5, and are preferably an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further substituted with known substituents such as hydrocarbon groups.

[0217] [Chemical Formula 18]

[0218]

[0219] When X 1 When X is a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), 1 Preferably, the group represented by formula (V-2-1) or formula (V-2-2) is preferred. From the viewpoint of reducing the amine value in the resin, the group represented by formula (V-2-2) is preferred. In this specification, the bond that crosses the edge of the ring structure refers to the bond that replaces any one of the hydrogen atoms in the ring structure. In the following formula, L X1 The symbol represents a single bond or -O-, and * represents the X in equation (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, R X1 The definition and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further substituted with known substituents such as hydrocarbon groups.

[0220] [Chemical Formula 19]

[0221]

[0222] When X 1 When X is a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), 1 Preferably, the group represented by formula (V-3-1) or formula (V-3-2) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-2) is preferred. In the following formulas, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, R X2 and R X3 The definition and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further substituted with known substituents such as hydrocarbon groups.

[0223] [Chemical Formula 20]

[0224]

[0225] When X 1 When X is a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), 1 Preferably, it is a group represented by the following formula (V-4-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups are denoted by n1, which is an integer from 0 to 5. Furthermore, the hydrogen atoms in the following structures can be further substituted with known substituents such as hydrocarbon groups. Preferably, the hydrogen atoms in the structure represented by (V-4-1) are all unsubstituted.

[0226] [Chemical Formula 21]

[0227]

[0228] In addition, X 1 It can be the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic acid dianhydride as described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0229] And, X 1 Preferably, the structure does not contain imide bonds.

[0230] And, X 1 The structure preferably does not contain urethane bonds, urea bonds, or amide bonds.

[0231] In this invention, the carbamate bond is *-OC(=O)-NR. N -* represents the key, R NRepresents a hydrogen atom or a monovalent organic group; * indicates the bonding site with a carbon atom, respectively. R N Preferably, it is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.

[0232] In this invention, the urea bond is *-NR. N -C(=O)-NR N -* represents the key, R N Each symbol represents a hydrogen atom or a monovalent organic group, and * indicates a bonding site with a carbon atom. R N The preferred method is as described above.

[0233] Additionally, X 1 Preferably, the structure does not contain ester bonds.

[0234] In this invention, the ester bond is represented by *-OC (=O)-*.

[0235] Among these, X 1 Preferably, it does not contain imide bonds, urethane bonds, urea bonds, and amide bonds; more preferably, it does not contain imide bonds, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0236] And, X 1 The structure can be represented by the following formula (X-2), or X in the structure represented by (X-2). 2 The hydrogen atom or L in the group represented 3 The hydrogen atoms of the group represented are represented by R in formula (1-1) 1 The structure represented by the base substitution.

[0237] [Chemical Formula 22]

[0238]

[0239] In equation (X-2), X 2 Each of the three independent linking groups, L 3 The symbol indicates a divalent linker group, and * indicates a bonding site with other structures.

[0240] In equation (X-2), X 2Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, these are straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, these are aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0241] The preferred linking groups are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these. More preferably, they are -O-, -S-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these.

[0242] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0243] The alkyl halide described above is preferably an alkyl halide with 1 to 20 carbon atoms, more preferably an alkyl halide with 1 to 10 carbon atoms, and even more preferably an alkyl halide with 1 to 4 carbon atoms. Furthermore, examples of halogen atoms in the alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The alkyl halide may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkyl halide include bis(trifluoromethyl)methylene.

[0244] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0245] And, X 2 Preferably, it is a tricarboxylic acid compound derived from at least one carboxyl group that can be halogenated. As the halogenation mentioned above, chlorination is preferred.

[0246] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0247] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-substituted.

[0248] Examples of tricarboxylic acid compounds that can be halogenated include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0249] These tricarboxylic acid compounds can be used in one or more ways.

[0250] X 2 The structure preferably does not contain an imide structure.

[0251] And, X 2 The structure preferably does not contain urethane bonds, urea bonds, or amide bonds.

[0252] Additionally, X 2 Preferably, the structure does not contain ester bonds.

[0253] Among these, X 2 Preferably, it does not contain an imide structure, a carbamate bond, a urea bond, or an amide bond; more preferably, it does not contain an imide structure, a carbamate bond, a urea bond, an amide bond, or an ester bond.

[0254] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a group formed by combining two or more of these groups through single bonds or linking groups. More preferably, it is a tricarboxylic acid compound containing an aromatic group with 6 to 20 carbon atoms or a group formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0255] Furthermore, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) is linked to benzoic acid via single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene oxide.

[0256] These compounds can be compounds in which two carboxyl groups are anhydrinated (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride acyl chloride).

[0257] In equation (X-2), L 3Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, these are straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, these are aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0258] The preferred linking groups are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these. More preferably, they are -O-, -S-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these.

[0259] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0260] The alkyl halide described above is preferably an alkyl halide with 1 to 20 carbon atoms, more preferably an alkyl halide with 1 to 10 carbon atoms, and even more preferably an alkyl halide with 1 to 4 carbon atoms. Furthermore, examples of halogen atoms in the alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The alkyl halide may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkyl halide include bis(trifluoromethyl)methylene.

[0261] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0262] And, X 1 The structure can be represented by the following formula (X-3), or X in the structure represented by (X-3). 2 The hydrogen atom or L in the group represented 3 The hydrogen atoms of the group represented are represented by R in formula (1-1) 1 The structure represented by the base substitution.

[0263] [Chemical Formula 23]

[0264]

[0265] In equation (X-3), X2 Each of the three independent linking groups, L 3 The symbol indicates a divalent linker group, and * indicates a bonding site with other structures.

[0266] In equation (X-3), X 2 and L 3 The preferred method is the same as X in equation (X-2). 2 and L 3 The preferred method is the same.

[0267] -Y 1 -

[0268] Y 1 The carbon number is 4 or more, preferably 4 to 50, and more preferably 4 to 40.

[0269] In equation (1-1), Y 1 It can be a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-4).

[0270] The chemical resistance and flatness of the cured material are improved by adding an organic group to the structure formed by removing two or more hydrogen atoms from the structure represented by any of the formulas (V-1) to (V-4).

[0271] When Y 1 When Y is a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), 1 Preferably, it is a group represented by the following formula (V-1-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms are denoted by n1, which is an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further substituted with known substituents such as hydrocarbon groups.

[0272] [Chemical Formula 24]

[0273]

[0274] When Y 1 When Y is a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), 1 Preferably, the group represented by formula (V-2-3) or formula (V-2-4) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-2-4) is preferred. In the following formula, L X1 * indicates a single bond or -O-, and * indicates a Y in equation (1-1) 1 The bonding sites of the two nitrogen atoms. Furthermore, R X1The preferred method is as described above. Furthermore, the hydrogen atoms in these structures can be further substituted with known substituents such as hydrocarbon groups.

[0275] [Chemical Formula 25]

[0276]

[0277] When Y 1 When Y is a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), 1 Preferably, the group represented by formula (V-3-3) or formula (V-3-4) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-3) is preferred. In the following formulas, * represents Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in these structures can be further substituted with known substituents such as hydrocarbon groups.

[0278] [Chemical Formula 26]

[0279]

[0280] When Y 1 When Y is a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), 1 Preferably, it is a group represented by the following formula (V-4-2) or (V-4-3). In the following formulas, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms are denoted by n1, which is an integer from 0 to 5. Furthermore, n1 being 0 is also one of the preferred embodiments of the present invention. Additionally, the hydrogen atoms in the following structure can be further substituted with known substituents such as hydrocarbon groups.

[0281] [Chemical Formula 27]

[0282]

[0283] In addition, Y 1 It can be the group described in paragraphs 0042 to 0053 of Japanese Patent Application Publication No. 2023-003421.

[0284] Furthermore, Y 1 Preferably, the structure does not contain imide bonds.

[0285] Furthermore, Y 1 The structure preferably does not contain urethane bonds, urea bonds, or amide bonds.

[0286] In addition, Y 1 Preferably, the structure does not contain ester bonds.

[0287] Among these, Y 1 Preferably, it does not contain imide bonds, urethane bonds, urea bonds, and amide bonds; more preferably, it does not contain imide bonds, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0288] Among these, X in equation (1-1) 1 and Y 1 Preferably, these are organic groups that comprise structures formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-4) described above. The preferred embodiments of these groups are as described above.

[0289] -n and m-

[0290] In formula (1-1), m is preferably an integer from 0 to 2, more preferably 0 or 1. Furthermore, m being 0 is also one of the preferred embodiments of the present invention.

[0291] In formula (1-1), n ​​is preferably 1 or 2, and more preferably 2.

[0292] -W 1 -

[0293] In equation (1-1), W 1 The preferred method is the same as Y in the above formula (1-1). 1 The preferred method is the same.

[0294] -V 1 -

[0295] V 1 The organic group represented by the following formula (2-1) is indicated.

[0296] [Chemical Formula 28]

[0297]

[0298] In equation (2-1), Q 1 The symbol represents a hydrogen atom or a group represented by the following formula (2-2), and * represents the W in formula (1-1). 1 The bonding sites.

[0299] [Chemical Formula 29]

[0300]

[0301] In equation (2-2), T 1 The symbol represents a monovalent organic group, and * indicates the bonding site with the nitrogen atom in formula (2-1).

[0302] In equation (2-2), T 1 The preferred method is the same as the above formula (R) TThe preferred method is the same.

[0303] -R 1 -

[0304] R in equation (1-1) 1 It is a group containing a polymerizable group. The preferred manner of the polymerizable group is as described above.

[0305] R in equation (1-1) 1 Preferably, it has the structure represented by the following formula (R-1).

[0306] [Chemical Formula 30]

[0307]

[0308] In equation (R-1), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an aromatic group or a cyclic aliphatic group. 1 Indicates a polymerizable group, a1 indicates 1 or more and Z 1 Integers below the largest substitution base, a2 represents integers above 1, and * represents X in equation (1-1). 1 Or Y 1 The bonding sites.

[0309] In equation (R-1), L 1 Preferably, it is a group represented by the following formula (L-1).

[0310] [Chemical Formula 31]

[0311]

[0312] In equation (L-1), L x2 This represents a linking group with a valence of a2+1, where a2 represents an integer greater than 1, and * represents a linking group with Y in equation (1-1). 1 The bonding site, # indicates the bond with Z in equation (R-1). 1 The bonding sites.

[0313] L x2 Preferably, it is an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and especially preferably a methylene group.

[0314] The preferred method for a2 in equation (L-1) is the same as the preferred method for a2 in equation (R-1).

[0315] Z in equation (R-1) 1 More preferably, it is an aromatic group.

[0316] As an aromatic group, it can be any of an aromatic hydrocarbon group or a heteroaromatic cyclic group, but is preferably an aromatic hydrocarbon cyclic group or a heteroaromatic cyclic group containing a nitrogen atom as a cyclic atom.

[0317] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group is preferably an aromatic hydrocarbon ring with 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring with 6 to 10 carbon atoms, and even more preferably a benzene ring.

[0318] Examples of heteroaromatic rings that are heteroaromatic ring groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, imidazole rings, triazole rings, tetraazole rings, oxazole rings, pyridine rings, pyridazine rings, pyrazine rings, triazine rings, indole rings, indazole rings, benzimidazole rings, and purine rings.

[0319] Aliphatic rings, which are cyclic aliphatic groups, can be exemplified by aliphatic hydrocarbon rings with 5 to 20 carbon atoms, pyrrolidine rings, pyrrolidine rings, pyrazolidine rings, imidazoidine rings, tetrahydrofuran rings, tetrahydrothiophene rings, piperidine rings, piperazine rings, tetrahydropiperanone rings, dioxane rings, and mofolin rings.

[0320] Among these, as Z 1 Preferably, it is a benzene ring, a cyclohexane ring, or an adamantane ring, and more preferably a benzene ring.

[0321] A in equation (R-1) 1 Preferably, it is methacryloyloxy, acryloyloxy, vinyl or vinyl ether group, more preferably vinyl or vinyl ether group, and even more preferably vinyl.

[0322] In particular, A in equation (R-1) 1 At least one of them is preferably vinyl.

[0323] In formula (R-1), a1 is preferably an integer from 1 to 4, and more preferably an integer from 1 to 2. Furthermore, a1 being 1 is also one of the preferred embodiments of the present invention.

[0324] In formula (R-1), a2 represents an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0325] Furthermore, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0326] Furthermore, R in equation (1-1) 1 It is also preferred to contain maleimide groups.

[0327] When R 1 When maleimide group is included, R 1 Preferably, it is a group represented by the following formula (A-1).

[0328] [Chemical Formula 32]

[0329]

[0330] In formula (A-1), L A1 R represents a linking group with a single bond or an m+1 valence. R1 Each of the two Rs can independently represent a hydrogen atom or an organic group. R1 They can be linked, where m represents an integer greater than 1, and * represents the bonding site with other atoms.

[0331] In formula (A-1), L A1 Preferably, it contains aromatic groups or aliphatic saturated hydrocarbon groups with 4 or more carbon atoms.

[0332] The aromatic group or the aliphatic saturated hydrocarbon group with 4 or more carbon atoms mentioned above is preferably bonded to the maleimide group (i.e., the nitrogen atom in formula A-1) by a single bond without a linking group.

[0333] The aromatic group can be any of an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group.

[0334] As an aromatic hydrocarbon group, it is preferably an aromatic hydrocarbon group with 6 to 10 carbon atoms, and more preferably an aromatic hydrocarbon group with 6 carbon atoms.

[0335] Examples of heteroatoms in aromatic heterocyclic groups include oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms in the aromatic heterocyclic group is preferably one or two. Furthermore, the aromatic heterocyclic group is preferably a 5-membered or 6-membered ring containing the aforementioned heteroatoms. Moreover, other aromatic heterocyclic groups or other aromatic hydrocarbon cyclic groups may be condensed within the aromatic heterocyclic group.

[0336] As an aliphatic saturated hydrocarbon group with 4 or more carbon atoms, it can be any of the following structures: straight-chain, branched-chain, cyclic, or a combination thereof.

[0337] The aliphatic saturated hydrocarbon group with 4 or more carbon atoms preferably has 4 to 20 carbon atoms, and more preferably 5 to 10 carbon atoms.

[0338] Furthermore, as L A1 It is also preferred to use the following formula (A-1-1) or formula (A-2-2).

[0339] [Chemical Formula 33]

[0340]

[0341] In equation (A-1-1), Z 1 Indicates -O- or -NR N -, R NR represents a hydrogen atom or a monovalent organic group. A1 The symbol represents an aromatic group or an aliphatic saturated hydrocarbon group with 4 or more carbon atoms, m represents an integer of 1 or more, * has the same meaning as in formula (A-1), and # represents the bonding site with the nitrogen atom in formula (A-1).

[0342] In equation (A-1-2), Z 2 Indicates -O- or -NR N -, R N Represents a hydrogen atom or a monovalent organic group, R A2 The symbol represents an aromatic group or an aliphatic saturated hydrocarbon group with 4 or more carbon atoms, m represents an integer of 1 or more, * has the same meaning as * in formula (A-1), and # represents the bonding site with the nitrogen atom in formula (A-1).

[0343] In equation (A-1-1), Z 1 Preferably -O-. Z 1 For -NR N -R at that time N Preferably, it is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.

[0344] In equation (A-1-1), R A1 The preferred manner of these groups is as described above, which may refer to aromatic groups or aliphatic saturated hydrocarbon groups having 4 or more carbon atoms.

[0345] In equation (A-1-1), m has the same meaning as m in equation (A-1), and the preferred method is also the same.

[0346] In equation (A-1-2), Z 2 Preferably -O-. R N The preferred method is as described above.

[0347] In equation (A-1-2), R A2 The preferred method is the same as R in equation (A-1-1) A1 The preferred method is the same.

[0348] In equation (A-1-2), m has the same meaning as m in equation (A-1), and the preferred method is also the same.

[0349] In equation (A-1), R R1 Each of the following is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, even more preferably a hydrogen atom or a methyl group, and especially preferably a hydrogen atom.

[0350] In equation (A-1), as a combination of 2 R R1 Ring structures formed by linkages can be exemplified by cyclohexene rings, etc.

[0351] In formula (A-1), m is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, even more preferably an integer from 1 to 3, and especially preferably 1 or 2. Furthermore, m being 1 is also one of the preferred embodiments of the present invention.

[0352] The heterocyclic polymer A-1 may contain repeating units represented by formula (4).

[0353] The repeating unit corresponding to the repeating unit represented by equation (1-1) does not belong to the repeating unit represented by equation (4).

[0354] [Chemical Formula 34]

[0355]

[0356] In equation (4), R 131 R represents a divalent organic group. 132 This indicates a tetravalent organic group.

[0357] R 131 This represents a divalent organic group. As R 131 Examples of functional groups described in paragraphs 0042 to 0053 of Japanese Patent Application Publication No. 2023-003421 may be listed. These descriptions are incorporated into this specification.

[0358] R 132 This indicates a tetravalent organic group. As R 132 The compounds described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421 can be listed. These descriptions are incorporated into this specification.

[0359] When the heterocyclic polymer A-1 is a polyimide, the content of the repeating unit represented by formula (1-1) relative to the total mass of the heterocyclic polymer A-1 is preferably 30% by mass or more, more preferably 50% by mass or more, even 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 can be 100% by mass.

[0360] Furthermore, when the heterocyclic polymer A-1 is a polyimide, the total content of the repeating units represented by formula (1-1) and the repeating units represented by formula (4) relative to the total mass of the heterocyclic polymer A-1 is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and can be 100% by mass.

[0361] Furthermore, when the heterocyclic polymer A-1 contains repeating units represented by formula (1-1), it may contain two or more repeating units represented by formula (1-1) with different structures. In this case, the total amount is preferably within the above-mentioned range.

[0362] When the heterocyclic polymer A-1 contains repeating units represented by formula (4), it may contain two or more repeating units represented by formula (4) with different structures. In this case, the total amount is preferably within the range described above.

[0363] [The repeating unit represented by equation (XA)]

[0364] The heterocyclic polymer A-1 can be a resin containing repeating units represented by the following formula (XA).

[0365] [Chemical Formula 35]

[0366]

[0367] In formula (XA), X X1 Y represents an organic group with 4 or more carbon atoms. X1 R represents an organic group with 4 or more carbon atoms. X1 Each of these groups independently represents a group containing a polymerizable group, where n and m independently represent integers from 0 to 4, and n+m is 1 or higher. X1 R represents an organic group with 4 or more carbon atoms. 123 Q represents a hydrogen atom or a monovalent organic group. 1 It represents a hydrogen atom or a group represented by the above formula (2-2).

[0368] In formula (XA), X X1 The preferred method is the same as X in the above formula (1-1). 1 The preferred method is the same.

[0369] In formula (XA), Y X1 Preferably, the group comprises at least one of an aliphatic group and an aromatic group. As the group comprising an aliphatic group, a straight-chain aliphatic group is preferred. The straight-chain aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25, further preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. As the group comprising an aromatic group, a group represented by -Ar- or -Ar-A-Ar- is preferred. Ar independently represents an aromatic ring structure, preferably a benzene ring structure. A is preferably a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2-, and -C(CH3)2-.

[0370] In formula (XA), RX1 The preferred methods for n and m are the same as R in the above formula (1-1). 1 The optimal selection methods for n and m are the same.

[0371] In formula (XA), W X1 The preferred method is the same as X in the above formula (1-1). 1 The preferred method is the same.

[0372] In formula (XA), Q 1 Hydrogen atoms are preferred. Furthermore, the preferred manner of the group represented by formula (2-2) is as described above.

[0373] In formula (XA), R 123 Hydrogen atoms are preferred.

[0374] The weight-average molecular weight (Mw) of the heterocyclic polymer A-1 is preferably 3,000 to 100,000.

[0375] The lower limit of Mw is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more.

[0376] The upper limit of Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

[0377] Furthermore, the aforementioned Mw being 26,000 or less is also one of the preferred embodiments of the present invention. In the above embodiment, the Mw is preferably 16,000 or less, more preferably 12,000 or less. Furthermore, in the above embodiment, the Mw is preferably 5,000 or more, more preferably 6,000 or more. By setting such a relatively low molecular weight, resolution can be improved.

[0378] The number-average molecular weight (Mn) of the heterocyclic polymer A-1 is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000.

[0379] The molecular weight dispersion of the heterocyclic polymer A-1 is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit for the molecular weight dispersion, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, and even more preferably 4.5 or less, and particularly preferably 3.0 or less.

[0380] In this specification, the molecular weight dispersion is a value calculated from weight-average molecular weight / number-average molecular weight.

[0381] When the resin composition comprises multiple resins as heterocyclic polymer A-1, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the above-mentioned multiple resins are treated as a single resin are each within the above-mentioned ranges.

[0382] When the heterocyclic polymer A-1 is a polyimide, from the viewpoint of the obtained organic film's strength and insulation properties, the imidization rate (also referred to as "ring-closing rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the above imidization rate is not particularly limited, as long as it is 100% or less.

[0383] Furthermore, when the heterocyclic polymer A-1 is a polyimide, the content of the imide structure in the heterocyclic polymer A-1 is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less. The lower limit of the above content is not particularly limited, for example, it can be set to 0.5 mmol / g or more.

[0384] In this specification, the imidization rate is determined, for example, by the following method.

[0385] The infrared absorption spectrum of the resin was measured, and the absorption peak at 1377 cm⁻¹, which is derived from the imide structure, was determined. -1 The peak intensity P1 near the target was determined. Then, after heat-treating the resin at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity at 1377 cm⁻¹ was calculated. -1 The peak intensity P2 is nearby. Using the obtained peak intensities P1 and P2, the imidization rate of the resin can be calculated according to the following formula.

[0386] Imidification rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0387] [Heterocyclic polymer A-2]

[0388] The first resin composition comprises a heterocyclic polymer A-2.

[0389] The heterocyclic polymer A-2 is preferably polyimide or polybenzoxazole, more preferably polyimide.

[0390] -polymeric groups-

[0391] Heterocyclic polymer A-2 has polymerizable groups.

[0392] Examples of polymerizable groups include groups with olefinic unsaturated bonds, epoxy groups, oxocyclobutyl groups, benzoxazolyl groups, etc., with groups having olefinic unsaturated bonds being preferred.

[0393] Examples of groups containing olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0394] Among these, (meth)acryloyl, (meth)acrylamido, vinylphenyl, or maleimide are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity. Furthermore, vinylphenyl or maleimide is preferred from the viewpoint of reducing dielectric loss tangent.

[0395] The content of polymerizable groups (polymerizable group value) relative to the total mass of heterocyclic polymer A-2 is preferably 0.2 to 5.0 mmol / g, more preferably 0.25 to 4.0 mmol / g, and even more preferably 0.3 to 3.0 mmol / g.

[0396] -Specific substituent A-2-

[0397] The carboxylic acid ester group is -C(=O)O - The group represented. The counter cation relative to the anionic moiety described above is not particularly limited; examples include protons, Na+, and others. + K + Metal cations, ammonium cations, and ammonium cations, etc.

[0398] The carboxyl group that can be protected in structure A is preferably an unsubstituted carboxyl group.

[0399] Furthermore, the protected carboxyl group is preferably alkoxycarbonyl or aryloxycarbonyl, and more preferably tert-butoxycarbonyl.

[0400] Furthermore, the protected carboxyl group is preferably a group that generates a carboxyl group through light, heat, acid, or alkali. Whether a group generates a carboxyl group through light, heat, acid, or alkali can be determined using the same method as described above for determining whether it is a group that generates an amino group. However, in the above determination method, the amino group is replaced with a carboxyl group.

[0401] Here, the linking chain length in structure A is the number of atoms contained in structure A, which refers to the minimum number of atoms between the carbonyl groups in the two groups selected from the group consisting of the carboxylic acid ester group and the protected carboxyl group contained in structure A.

[0402] The heterocyclic polymer A-2 preferably contains a group represented by any one of the following formulas (S-1) to (S-4) as a specific substituent A-2.

[0403] [Chemical Formula 36]

[0404]

[0405] In equations (S-1) to (S-4), R S1 Represents -OH, -O - or -OR S2 R S2 Indicates a protecting group, Cy indicates an aliphatic ring structure, and L represents a protecting group. 1 This indicates a single bond or an aliphatic group with a chain length of 1 or 2, where n represents an integer of 1 or 2, and * indicates a bonding site with other structures.

[0406] In equations (S-1) to (S-4), R S1 Preferably -OH or -O - R S1 -O - The counter cations at that time are not particularly limited; examples include protons and Na+. + K + Metal cations, ammonium cations, and ammonium cations, etc.

[0407] When R S1 Indicates -OR S2 At that time, R S2 Preferably alkyl or aryl, more preferably alkyl with 1 to 4 carbon atoms, and even more preferably tert-butyl.

[0408] Cy is preferably a cycloalkane structure, and more preferably a cyclohexane ring structure.

[0409] n is preferably 1.

[0410] L 1 Preferably, it is a single bond, methylene, or ethylene, and more preferably a single bond.

[0411] Furthermore, the heterocyclic polymer A-2 preferably contains a group represented by any one of the following formulas (CA-1) or (CA-2) as a specific substituent A-2.

[0412] [Chemical Formula 37]

[0413]

[0414] In equation (CA-1), R C1 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. C2 The symbol represents a substituent, a represents an integer from 0 to 3, * represents a bonding site with other structures, b represents 1 or 2, and the total of a and b is less than 4.

[0415] In equation (CA-2), R C1 Represent -OH and -O independently, respectively. - or -ORC R C R represents an organic group. C2 The symbol represents a substituent, a represents an integer from 0 to 9, * represents a bonding site with other structures, b represents 1 or 2, and the total of a and b is less than 10.

[0416] In equation (CA-1), R C1 Preferably -OH or -O - R C1 -O - The counter cations at that time are not particularly limited; examples include protons and Na+. + K + Metal cations, ammonium cations, and ammonium cations, etc.

[0417] R C1 For -OR C R at that time C Preferably alkyl or aryl, more preferably alkyl with 1 to 4 carbon atoms, and even more preferably tert-butyl.

[0418] In equation (CA-1), R C2 Preferably, it is an alkyl or aryl group, more preferably an alkyl group having 1 to 4 carbon atoms.

[0419] In formula (CA-1), a is preferably 0 or 1.

[0420] In formula (CA-1), b is preferably 1.

[0421] In equation (CA-2), R C1 R C2 The preferred methods for a and b are the same as R in equation (CA-1). C1 R C2 The preferred methods for a and b are the same.

[0422] -The repeating unit represented by equation (1-2) or equation (1-3)-

[0423] The heterocyclic polymer A-2 preferably contains repeating units represented by formula (1-2) or formula (1-3) below.

[0424] [Chemical Formula 38]

[0425]

[0426] In equation (1-2), X 2 Y represents an organic group with 4 or more carbon atoms. 2 W represents an organic group with 4 or more carbon atoms. 2 G represents an organic group with 4 or more carbon atoms. 1 and G 2Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. 2 Each of the above groups independently represents a group containing a polymerizable group, and n and m independently represent integers from 0 to 4, with n+m being 1 or higher.

[0427] In equation (1-3), X 3 Y represents an organic group with 4 or more carbon atoms. 3 W represents an organic group with 4 or more carbon atoms. 3 V represents a single bond or an organic group with 4 or more carbon atoms. 3 R represents the organic group represented by formula (3-1) or formula (3-2) below. 3 Each of the above groups independently represents a group containing a polymerizable group, and n and m independently represent integers from 0 to 4, with n+m being 1 or higher.

[0428] [Chemical Formula 39]

[0429]

[0430] In equation (3-1), R C1 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. C2 The substituent is represented by 'a', which represents an integer from 0 to 3, and '*' represents the substituent in equation (1-3). 3 The bonding sites.

[0431] In equation (3-2), R C1 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. C2 The substituent is represented by 'a', which represents an integer from 0 to 9, and '*' represents the substituent in equation (1-3). 3 The bonding sites.

[0432] In equation (1-2), X 2 Y 2 and R 2 The preferred method is the same as X in the above formula (1-1). 1 Y 1 and R 1 The preferred method is the same.

[0433] In equation (1-2), W 2 The preferred method is the same as X in the above formula (1-1). 1 The preferred method is the same.

[0434] In equation (1-2), G 1 and G 2 The preferred method is the same as R in the above formula (CA-1). C1 The preferred method is the same.

[0435] In equation (1-3), X 3 Y 3 and R 3 The preferred method is the same as X in the above formula (1-1). 1 Y 1 and R 1 The preferred method is the same.

[0436] In equation (1-3), W 3 Preferably, it is a single bond or an aliphatic hydrocarbon group, an aromatic group, or a combination thereof.

[0437] In equation (3-1), R C1 R C2 The preferred method of a is the same as R in the above formula (CA-1). C1 R C2 The preferred method for a is the same.

[0438] In equation (3-2), R C1 R C2 The preferred method of a is the same as R in the above formula (CA-2). C1 R C2 The preferred method for a is the same.

[0439] The heterocyclic polymer A-2 may contain repeating units represented by the above formula (4).

[0440] When the heterocyclic polymer A-2 is a polyimide, the total content of the repeating units represented by formula (1-2) and formula (1-3) relative to the total mass of the heterocyclic polymer A-2 is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and especially preferably 80% by mass or more. The upper limit of the above content is not particularly limited and can be 100% by mass.

[0441] Furthermore, when the heterocyclic polymer A-2 is a polyimide, the total content of the repeating units represented by formula (1-2), formula (1-3), and formula (4) relative to the total mass of the heterocyclic polymer A-2 is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and can be 100% by mass.

[0442] Furthermore, when the heterocyclic polymer A-2 contains repeating units represented by formula (1-2), it may contain two or more repeating units represented by formula (1-2) with different structures. In this case, the total amount is preferably within the above-mentioned range.

[0443] Furthermore, when the heterocyclic polymer A-2 contains repeating units represented by formula (1-3), it may contain two or more repeating units represented by formula (1-3) with different structures. In this case, the total amount is preferably within the range described above.

[0444] When the heterocyclic polymer A-2 contains repeating units represented by formula (4), it may contain two or more repeating units represented by formula (4) with different structures. In this case, the total amount is preferably within the range described above.

[0445] [The repeating unit represented by equation (XB)]

[0446] The heterocyclic polymer A-1 can be a resin containing repeating units represented by the following formula (XB).

[0447] [Chemical Formula 40]

[0448]

[0449] In formula (XB), X X1 Y represents an organic group with 4 or more carbon atoms. X1 R represents an organic group with 4 or more carbon atoms. X1 Each of these groups independently represents a group containing a polymerizable group, where n and m independently represent integers from 0 to 4, and n+m is 1 or higher. X2 R represents an organic group with 4 or more carbon atoms. X2 It represents a hydrogen atom or an organic group with a valence of 1.

[0450] In formula (XB), X X1 Y X1 R X1 The preferred methods for n and m are the same as those for X in the above formula (XA). X1 Y X1 R X1 The optimal selection methods for n and m are the same.

[0451] In formula (XB), W X2 The preferred method is the same as Y in the above formula (XA). X1 The preferred method is the same.

[0452] In formula (XB), R X2 Preferably, it is a hydrogen atom. When R X2 When the organic group is monovalent, it is preferably alkyl or aryl, and more preferably alkyl with 1 to 4 carbon atoms.

[0453] The weight-average molecular weight (Mw) of the heterocyclic polymer A-2 is preferably 3,000 to 100,000.

[0454] The lower limit of Mw is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more.

[0455] The upper limit of Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

[0456] Furthermore, the aforementioned Mw being 26,000 or less is also one of the preferred embodiments of the present invention. In the above embodiment, the Mw is preferably 16,000 or less, more preferably 12,000 or less. Furthermore, in the above embodiment, the Mw is preferably 5,000 or more, more preferably 6,000 or more. By setting such a relatively low molecular weight, resolution can be improved.

[0457] The number-average molecular weight (Mn) of the heterocyclic polymer A-2 is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000.

[0458] The molecular weight dispersion of the heterocyclic polymer A-2 is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit for the molecular weight dispersion, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, and even more preferably 4.5 or less, and particularly preferably 3.0 or less.

[0459] When the resin composition comprises multiple resins as heterocyclic polymer A-2, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the above-mentioned multiple resins are treated as a single resin are each within the above-mentioned ranges.

[0460] When the heterocyclic polymer A-2 is a polyimide, from the viewpoint of the obtained organic film's strength and insulation properties, the imidization rate (also referred to as "ring-closing rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the above imidization rate is not particularly limited, as long as it is 100% or less.

[0461] Furthermore, when the heterocyclic polymer A-2 is a polyimide, the content of the imide structure in the heterocyclic polymer A-2 is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less. The lower limit of the above content is not particularly limited, for example, it can be set to 0.5 mmol / g or more.

[0462] The embodiment in which the heterocyclic polymer A-1 has two or more of the above-mentioned protected amino groups and the heterocyclic polymer A-2 has two or more of the above-mentioned structure A is also one of the preferred embodiments of the present invention.

[0463] [Resin 1]

[0464] The second resin composition contains resin 1 comprising repeating units represented by formula (1-1).

[0465] The preferred mode of the repeating unit represented by formula (1-1) in resin 1 is the same as the preferred mode of the repeating unit represented by formula (1-1) in the heterocyclic polymer A-1 described above.

[0466] Furthermore, resin 1 may contain repeating units as represented by the above formula (4).

[0467] The content of the repeating unit represented by formula (1-1) relative to the total mass of resin 1 is preferably 30% by mass or more, more preferably 50% by mass or more, even 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 can be 100% by mass.

[0468] Furthermore, the total content of the repeating units represented by formula (1-1) and the repeating units represented by formula (4) relative to the total mass of resin 1 is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and can be 100% by mass.

[0469] Furthermore, resin 1 may contain two or more repeating units represented by formula (1-1) with different structures. In this case, the total amount is preferably within the range described above.

[0470] When resin 1 contains the repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) with different structures. In this case, the total amount is preferably within the range described above.

[0471] The content of polymeric groups relative to the total mass of resin 1 (polymeric group value) is preferably 0.2 to 5.0 mmol / g, more preferably 0.25 to 4.0 mmol / g, and even more preferably 0.3 to 3.0 mmol / g.

[0472] The weight-average molecular weight (Mw) of resin 1 is preferably 3,000 to 100,000.

[0473] The lower limit of Mw is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more.

[0474] The upper limit of Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

[0475] Furthermore, the aforementioned Mw being 26,000 or less is also one of the preferred embodiments of the present invention. In the above embodiment, the Mw is preferably 16,000 or less, more preferably 12,000 or less. Furthermore, in the above embodiment, the Mw is preferably 5,000 or more, more preferably 6,000 or more. By setting such a relatively low molecular weight, resolution can be improved.

[0476] The number-average molecular weight (Mn) of resin 1 is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000.

[0477] The molecular weight dispersion of resin 1 is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit for the molecular weight dispersion, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, and even more preferably 4.5 or less, and particularly preferably 3.0 or less.

[0478] When the resin composition comprises multiple resins as resin 1, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple resins are treated as a single resin are each within the above-mentioned ranges.

[0479] From the viewpoint of the obtained organic membrane's strength, insulation, etc., the imidization rate (also referred to as "ring-closing rate") of resin 1 is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the above imidization rate is not particularly limited, as long as it is 100% or less.

[0480] Furthermore, the content of imide structures in resin 1 is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less. The lower limit of the above content is not particularly limited, for example, it can be set to 0.5 mmol / g or more.

[0481] [Resin 2]

[0482] The second resin composition contains resin 1 comprising repeating units represented by formula (1-2) or formula (1-3).

[0483] The preferred manner of the repeating unit represented by formula (1-2) or formula (1-3) in resin 2 is the same as the preferred manner of the repeating unit represented by formula (1-2) or formula (1-3) in the heterocyclic polymer A-2 described above.

[0484] Furthermore, resin 2 may contain repeating units as represented by the above formula (4).

[0485] The total content of repeating units represented by formulas (1-2) and (1-3) relative to the total mass of resin 2 is preferably 30% by mass or more, more preferably 50% by mass or more, even 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 can be 100% by mass.

[0486] Furthermore, the total content of the repeating units represented by formula (1-2), formula (1-3), and formula (4) relative to the total mass of resin 2 is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and can be 100% by mass.

[0487] Furthermore, when resin 2 contains repeating units represented by formula (1-2), it may contain two or more repeating units represented by formula (1-2) with different structures. In this case, the total amount is preferably within the above-mentioned range.

[0488] Furthermore, when resin 2 contains repeating units represented by formula (1-3), it may contain two or more repeating units represented by formula (1-3) with different structures. In this case, the total amount is preferably within the above-mentioned range.

[0489] Furthermore, when resin 2 contains the repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) with different structures. In this case, the total amount is preferably within the above range.

[0490] The content of polymeric groups relative to the total mass of resin 2 (polymeric group value) is preferably 0.2 to 5.0 mmol / g, more preferably 0.25 to 4.0 mmol / g, and even more preferably 0.3 to 3.0 mmol / g.

[0491] The weight-average molecular weight (Mw) of resin 2 is preferably 3,000 to 100,000.

[0492] The lower limit of Mw is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more.

[0493] The upper limit of Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

[0494] Furthermore, the aforementioned Mw being 26,000 or less is also one of the preferred embodiments of the present invention. In the above embodiment, the Mw is preferably 16,000 or less, more preferably 12,000 or less. Furthermore, in the above embodiment, the Mw is preferably 5,000 or more, more preferably 6,000 or more. By setting such a relatively low molecular weight, resolution can be improved.

[0495] The number-average molecular weight (Mn) of resin 2 is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000.

[0496] The molecular weight dispersion of resin 2 is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit for the molecular weight dispersion, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, and even more preferably 4.5 or less, and particularly preferably 3.0 or less.

[0497] When the resin composition comprises multiple resins as resin 2, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple resins are treated as a single resin are each within the above-mentioned ranges.

[0498] From the viewpoint of the obtained organic membrane's strength, insulation, etc., the imidization rate (also referred to as "ring-closing rate") of resin 2 is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the above imidization rate is not particularly limited, as long as it is 100% or less.

[0499] Furthermore, the content of imide structures in resin 2 is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less. The lower limit of the above content is not particularly limited, for example, it can be set to 0.5 mmol / g or more.

[0500] Here, when the resin composition of the present invention contains a resin comprising a repeating unit represented by formula (1-1) and a resin comprising a repeating unit represented by formula (1-2) or formula (1-3) as a specific resin, R of formula (1-1) is preferred. 1 R in equation (1-2) 2and R in equation (1-3) 3 This represents the structure indicated by the above equation (R-1).

[0501] Furthermore, in this way, A in equation (R-1) 1 At least one of them is preferably vinyl.

[0502] In this method, R in equation (1-1) 1 R in equation (1-2) 2 and R in equation (1-3) 3 The preferred embodiment of formula (R-1) is as described above.

[0503] Furthermore, when the resin composition of the present invention contains a resin comprising a repeating unit represented by formula (1-1) and a resin comprising a repeating unit represented by formula (1-2) or formula (1-3) as a specific resin, R of formula (1-1) is preferred. 1 R in equation (1-2) 2 and R in equation (1-3) 3 It contains maleimide groups.

[0504] In this method, R in equation (1-1) 1 R in equation (1-2) 2 and R in equation (1-3) 3 The preferred method is as described above.

[0505] Furthermore, when the resin composition of the present invention contains a resin comprising a repeating unit represented by formula (1-1) and a resin comprising a repeating unit represented by formula (1-2) or formula (1-3) as a specific resin, G in formula (1-2) is preferred. 1 and G 2 R in equation (3-1) C1 and R in equation (3-2) C1 All are hydrogen atoms.

[0506] [Manufacturing method of specific resins]

[0507] For example, certain resins can be obtained by methods such as: reacting tetracarboxylic dianhydride with diamine at low temperature; reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamic acid, and then esterifying it using a condensing agent or an alkylating agent; obtaining a diester from tetracarboxylic dianhydride and alcohol, and then reacting it in the presence of diamine and a condensing agent; and obtaining a diester from tetracarboxylic dianhydride and alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine, etc. In the above manufacturing methods, a more preferred method is to obtain a diester from tetracarboxylic dianhydride and alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine.

[0508] Here, for example, by using an excess of diamine in the above reaction, amino groups can be introduced into the resin, and by using an excess of tetracarboxylic acid dianhydride in the above reaction, carboxyl groups can be introduced into the resin. Furthermore, these amino groups can be protected with protecting groups using known methods, and these carboxyl groups can be carboxylated.

[0509] Examples of condensing agents mentioned above 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.

[0510] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0511] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0512] Furthermore, when a polyimide is desired as a specific resin, it can be synthesized using the following methods: a method of completely imidizing the resin obtained by the above methods using a known imidization reaction; a method of stopping the imidization reaction midway and introducing a partial imide structure; and a method of introducing a partial imide structure by mixing the fully imidized polymer with the polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0513] In the manufacturing method of a particular resin, an organic solvent is preferably used during the reaction. The organic solvent may be one type or two or more.

[0514] As organic solvents, examples include pyridine, diethylene glycol dimethyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone, depending on the appropriate specifications of the raw materials.

[0515] In a particular resin manufacturing method, it is preferable to add an alkaline compound during the reaction. The alkaline compound can be one type or two or more.

[0516] Basic compounds can be appropriately specified according to the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0517] -End- Capping Agent-

[0518] In the manufacturing method of a specific resin, to further improve storage stability, it is preferable to seal the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin end of the specific resin. When sealing the carboxylic anhydride and anhydride derivative remaining at the resin end, end-capping agents include monools, phenols, thiols, thiophenols, and monoamines. From the viewpoint of reactivity and film stability, monools, phenols, or monoamines are more preferred. Preferred monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tert-butanol, adamantanol, etc. Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds as monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminenaphthalene, 1-hydroxy-6-aminenaphthalene, 1-hydroxy-5-aminenaphthalene, 1-hydroxy-4-aminenaphthalene, 2-hydroxy-7-aminenaphthalene, 2-hydroxy-6-aminenaphthalene, 2-hydroxy-5-aminenaphthalene, 1-carboxy-7-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-5-aminenaphthalene, 2 ...6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-6-aminena Examples of amino compounds include 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, and 4-aminobenzenethiophenol. Two or more of these can be used, or multiple different end groups can be introduced by reacting various end-capping agents.

[0519] Furthermore, when sealing the amino group at the end of the resin, a compound having a functional group capable of reacting with the amino group can be used for sealing. Preferred sealants for the amino group include carboxylic anhydride, carboxylic acid chloride, carboxylic bromide, sulfonyl chloride, sulfonic anhydride, and sulfonic acid carboxylic anhydride, with carboxylic anhydride and carboxylic acid chloride being more preferred. Examples of preferred carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of preferred carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexane carbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0520] Furthermore, by bonding a capping material having a specific substituent A-1 or a specific substituent A-2 to the end of the resin, it is also possible to introduce the specific substituent A-1 or the specific substituent A-2 into the resin.

[0521] Specifically, the structure represented by the above formula (1-1) can be introduced into the resin by reacting the compound represented by the following formula (T-1) with a resin whose terminal is a carboxylic acid (or carboxylic anhydride).

[0522] [Chemical Formula 41]

[0523]

[0524] In equation (T-1), W 1 V represents an organic group with 4 or more carbon atoms. 1 This represents the organic group represented by the above formula (2-1).

[0525] In equation (T-1), W 1 and V 1 The preferred method is the same as W in equation (1-1) 1 and V 1 The preferred method is the same.

[0526] Furthermore, by reacting the compound represented by the following formula (T-2) with a resin terminally containing an amino group, the structure represented by the above formula (1-2) can be introduced into the resin.

[0527] [Chemical Formula 42]

[0528]

[0529] In equation (T-2), W 2 G represents an organic group with 4 or more carbon atoms. 1 and G 2 Represent -OH and -O independently, respectively. - or -OR C R C It represents an organic group.

[0530] In equation (T-2), W 2 G 1 and G 2 The preferred method is the same as W in equation (1-2) 2 G 1 and G 2 The preferred method is the same.

[0531] By reacting the compound represented by the following formula (T-3) with a resin whose terminal component is a carboxylic acid (or carboxylic anhydride), the structure represented by the above formula (1-3) can also be introduced into the resin.

[0532] [Chemical Formula 43]

[0533]

[0534] In equation (T-3), W 3 V represents a single bond or an organic group with 4 or more carbon atoms. 3 This represents the organic group represented by formula (3-1) or formula (3-2) above.

[0535] In equation (T-3), W 2 and V 3 The preferred method is the same as W in equation (1-3). 2 and V 3 The preferred method is the same.

[0536] -Solid precipitation-

[0537] The manufacturing method of a specific resin may include a step of precipitating a solid. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof to precipitate the polymer component, thereby precipitating it as a solid and drying it to obtain the specific resin. To improve the purification degree, the specific resin may be repeatedly subjected to operations such as redissolving, redepositing, and drying. The method may further include a step of removing ionic impurities using an ion exchange resin.

[0538] [Specific example]

[0539] Specific examples of particular resins include polyimides SA-1 to SA-6, SB-1 to SB-10, etc., in the examples described later, but the present invention is not limited thereto.

[0540] 〔content〕

[0541] The content of a specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, even more preferably 50% by mass or more, and most preferably 60% by mass or more, relative to the total solids content of the resin composition. Furthermore, the content of a specific resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the resin composition.

[0542] The resin composition of the present invention comprises two or more specific resins. The above-mentioned content values ​​represent the total amount of the specific resins.

[0543] Relative to the total solids content of the resin composition, the content of the heterocyclic polymer A-1 in the first resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and most preferably 30% by mass or more. Furthermore, the above-mentioned content is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0544] Relative to the total solids content of the resin composition, the content of the heterocyclic polymer A-2 in the first resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and most preferably 30% by mass or more. Furthermore, the above-mentioned content is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0545] Relative to the total solids content of the resin composition, the content of resin 1 in the second resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and most preferably 30% by mass or more. Furthermore, the above-mentioned content is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0546] Relative to the total solids content of the resin composition, the content of resin 2 in the second resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and most preferably 30% by mass or more. Furthermore, the above-mentioned content is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0547] The content of heterocyclic polymer A-1 in the first resin composition is preferably 50 to 150% by mass, more preferably 60 to 140% by mass, and even more preferably 70 to 130% by mass, relative to the content of heterocyclic polymer A-2.

[0548] The content of resin 1 in the second resin composition is preferably 50 to 150% by mass relative to the content of resin 2, more preferably 60 to 140% by mass, and even more preferably 70 to 130% by mass.

[0549] The resin composition of the present invention preferably contains at least two resins.

[0550] Specifically, the resin composition of the present invention may contain a total of two or more specific resins and resin C or other resins described later, or may contain two or more specific resins, but preferably contains two or more specific resins.

[0551] The first resin composition preferably further comprises resin C, which is a resin containing repeating units represented by formula (4-1) or formula (4-2) and not belonging to heterocyclic polymer A-1 and heterocyclic polymer A-2.

[0552] The second resin composition preferably further comprises resin C, which is a resin containing repeating units represented by formula (4-1) or formula (4-2) and not belonging to resin 1 and resin 2.

[0553] [Chemical Formula 44]

[0554]

[0555] In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each is an independent hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of them is a monovalent organic group having an olefinic unsaturated bond.

[0556] [Chemical Formula 45]

[0557]

[0558] In equation (4-2), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Let each independently represent the structure represented by the following formula (R-2), where n and m independently represent integers from 0 to 4, and n+m is 1 or higher.

[0559] [Chemical Formula 46]

[0560]

[0561] In equation (R-2), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an organic group with a valence of a1+1. 1The terms represent vinyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, or epoxy, where a1 represents an integer greater than or equal to 1, a2 represents an integer greater than or equal to 1, and * represents X in formula (4-2). 1 Or Y 1 The bonding sites.

[0562] In equation (4-1), X 1 and Y 1 The preferred method is the same as X in equation (1-1) 1 and Y 1 The preferred method is the same.

[0563] In equation (4-1), R 1 and R 2 Each of the organic groups is independently a hydrogen atom or a monovalent organic group, preferably all of which are monovalent organic groups, more preferably all of which are monovalent organic groups having an olefinic unsaturated bond.

[0564] Examples of monovalent organic groups having an olefinic unsaturated bond include those having a vinyl, allyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, or maleimide group, with a monovalent organic group having a (meth)acryloyloxy group being preferred.

[0565] In equation (4-2), X 1 Y 1 The preferred methods for n and m are the same as those for X in equation (1-1). 1 Y 1 The optimal selection methods for n and m are the same.

[0566] In equation (R-2), L 1 Z 1 A 1 The preferred methods for a1 and a2 are the same as those for L in the above formula (R-1). 1 Z 1 A 1 The preferred methods for a1 and a2 are the same.

[0567] The content of resin C relative to the total solids content of the resin composition of the present invention is preferably 0 to 70% by mass, more preferably 0 to 50% by mass, and even more preferably 0 to 30% by mass. When resin C is present, the lower limit of the above content is preferably 5% by mass or more, more preferably 10% by mass or more.

[0568] <Other Resins>

[0569] The resin composition of the present invention may contain other resins (hereinafter also referred to as "other resins") that are different from the specific resins and resin C described above.

[0570] Other resins include resins that are different from specific resins and resin C, corresponding to polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, polyamide-imide precursors, polyamide-imides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, polyester resins, etc.

[0571] As other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazole, polyamide-imide precursors, and polyamide-imides, compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355 may be listed. The above description is incorporated herein by reference.

[0572] When the resin composition of the present invention contains other resins, the content of other resins relative to the total solid content of the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0573] The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solids content of the resin composition.

[0574] As a preferred embodiment of the resin composition of the present invention, it is also possible to configure the content of other resins to be low. In the above embodiment, the content of other resins relative to the total solids content of the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0575] The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, the total amount is preferably within the range described above.

[0576] <Polymerizing compounds>

[0577] The resin composition of the present invention preferably contains a polymerizable compound.

[0578] The melting point of the polymerizable compound is preferably below 25°C.

[0579] By setting the melting point below 25°C, the coating film flows easily during drying and heating, which improves the flatness of the cured product.

[0580] In particular, from the viewpoint of reducing the dielectric constant of the cured product, as a polymerizable compound, it is preferred to include a compound with a ClogP value of 3.0 or higher, and more preferably a compound with a ClogP value of 3.0 or higher and having an aromatic ring structure or an aliphatic ring structure with 6 or more carbon atoms.

[0581] In this specification, the ClogP value of the compound is based on the following definition.

[0582] The octanol-water partition coefficient (logP value) can generally be determined by the flask permeation method described in JIS Japanese Industrial Standard Z7260-107 (2000). Furthermore, the octanol-water partition coefficient (logP value) can also be estimated using computational chemistry methods or empirical methods instead of actual measurement. As calculation methods, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989)), and Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984)) are known. In this invention, Crippen's fragmentation method is used (J. Chem. Inf. Comput. Sci., 27, 21 (1987)).

[0583] The ClogP value refers to the commonly used logarithm logP, which is used to calculate the partition coefficient P between 1-octanol and water. Regarding the methods or software used in calculating the ClogP value, well-known sources can be used; unless otherwise specified, the ClogP program of PCModels, a system assembled by Daylight Chemical Information Systems, is used in this invention.

[0584] The ClogP value is preferably 4.0 or higher, and more preferably 6.0 or higher.

[0585] Furthermore, the upper limit of the above ClogP value is not particularly limited, but it is preferably below 15.0.

[0586] The aromatic ring structure described above can be an aromatic hydrocarbon ring or an aromatic heterocycle, but is preferably an aromatic hydrocarbon ring, and more preferably contains a benzene ring. Furthermore, from the viewpoint of reducing the dielectric constant of the cured product, fused rings such as fluorene rings are preferred.

[0587] 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.

[0588] Aliphatic ring structures with 6 or more carbon atoms can be listed as monocyclic rings such as cyclohexane, bicyclic pentane, and tricyclic rings [5.2.1.0]. 2,6 Heterocyclic rings such as decane rings are preferred.

[0589] Polymerizable compounds with a ClogP value of 3.0 or higher (especially compounds with a ClogP value of 3.0 or higher and having an aromatic ring structure or an aliphatic ring structure with 6 or more carbon atoms) are preferably compounds containing groups having olefinic unsaturated bonds, more preferably compounds containing two or more groups having olefinic unsaturated bonds. Furthermore, compounds containing two groups having olefinic unsaturated bonds are also preferred.

[0590] Furthermore, polymerizable compounds with a ClogP value of 3.0 or higher (especially compounds with a ClogP value of 3.0 or higher and having an aromatic ring structure or an aliphatic ring structure with 6 or more carbon atoms) are preferably compounds corresponding to the free radical crosslinking agents described later.

[0591] Specific examples of polymeric compounds with a ClogP value of 3.0 or higher include the following compounds, but are not limited to them.

[0592] [Chemical Formula 47]

[0593]

[0594] [Chemical Formula 48]

[0595]

[0596] [Chemical Formula 49]

[0597]

[0598] As polymerizable compounds, free radical crosslinking agents or other crosslinking agents can be listed.

[0599] [Free radical cross-linking agent]

[0600] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0601] A free radical crosslinking agent is a compound having a free radical polymerizable group. Preferably, the free radical polymerizable group is a group containing an olefinic unsaturated bond. Examples of such groups containing an olefinic unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0602] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0603] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, but more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may also have three or more olefinic unsaturated bonds.

[0604] The compounds having two or more olefinic unsaturated bonds are preferably compounds having 2 to 15 olefinic unsaturated bonds, more preferably compounds having 2 to 10 olefinic unsaturated bonds, and even more preferably compounds having 2 to 6 olefinic unsaturated bonds.

[0605] From the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention is preferably a compound having two olefinic unsaturated bonds and a compound having three or more of the above-mentioned olefinic unsaturated bonds.

[0606] The molecular weight of the free radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the free radical crosslinking agent is preferably 100 or more.

[0607] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids, are also preferred. Additionally, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Furthermore, as another example, compounds that replace the aforementioned unsaturated carboxylic acids with unsaturated phosphonic acids, styrene or other vinylbenzene derivatives, vinyl ethers, allyl ethers, etc., can also be used. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0608] The free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include those described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated into this specification.

[0609] Preferred free radical crosslinking agents, other than those mentioned above, include free radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0610] As a free radical crosslinking agent, preferred are dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0611] Commercially available free radical crosslinking agents include, for example, tetrafunctional acrylates SR-494 with four ethoxy groups, difunctional methacrylates SR-209, 231, and 239 with four ethoxy groups (manufactured by Sartomer Company, Inc.), hexafunctional acrylates DPCA-60 with six pentylioxy groups, trifunctional acrylates TPA-330 with three isobutyryloxy groups (manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.). (Manufactured by Kyoisha Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOFCORPORATION.), etc.

[0612] As a free radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, or urethane compounds having an ethylene oxide backbone as described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418, are also preferred. Compounds having an amino or thioether structure within the molecule as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238 can also be used as a free radical crosslinking agent.

[0613] The free radical crosslinking agent can also be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent having acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a free radical crosslinking agent that has acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred is that, in the free radical crosslinking agent that has acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. Commercially available examples include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO.,LTD., such as M-510 and M-520.

[0614] The acid value of the free radical crosslinking agent containing acid groups is preferably 0.1 to 300 mg KOH / g, more preferably 1 to 100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and developability. Furthermore, it demonstrates good polymerizability. The above acid value is determined according to the description in JIS K 0070:1992.

[0615] From the viewpoint of pattern resolution and film elasticity, it is preferable to use a difunctional methacrylate or acrylate resin composition.

[0616] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1 6-Hexanediol dimethacrylate, dimethylol-tricyclodecane dimethacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct dimethacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct dimethacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, cyanuric acid EO-modified dimethacrylate, cyanuric acid EO-modified dimethacrylate, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. These can be mixed in combination for use as needed.

[0617] Additionally, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate, and the molecular weight of the polyethylene glycol chain is around 200.

[0618] From the viewpoint of suppressing warping of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are 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, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinyl caprolactam, and other N-vinyl compounds, allyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, in order to suppress volatilization before exposure, compounds having a boiling point of 100°C or higher under normal pressure are also preferred.

[0619] In addition, as free radical crosslinking agents with two or more functions, examples include allyl compounds such as diallyl phthalate and trimellitic acid triallyl ester.

[0620] When a free radical crosslinking agent is present, the content of the free radical crosslinking agent relative to the total solids content of the resin composition is preferably more than 0% by mass and less than 60% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0621] Free radical crosslinking agents can be used alone or in combination of two or more. When two or more are used together, the total amount is preferably within the range described above.

[0622] [Other crosslinking agents]

[0623] The resin composition of the present invention is also preferably composed of other crosslinking agents different from the free radical crosslinking agents described above.

[0624] Other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents mentioned above. Preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds in the composition or their reaction products by photosensitization by the photoacid generator or photoalkali generator mentioned above. They are also preferably compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds in the composition or their reaction products by the action of acid or base.

[0625] The acid or base mentioned above is preferably an acid or base generated by a photoacid generator or a photoalkali generator during the exposure process.

[0626] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0627] [Polymerization initiator]

[0628] The resin composition of the present invention comprises a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, and is particularly preferably a photopolymerization initiator.

[0629] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitizing to light from the ultraviolet region to the visible region is preferred. Furthermore, an active agent that generates active free radicals by interacting with a photoexcited sensitizer can also be used.

[0630] The photoradical polymerization initiator preferably contains at least one component having a wavelength of at least about 50 L·mol⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 ·cm -1The molar absorptivity of a compound can be determined using known methods. For example, it is preferred to use a UV-Vis spectrophotometer (a Cary-5 spectrophotometer manufactured by Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0631] As photoradical polymerization initiators, any known compounds can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl diimidazoles, 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, organoboron compounds, iron aromatic hydrocarbon complexes, etc. For detailed information on these, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, the following can be cited as examples: paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173; compounds described in Japanese Patent Publication No. 6301489; peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019; photopolymerization initiators described in International Publication No. 2018 / 221177; photopolymerization initiators described in International Publication No. 2018 / 110179; photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864; photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030; and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313. These contents are incorporated into this specification.

[0632] Examples of ketone compounds include, for instance, those described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0633] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators as described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators as described in Japanese Patent No. 4225898 can be used, as these contents are incorporated herein by reference.

[0634] As α-hydroxyketone initiators, 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, and IRGACURE 127 (all manufactured by BASF) can be used.

[0635] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0636] As an aminoacetophenone-based initiator, an acylphosphine oxide-based initiator, or a metallocene compound, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 may also be used, for example. This content is incorporated herein by reference.

[0637] Oxime compounds are more preferably used as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they offer a wide exposure latitude (exposure margin) and also function as photocuring accelerators.

[0638] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science. The compounds described in andTechnology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Publication No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent Application Publication 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 Application Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, and the compounds described in International Publication No. 2013 / 167515, etc., are included in this specification.

[0639] Preferred oxime compounds include, for example, compounds with the following structures, or 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pent-3-one, 2-(acetoxy(imino))-1-phenylprop-1-one, 2-(benzoyloxy(imino))-1-phenylprop-1-one, 3-((4-toluenesulfonyloxy)imino)but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylprop-1-one, etc. In resin compositions, oxime compounds are particularly preferred as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=NOC (=O)- linking group within the molecule.

[0640] [Chemical Formula 50]

[0641]

[0642] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKACORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New ElectronicMaterials CO.,LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Co.,Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Furthermore, oxime compounds with the following structures can also be used.

[0643] [Chemical Formula 51]

[0644]

[0645] As photoradical polymerization initiators, for example, oxime compounds with fluorene rings, oxime compounds with at least one benzene ring forming a naphthalene ring skeleton, and oxime compounds with fluorine atoms can also be used.

[0646] Furthermore, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl substituent bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, are also permitted to be used. These contents are incorporated herein by reference.

[0647] Furthermore, compounds described in paragraphs 0113 to 0117 of Japanese Patent Application Publication No. 2023-058585 can also be used as photopolymerization initiators. This description is incorporated into the specification of this application.

[0648] When the resin composition contains a photopolymerization initiator, its content relative to the total solids content of the resin composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may be one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[0649] In addition, photopolymerization initiators sometimes also function as thermal polymerization initiators, and therefore crosslinking based on photopolymerization initiators can sometimes be further carried out by heating in an oven or heating plate.

[0650] [Sensitizer]

[0651] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, thereby generating free radicals, acids, or bases.

[0652] As usable sensitizers, compounds such as benzophenone, michler's ketone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzylidene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethine, xanthones, phthalocyanines, benzopiperanones, and indigo compounds can be used.

[0653] Examples of sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and cinnamylidene dihydroindone. p-Dimethylaminobenzyl dihydroindone, 2-(p-dimethylaminophenylbenzyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)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-morphofolinylbenzophenone, isoamyl dimethylaminobenzoate Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0654] In addition, other sensitizing pigments can also be used.

[0655] For details regarding the sensitizing pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0656] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. A single sensitizer may be used, or two or more may be used in combination.

[0657] [Chain transfer agent]

[0658] 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 Polymer Society, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecular -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc., with thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. Thiol compounds are particularly preferred.

[0659] Furthermore, the chain transfer agent can also be the compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0660] When the resin composition contains a chain transfer agent, the content of the chain transfer agent relative to the total solids content of the resin composition is 100 parts by weight, preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, their total amount is preferably within the above-mentioned range.

[0661] Furthermore, the polymerization initiator is preferably a photoacid generator. As a photoacid generator, a free radical-generating photoacid generator is preferred.

[0662] Specifically, the preferred compounds are those that absorb light to decompose and generate free radicals, and that abstract hydrogen from the solvent or the acid-generating agent itself to generate acids.

[0663] Examples of photoacid-generating agents include quinone diazide compounds, oxime sulfonate compounds, organohalides, organoborates, disulfones, and onium salts, with onium salts being preferred.

[0664] Examples of onium salts include diazonium salts, phosphonium salts, sulfonium salts, and iodized salts.

[0665] Furthermore, onium salts are salts of cations and anions with onium structures, and these cations and anions may or may not be bonded by covalent bonds.

[0666] That is, the onium salt can be an intramolecular salt having a cation and anion portion within the same molecular structure, or it can be an intermolecular salt formed by ionic bonding of different cation and anion molecules, but is preferably an intermolecular salt. Furthermore, in the composition of the present invention, the aforementioned cation portion or cation molecule and the aforementioned anion portion or anion molecule can be bonded by ionic bonds or can be dissociated.

[0667] [Sulfur]

[0668] In this invention, sulfonium salt refers to a salt of sulfonium cation and anion.

[0669] -sulfonium cation-

[0670] As a sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.

[0671] Furthermore, the preferred cation as a sulfonium cation is the cation represented by the following formula (103).

[0672] [Chemical Formula 52]

[0673]

[0674] In equation (103), R 8 ~R 10 Each hydrocarbon group can be represented independently.

[0675] R 8 ~R 10 Each is preferably alkyl or aryl, more preferably alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, even more preferably aryl with 6 to 12 carbon atoms, and even more preferably phenyl.

[0676] R 8 ~R 10 It may have substituents, and examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, etc. Among these, it is preferable to have alkyl or alkoxy groups as substituents, more preferably to have branched alkyl or alkoxy groups, and even more preferably to have branched alkyl groups having 3 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms.

[0677] R 8 ~R 10 The groups can be the same or different groups, but from the point of view of synthetic suitability, the same groups are preferred.

[0678] -Anion-

[0679] Regarding anions, there are no particular limitations; the choice should be based on the acid produced. For example, B(C6F5)4... - BF4 - Boron-based anions, (Rf) n PF 6-n - PF3 (C2F5) 3- PF6 - Phosphine anions, SbF6 - Antimony anions, other carboxylic acid anions, sulfonic acid anions, etc.

[0680] Iodized salt

[0681] In this invention, iodine salt refers to a salt of iodine cation and anion. Examples of anions include those identical to the anions in the aforementioned matte salts, and the preferred embodiments are also the same.

[0682] -iodocation-

[0683] As an iodine cation, a diaryliodocation is preferred.

[0684] Furthermore, the iodine cation is preferably the cation represented by the following formula (104).

[0685] [Chemical Formula 53]

[0686]

[0687] In equation (104), R 11 and R 12 Each hydrocarbon group can be represented independently.

[0688] R 11 and R 12 Each is preferably alkyl or aryl, more preferably alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, even more preferably aryl with 6 to 12 carbon atoms, and even more preferably phenyl.

[0689] R 11 and R 12 It may have substituents, and examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, etc. Among these, it is preferable to have alkyl or alkoxy groups as substituents, more preferably to have branched alkyl or alkoxy groups, and even more preferably to have branched alkyl groups having 3 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms.

[0690] R 11 and R 12The groups can be the same or different groups, but from the point of view of synthetic suitability, the same groups are preferred.

[0691] [phosphorus salt]

[0692] In this invention, a phosphonium salt refers to a salt of a phosphonium cation and an anion. Examples of anions that are the same as the anions in the sulfonium salts described above are provided, and the preferred embodiments are also the same.

[0693] -Lonium cation-

[0694] As a phosphonium cation, a quaternary phosphonium cation is preferred, and examples include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations.

[0695] Furthermore, the preferred cation is the one represented by the following formula (105).

[0696] [Chemical Formula 54]

[0697]

[0698] In equation (105), R 13 ~R 16 Each can be used to represent a hydrogen atom or a hydrocarbon group independently.

[0699] R 13 ~R 16 Each is preferably alkyl or aryl, more preferably alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, even more preferably aryl with 6 to 12 carbon atoms, and even more preferably phenyl.

[0700] R 13 ~R 16 It may have substituents, and examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, etc. Among these, it is preferable to have alkyl or alkoxy groups as substituents, more preferably to have branched alkyl or alkoxy groups, and even more preferably to have branched alkyl groups having 3 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms.

[0701] R 13 ~R 16 The groups can be the same or different groups, but from the point of view of synthetic suitability, the same groups are preferred.

[0702] The content of photoacid generator relative to the total solids content of the resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.

[0703] Photoacid-generating agents can be used alone or in combination of multiple agents. In the case of multiple combinations, the total amount of these agents is preferably within the range described above.

[0704] Furthermore, in order to impart photosensitivity to the desired light source, it is preferable to use it in combination with a sensitizer.

[0705] Furthermore, the resin composition of the present invention comprising two or more polymerization initiators is also one of the preferred embodiments of the present invention.

[0706] Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0707] By including photopolymerization initiators and thermal polymerization initiators (described later), it is sometimes possible to form exposure-based patterns, and free radical polymerization can be easily carried out during curing based on the heating process described later, thereby improving properties such as chemical resistance.

[0708] As the ratio of the photopolymerization initiator and the thermal polymerization initiator described later, the content of the thermal polymerization initiator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0709] By including photoradical polymerization initiators and photoacid-producing agents, performance such as resolution can sometimes be improved.

[0710] As for the content ratio when photopolymerization initiator and photoacid generator are included, the content of photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of photopolymerization initiator and photoacid generator.

[0711] [Thermal polymerization initiator]

[0712] Examples of thermal polymerization initiators include thermal free radical polymerization initiators. Thermal free radical polymerization initiators are compounds that generate free radicals through thermal energy to initiate or promote the polymerization reaction of polymerizable compounds. By adding thermal free radical polymerization initiators, polymerization reactions of resins and polymerizable compounds can be carried out, thus further improving solvent resistance.

[0713] As thermal free radical polymerization initiators, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated herein by reference, can be listed.

[0714] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may be one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[0715] <Solvent>

[0716] The resin composition of the present invention preferably contains a solvent.

[0717] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0718] Examples of esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetic acid, ethyl alkoxyacetic acid, butyl alkoxyacetic acid (e.g., methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, methyl 3-ethoxypropionic acid). Ethyl propionate, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred esters.

[0719] Examples of 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 celusone acetate, ethyl celusone acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0720] Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydro L-glucanone.

[0721] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred examples of cyclic hydrocarbons.

[0722] As a sulfoxide, dimethyl sulfoxide can be listed as a preferred sulfoxide.

[0723] Preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorphofolin, and N-acetylmorphofolin.

[0724] Examples of preferred urea types include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolium ketone.

[0725] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

[0726] From the perspective of improving the properties of the coating surface, it is also preferable that the solvent is a mixture of two or more forms.

[0727] In this invention, the solvent is preferably selected from one or more of the following: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celusone 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, L-glucosidone, and dihydroL-glucosidone. Particularly preferred methods include the use of dimethyl sulfoxide with γ-butyrolactone, dimethyl sulfoxide with γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone with ethyl lactate. Further addition of approximately 1 to 10% by mass relative to the total mass of these solvents is also a preferred method of the invention.

[0728] In particular, from the viewpoint of the storage stability of the resin composition, including γ-valerolactone as a solvent is one of the preferred embodiments of the present invention. In this embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and can be 100% by mass. The above content can be determined by considering the solubility of specific resins and other components contained in the resin composition.

[0729] Furthermore, when dimethyl sulfoxide and γ-valerolactone are used together, the total mass of the solvent preferably contains 60-90% by mass of γ-valerolactone and 10-40% by mass of dimethyl sulfoxide, more preferably 70-90% by mass of γ-valerolactone and 10-30% by mass of dimethyl sulfoxide, and even more preferably 75-85% by mass of γ-valerolactone and 15-25% by mass of dimethyl sulfoxide.

[0730] Furthermore, the resin composition of the present invention contains a solvent with a boiling point preferably between 100 and 260°C. In the present invention, the boiling point of the solvent is the boiling point at 1 atmosphere.

[0731] Based on this approach, it is believed that cured products with excellent solvent removal properties and high resolution can be obtained.

[0732] The boiling point is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. The upper limit of the boiling point is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower.

[0733] Furthermore, the resin composition of the present invention contains two or more solvents with boiling points preferably between 100 and 260°C, more preferably two or more solvents with boiling points between 150 and 250°C, and even more preferably two or more solvents with boiling points between 180 and 230°C.

[0734] Furthermore, relative to the total mass of the composition, the content of solvents with boiling points of 100–260°C is preferably 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more. When two or more solvents with boiling points of 100–260°C are included, the total amount of these is preferably within the above-mentioned range.

[0735] From the viewpoint of coatability, the solvent content is preferably set to a total solids concentration of 5 to 80% by mass in the resin composition of the present invention, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating and the coating method. When two or more solvents are contained, their total content is preferably within the above range.

[0736] <Metal Adhesion Modifier>

[0737] From the viewpoint of improving adhesion to metal materials used in electrodes or wiring, the resin composition of the present invention preferably contains a metal adhesion modifier. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilane groups, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

[0738] [Silane coupling agent]

[0739] As silane coupling agents, examples include compounds described in paragraph 0316 of International Patent Publication No. 2021 / 112189 and compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, which are incorporated herein by reference. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. The following compounds are also preferred as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl. Furthermore, the following R can represent structures derived from the blocking agent in the isocyanate group. The blocking agent can be selected according to the deactivation temperature, and examples include alcohol compounds, phenolic compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the deactivation temperature to 160–180°C, caprolactam is preferred. Commercially available examples of this compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0740] [Chemical Formula 55]

[0741]

[0742] [Chemical Formula 56]

[0743]

[0744] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimeth ... The following are listed: 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0745] Furthermore, oligomer-type compounds having multiple alkoxysilane groups can also be used as silane coupling agents.

[0746] Examples of such oligomer-type compounds include compounds containing repeating units represented by the formula (S-1) below.

[0747] [Chemical Formula 57]

[0748]

[0749] In equation (S-1), R S1 R represents a monovalent organic group. S2 It represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer from 0 to 2.

[0750] R S1The preferred structure includes a polymerizable group. Examples of polymerizable groups include groups having an olefinic unsaturated bond, epoxy groups, oxobutyl groups, benzoxazolyl groups, terminal isocyanate groups, amino groups, etc. Examples of groups having an olefinic unsaturated bond include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, etc., vinylphenyl, (meth)acrylamido, or (meth)acryloyloxy, more preferably vinylphenyl or (meth)acryloyloxy, and even more preferably (meth)acryloyloxy.

[0751] R S2 Preferably, it is alkoxy, more preferably methoxy or ethoxy.

[0752] n represents an integer from 0 to 2, preferably 1.

[0753] Here, the repeating units represented by multiple formulas (S-1) contained in the oligomer type compound may have the same structure.

[0754] Here, among the repeating units represented by the plurality of formulas (S-1) contained in the oligomer-type compound, it is preferable that at least one has n=1 or 2, more preferably at least two have n=1 or 2, and even more preferably at least two have n=1.

[0755] As such oligomer-type compounds, commercially available products can be used, such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0756] [Aluminum-based adhesive additives]

[0757] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethyl acetoacetate aluminum diisopropyl ester.

[0758] As other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are incorporated in this specification.

[0759] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting the content above the lower limit, the adhesion between the pattern and the metal layer becomes good; by setting the content below the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion modifier may be only one type or may be two or more types. When two or more types are used, their total content is preferably within the above range.

[0760] <Migration Inhibitor>

[0761] The resin composition of the present invention preferably further comprises a migration inhibitor. By comprising a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0762] There are no particular limitations on the migration inhibitors, and examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, mofolin ring, 2H-piperanone ring and 6H-piperanone ring, triazine ring), thioureas and compounds having hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0763] Among these, the resin composition of the present invention preferably contains an azole compound.

[0764] Azole compounds are compounds containing a azole structure, which refers to a 5-membered ring structure containing a nitrogen atom as a cyclic atom, preferably a 5-membered ring structure containing two or more nitrogen atoms as cyclic atoms. Specifically, examples of azole structures include imidazole, triazole, and tetraazole structures. Like benzimidazole and benzotriazole, these structures can form polycyclic rings with other ring structures through condensation or other processes.

[0765] Furthermore, as a compound having an azole structure, it is preferred to be a compound having a group represented by the following formula (R-1) or the following formula (R-2) directly bonded to the azole structure.

[0766] [Chemical Formula 58]

[0767]

[0768] In equation (R-1), R1 The symbol represents a monovalent organic group, and * indicates the bonding site with the azole structure.

[0769] In equation (R-2), R 2 R represents a hydrogen atom or a monovalent organic group. 3 The symbol represents a monovalent organic group, and * indicates the bonding site with the azole structure.

[0770] In equation (R-1), R 1 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by a bond of at least one base in the group consisting of R. N As stated above.

[0771] The hydrocarbon group described above is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.

[0772] Furthermore, R 1 The total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.

[0773] R 1 The bonding site between the carbonyl group in formula (R-1) and the carbonyl group is preferably a hydrocarbon group or -NR. N -

[0774] In formula (R-1), * represents the bonding site with the azole structure, preferably the bonding site with the carbon atom that is the cyclic atom of the azole structure.

[0775] In equation (R-2), R 2 Hydrogen atoms are preferred.

[0776] When R 2 When R is a monovalent organic group, 2 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by a bond of at least one base in the group consisting of R. N As stated above.

[0777] The hydrocarbon group described above is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.

[0778] Furthermore, R 2 When the organic group is monovalent, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.

[0779] When R 2 When R is a monovalent organic group, 2The bonding site between the nitrogen atom in formula (R-2) and the nitrogen atom is preferably a hydrocarbon group or -C(=O)-.

[0780] In equation (R-2), R 3 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by a bond of at least one base in the group consisting of R. N It represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom.

[0781] The hydrocarbon group described above is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.

[0782] Furthermore, R 3 When the organic group is monovalent, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.

[0783] R 3 The bonding site between the nitrogen atom in formula (R-2) and the nitrogen atom is preferably a hydrocarbon group or -C(=O)-.

[0784] In formula (R-2), * represents the bonding site with the azole structure, preferably the bonding site with the carbon atom that is the cyclic atom of the azole structure.

[0785] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[0786] Other migration inhibitors include rust inhibitors described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are incorporated herein by reference.

[0787] The following compounds can be listed as specific examples of migration inhibitors.

[0788] [Chemical Formula 59]

[0789]

[0790] When the resin composition of the present invention has 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, relative to the total solid content of the resin composition.

[0791] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, their total number is preferably within the range described above.

[0792] <Light Absorber>

[0793] The resin composition of the present invention is also preferably a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.

[0794] Examples of light absorbers include compounds described in paragraphs 0159 to 0183 of International Patent Publication No. 2022 / 202647 and compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These are included in this specification.

[0795] In particular, from the viewpoint of improving adhesion to the substrate, the resin composition of the present invention preferably further comprises the above-mentioned azole compound and the above-mentioned silane coupling agent. By containing these compounds, adhesion to the substrate is easily maintained, especially after the cured product is exposed to high temperature and high humidity conditions.

[0796] <Polymerization inhibitor>

[0797] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0798] Specific compounds that can be used as polymerization inhibitors include those described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. This content is incorporated herein by reference.

[0799] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0800] The polymerization inhibitor may be only one type or two or more types. When there are two or more polymerization inhibitors, their total amount is preferably within the range described above.

[0801] <Other Additives>

[0802] The resin composition of the present invention may contain various additives as needed, within the scope of achieving the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, alkali generators, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the physical properties of the membrane can be adjusted. These components can be described, for example, by referring to paragraphs 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 in U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 in Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are incorporated, it is preferable that their total content be set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0803] [Inorganic particles]

[0804] Specifically, inorganic particles include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0805] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and especially preferably 0.04 to 0.5 μm.

[0806] The aforementioned average particle size of the inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be determined, for example, by dynamic light scattering based on the Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO.,LTD.).

[0807] When the above measurements are difficult to perform, centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method can also be used for measurement.

[0808] [Organotitanium compounds]

[0809] By incorporating organotitanium compounds into the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0810] As usable organotitanium compounds, examples include compounds in which organic groups are covalently or ionicly bonded to titanium atoms.

[0811] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0812] I) Titanium chelate compounds: From the viewpoint of excellent storage stability of the resin composition and the ability to obtain good cured patterns, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples include bis(triethanolamine)diisopropoxy titanium, bis(2,4-glutarate)di(n-butoxy) titanium, bis(2,4-glutarate)diisopropoxy titanium, bis(tetramethylheptidine)diisopropoxy titanium, bis(ethyl acetoacetate)diisopropoxy titanium, etc.

[0813] II) Tetraalkoxy titanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoyloxytitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc.

[0814] III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0815] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecylbenzenesulfonate) isopropoxy titanium, etc.

[0816] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0817] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0818] VII) Titanate coupling agents: such as isopropyltris(dodecyl)benzenesulfonyl titanate, etc.

[0819] From the viewpoint of better drug resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dicarboxylated titanium compounds is preferred as the organotitanium compound. Particularly preferred are bis(ethyl acetoacetate)diisopropoxy titanium, tetra(n-butoxy) titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium.

[0820] Furthermore, it is also preferred to include, as an organotitanium compound or instead of an organotitanium compound, a compound represented by the following formula (T-1).

[0821] [Chemical Formula 60]

[0822]

[0823] In equation (T-1), M represents titanium, zirconium, or hafnium; l1 is an integer from 0 to 2; l2 is 0 or 1; l1 + l2 × 2 is an integer from 0 to 2; m is an integer from 0 to 4; n is an integer from 0 to 2; l1 + l2 + m + n × 2 = 4; R 11 Each is independently a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted alkoxy, or a substituted or unsubstituted phenoxy, R 12 R is a substituted or unsubstituted hydrocarbon group. 2 Each is an independent group comprising the structure represented by the following formula (T-2), R 3 Each is an independent group comprising the structure represented by the following formula (T-2), X A Each can be an oxygen atom or a sulfur atom, independently.

[0824] [Chemical Formula 61]

[0825]

[0826] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= can be represented independently, with * indicating the bonding site with other structures and # indicating the bonding site with metal atoms.

[0827] In formula (T-1), from the viewpoint of the storage stability of the composition, M is preferably titanium.

[0828] In equation (T-1), the setting of l1 and l2 to 0 is also one of the preferred embodiments of the present invention.

[0829] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0830] In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1.

[0831] In this case, in equation (T-1), it is also preferable that l1 and l2 are 0 and m is 0, 2 or 4.

[0832] In equation (T-1), from the perspective of the stability of a specific metal complex, R 11 Preferably, it is a substituted or unsubstituted cyclopentadiene ligand.

[0833] Furthermore, R 11 The cyclopentadienyl, alkoxy, and phenoxy groups in the present invention can be substituted, but the unsubstituted form is also one of the preferred forms of the present invention.

[0834] In equation (T-1), R 12Preferably, it is a hydrocarbon group with 1 to 20 carbon atoms, and more preferably a hydrocarbon group with 2 to 10 carbon atoms.

[0835] As R 12 The hydrocarbon group in the form can be any one of aliphatic hydrocarbon group or aromatic hydrocarbon group, but is preferably an aromatic hydrocarbon group.

[0836] As an aliphatic hydrocarbon group, it can be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.

[0837] As an aromatic hydrocarbon group, it is preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 10 carbon atoms, and even more preferably a phenylene group.

[0838] As R 12 The substituents in R are preferably monovalent substituents, such as halogen atoms. Furthermore, when R... 12 When it is an aromatic hydrocarbon group, it can have alkyl groups as substituents.

[0839] Among these, in equation (T-1), R 12 Preferably, it is an unsubstituted phenylene oxide. Furthermore, R 12 The phenylene oxide in the sample is preferably 1,2-phenylene oxide.

[0840] In equation (T-1), when m is 2 or more and contains more than 2 R... 2 At that time, the two or more R 2 The structures can be the same or different.

[0841] In equation (T-1), when n is 2 or more and contains more than 2 R... 3 At that time, the two or more R 3 The structures can be the same or different.

[0842] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= can be represented independently, preferably at least one representation of -C(-*)=, more preferably at least two representations of -C(-*)=.

[0843] As specific examples of compounds represented by formula (T-1), compounds corresponding to I-3 in the examples can be listed, but are not limited to these.

[0844] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of a specific resin. When the content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when it is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0845] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of a specific resin. When the content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when it is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0846] Other additives may include compounds described in paragraphs 0249–0282 and 0316–0358 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0847] <Characteristics of the Resin Composition>

[0848] The viscosity of the resin composition of the present invention can be adjusted by utilizing the concentration of the solid components in the resin composition. From the viewpoint of coating film thickness, 1,000 mm is preferred. 2 / s~12,000mm 2 / s, more preferably 2,000 mm 2 / s~10,000mm 2 / s, further preferably 2,500mm 2 / s~8,000mm 2 / s. If within the above range, a highly uniform coating film can be easily obtained. For example, if it is 1,000 mm... 2 If the speed is above 12,000 mm, it is easy to coat with the film thickness required for reinsertion insulation. 2 When the speed is below / s, a coating film with excellent surface finish can be obtained.

[0849] <Restrictions on the Contents of Substances in Resin Compositions>

[0850] The moisture content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved.

[0851] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container.

[0852] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained in the form of complexes of organic compounds and metals. When multiple metals are included, the total amount of these metals is preferably within the above-mentioned range.

[0853] Furthermore, as a method for reducing unintentionally contained metallic impurities in the resin composition of the present invention, the following methods can be listed: selecting raw materials with low metal content as raw materials constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention using a filter; and performing distillation in an apparatus with a lining such as polytetrafluoroethylene to suppress contamination as much as possible.

[0854] In the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. Of this, the content existing in the form of halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is preferably within the above-mentioned ranges.

[0855] Methods for adjusting the content of halogen atoms can preferably include ion exchange treatment, etc.

[0856] As a container for the resin composition of the present invention, conventionally known containers can be used. For the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, multi-layered bottles with an inner wall composed of six layers of six different resins or bottles with a seven-layer structure formed by six different resins are preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0857] <Cure of Resin Composition>

[0858] By curing the resin composition of the present invention, a cured resin composition can be obtained.

[0859] The cured product of the present invention is a cured product obtained by curing a resin composition.

[0860] The curing of the resin composition is preferably carried out by heating, with a heating temperature more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The morphology of the cured resin composition is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured product is preferably in film form. The shape of the cured product can also be selected according to applications such as forming a protective film on a wall surface through pattern processing of the resin composition, forming conductive through-holes, adjusting impedance or electrostatic capacitance or internal stress, or imparting heat dissipation function. The film thickness of the cured product (the film formed by the cured product) is preferably 0.5 μm or more and 150 μm or less.

[0861] The shrinkage rate during curing of the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, which can be calculated by the following formula.

[0862] Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0863] <Characteristics of cured resin compositions>

[0864] The imidization reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, it may sometimes result in a cured product with excellent mechanical properties.

[0865] The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[0866] The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0867] <Preparation of Resin Compositions>

[0868] The resin composition of the present invention can be prepared by mixing the above-described components. The mixing method is not particularly limited and can be carried out using conventionally known methods.

[0869] Examples of mixing methods include mixing based on stirring blades, mixing based on ball mills, and mixing by rotating a tank.

[0870] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0871] For the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration using a filter is preferred. The filter pore size is preferably 5 μm or less, more preferably 1 μm or less, further preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be pre-cleaned with an organic solvent. In the filter filtration process, multiple filters can be connected in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be combined. As a connection method, for example, an HDPE filter with a pore size of 1 μm as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage can be connected in series. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a circulating filtration. Furthermore, filtration can be performed by pressurization. When filtration is performed under pressure, the applied pressure is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[0872] In addition to filtration using filters, impurities can also be removed using adsorption materials. Filtration and impurity removal using adsorption materials can also be combined. Known adsorption materials can be used. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0873] After filtration using a filter, a process can be performed whereby the resin composition filled in the bottle is placed under reduced pressure for degassing.

[0874] (Method for manufacturing solidified products)

[0875] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

[0876] A more preferred method for manufacturing a cured material is to include the above-described film forming step, an exposure step for selectively exposing the film formed in the film forming step, and a developing step for developing the film exposed in the exposure step using a developing solution to form a pattern.

[0877] The method for manufacturing the cured material is particularly preferred to include at least one of the above-described film forming step, the above-described exposure step, the above-described developing step, a heating step for heating the pattern obtained by the developing step, and a post-developing exposure step for exposing the pattern obtained by the developing step.

[0878] Furthermore, the method for manufacturing the cured material is preferably to include the above-described film formation process and the process of heating the above-described film.

[0879] The following is a detailed explanation of each process.

[0880] <Membrane Formation Process>

[0881] The resin composition of the present invention can be used in a film forming process applicable to a substrate for forming a film.

[0882] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

[0883] [Substrate]

[0884] The type of substrate can be appropriately specified according to the application and is not particularly limited. Examples of substrates include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any of the substrates formed of metal and substrates with metal layers formed by plating, deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). Semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred.

[0885] On the surface of these substrates, a layer such as a sealing layer or an oxide layer formed of hexamethyldisilazane (HMDS) can be provided.

[0886] The shape of the substrate is not particularly limited; it can be circular or rectangular.

[0887] Regarding the dimensions of the substrate, for a circular shape, the diameter is preferably 100–450 mm, more preferably 200–450 mm. For a rectangular shape, the length of the shorter side is preferably 100–1000 mm, more preferably 200–700 mm.

[0888] As a substrate, for example, a plate-shaped substrate (substrate) can be used, preferably a panel-shaped substrate.

[0889] When a resin composition is applied to the surface of a resin layer (e.g., a layer formed by curing) or a metal layer to form a film, the resin layer or the metal layer becomes a substrate.

[0890] As a method for applying the resin composition to a substrate, coating is preferred.

[0891] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating is preferred. From the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are more preferred. By adjusting the solid content concentration of the resin composition or the coating conditions according to the applicable method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[0892] Furthermore, it is also possible to apply a method for transferring a coating film formed by pre-applying it to a temporary support through the above-described application method onto a substrate.

[0893] Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 is preferably used.

[0894] Furthermore, a process for removing excess film can be performed at the ends of the substrate. Examples of such processes include edge beaded residue rinsing (EBR) and back rinse.

[0895] Alternatively, a pre-wetting process can be used: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve its wettability, and then the resin composition is applied.

[0896] <Drying Process>

[0897] After the film formation process (layer formation process), in order to remove the solvent, the above-mentioned film can be used for a process of drying the formed film (layer) (drying process).

[0898] That is, the method for manufacturing the cured product of the present invention may include a drying step of drying the film formed by the film forming step.

[0899] The drying process described above is preferably performed after the film formation process and before the exposure process.

[0900] The drying temperature of the membrane in the drying process is preferably 50–150°C, more preferably 70–130°C, and even more preferably 90–110°C. Furthermore, drying can also be performed under reduced pressure. Examples of drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0901] <Exposure Process>

[0902] The above-mentioned film can be used in an exposure process that selectively exposes the film.

[0903] Methods for manufacturing cured materials may include exposure processes that selectively expose films formed by film formation processes.

[0904] Selective exposure refers to exposing only a portion of the film. Furthermore, through selective exposure, exposed areas (exposed areas) and unexposed areas (non-exposed areas) are formed on the film.

[0905] Regarding the exposure amount, it is not particularly limited as long as it is sufficient to cure the resin composition of the present invention. For example, it is preferably 50 to 10,000 mJ / cm based on the exposure energy at a wavelength of 365 nm. 2 More preferably 200–8,000 mJ / cm 2 .

[0906] The exposure wavelength can be appropriately specified in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0907] Regarding the exposure wavelength, in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (gamma, h, and i-ray wavelengths), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. For the resin composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and from the viewpoint of exposure sensitivity, exposure based on i-rays is more preferred.

[0908] The exposure method is not particularly limited, as long as at least a portion of the film formed by the resin composition of the present invention is exposed. Examples include exposure using a photomask and exposure based on direct laser imaging.

[0909] <Post-exposure heating process>

[0910] The above-mentioned film can be used in the post-exposure heating process (post-exposure heating process).

[0911] That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.

[0912] The post-exposure heating process can be performed after the exposure process and before the development process.

[0913] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0914] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0915] The heating rate during the post-exposure heating process, from the initial heating temperature to the maximum heating temperature, is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[0916] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0917] As a heating mechanism in the post-exposure heating process, it is not particularly limited and can use known heating plates, ovens, infrared heaters, etc.

[0918] Furthermore, heating is preferably carried out in a low-oxygen environment by circulating inert gases such as nitrogen, helium, or argon.

[0919] <Developing Process>

[0920] The exposed film can be used in the developing process to form a pattern by developing it with a developing solution.

[0921] That is, the method for manufacturing the cured product of the present invention may include a developing step of developing a film exposed by an exposure step to form a pattern using a developing solution.

[0922] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[0923] Here, the development process that removes the non-exposed portions of the film is called negative development, and the development process that removes the exposed portions of the film is called positive development.

[0924] [Developing solution]

[0925] Examples of developing solutions used in the developing process include alkaline aqueous solutions and developing solutions containing organic solvents.

[0926] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, 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 preferably, TMAH is preferred. In the total mass of the developer, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0927] When the developer contains an organic solvent, compounds described in paragraph 0387 of International Publication No. 2021 / 112189 may be used as the organic solvent. This content is incorporated into this specification. Furthermore, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., may be preferably listed as alcohols, and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., may be preferably listed as amides.

[0928] When the developer contains an organic solvent, one or more organic solvents can be used. In this invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, more preferably a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide, and especially preferably a developer containing cyclopentanone.

[0929] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content may also be 100% by mass.

[0930] The developer may further contain other ingredients.

[0931] Other components include, for example, well-known surfactants or well-known defoamers.

[0932] [Method for supplying developer]

[0933] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the developer. Methods include immersing the substrate with the film formed in the developer, swirling immersion development using a nozzle to supply the developer to the film formed on the substrate, or continuous supply of developer. There are no particular restrictions on the type of nozzle, such as straight nozzles, spray nozzles, and mist nozzles.

[0934] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, a method of supplying developer using a straight nozzle or a method of continuous supply using a spray nozzle is preferred. From the viewpoint of developer penetration into the image area, a method of supplying using a spray nozzle is more preferred.

[0935] Furthermore, the process can be performed by continuously supplying developer using a straight nozzle, rotating the substrate to remove the developer from the substrate, performing rotary drying, and then continuously supplying developer again using a straight nozzle, rotating the substrate to remove the developer from the substrate. This process can be repeated multiple times.

[0936] Methods for supplying developer in the developing process include processes such as continuously supplying developer to a substrate, maintaining developer on a substrate in a roughly static state, using ultrasound or the like to vibrate developer on a substrate, and combining these methods.

[0937] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution during development is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0938] In the developing process, after treatment with the developer, the pattern can be further cleaned (rinsed) using a rinsing solution. Furthermore, methods such as supplying the rinsing solution while the developer in contact with the pattern is not completely dry can be employed.

[0939] [Rinse solution]

[0940] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0941] When the rinsing solution contains an organic solvent, the same organic solvents as those exemplified when the developing solution contains an organic solvent can be listed.

[0942] The organic solvent contained in the rinsing solution is an organic solvent that is different from the organic solvent contained in the developing solution. Preferably, it is an organic solvent with low solubility in the pattern compared to the organic solvent contained in the developing solution.

[0943] When the rinsing solution contains an organic solvent, one or more organic solvents may be used. Preferred organic solvents include cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME; more preferably, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME; and even more preferably, cyclohexanone and PGMEA.

[0944] When the rinsing solution contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Furthermore, the organic solvent may also be 100% by mass, relative to the total mass of the rinsing solution.

[0945] The rinsing solution may further contain other ingredients.

[0946] Other components include, for example, well-known surfactants or well-known defoamers.

[0947] [Method for supplying flushing fluid]

[0948] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the rinsing liquid. Methods include immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by holding the liquid, supplying the rinsing liquid to the substrate by spraying, and continuously supplying the rinsing liquid to the substrate using a mechanism such as a straight nozzle.

[0949] From the viewpoints of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, a method of supplying the rinsing fluid using a spray nozzle, a straight nozzle, or a mist nozzle is preferred. From the viewpoint of the penetrability of the rinsing fluid to the image area, a method of supplying the rinsing fluid using a mist nozzle is more preferred. There are no particular limitations on the type of nozzle; examples include straight nozzles, spray nozzles, and mist nozzles.

[0950] That is, the rinsing process is preferably a process of supplying or continuously supplying rinsing liquid to the exposed film using a straight nozzle, and more preferably a process of supplying rinsing liquid using a spray nozzle.

[0951] As a method for supplying rinsing fluid in the rinsing process, methods such as continuously supplying rinsing fluid to the substrate, maintaining the rinsing fluid on the substrate in a substantially static state, vibrating the rinsing fluid on the substrate using ultrasound or the like, and combining these methods are all possible.

[0952] The preferred rinsing time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0953] <Heating Process>

[0954] The pattern obtained by the developing process (or the washed pattern in the case of the washing process) can be used in a heating process for heating the pattern obtained by the developing process described above.

[0955] That is, the method for manufacturing the cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.

[0956] Furthermore, the method for manufacturing the cured product of the present invention may also include a heating step of heating a pattern obtained by other methods without a developing step or a film obtained by a film forming step.

[0957] During the heating process, resins such as polyimide precursors undergo cyclization to become polyimide resins.

[0958] Furthermore, crosslinking of unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins is also performed.

[0959] The heating temperature (maximum heating temperature) in the heating process is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, and even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0960] The heating process is preferably a process in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of an alkali or the like generated by the alkali generating agent through heating.

[0961] From the initial heating temperature to the maximum heating temperature, the heating process is preferably carried out at a heating rate of 1 to 12°C / minute. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. Setting the heating rate to 1°C / minute or higher ensures productivity and prevents excessive evaporation of acid or solvent; setting the heating rate to 12°C / minute or lower helps to mitigate residual stress in the cured product.

[0962] Furthermore, in the case of an oven capable of rapid heating, the heating rate from the initial temperature to the maximum heating temperature is preferably 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0963] The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the heating process begins and reaches the maximum heating temperature. For example, in the case of applying the resin composition of the present invention to a substrate and then drying it, it is the temperature of the dried film (layer), preferably starting from a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0964] The heating time (heating time under the highest heating temperature condition) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0965] In particular, when forming a multi-layered laminate, from the viewpoint of interlayer tightness, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher.

[0966] The upper limit of the above heating temperature is preferably below 350°C, more preferably below 250°C, and even more preferably below 240°C.

[0967] Heating can be performed in stages. For example, the following steps can be performed: increasing the temperature from 25°C to 120°C at a rate of 3°C / minute, holding at 120°C for 60 minutes, and increasing the temperature from 120°C to 180°C at a rate of 2°C / minute, holding at 180°C for 120 minutes. Furthermore, as described in U.S. Patent No. 9,159,547, it is preferable to perform the treatment while irradiating with ultraviolet light. This pretreatment process can improve the properties of the membrane. A short pretreatment time of approximately 10 seconds to 2 hours is sufficient, more preferably 15 seconds to 30 minutes. The pretreatment process can be divided into two or more stages; for example, a first stage pretreatment can be performed in the range of 100 to 150°C, followed by a second stage pretreatment in the range of 150 to 200°C.

[0968] Furthermore, heating followed by cooling is possible, and the preferred cooling rate at this time is 1 to 5°C / minute.

[0969] Regarding the heating process, from the viewpoint of preventing the decomposition of specific resins, it is preferable to carry out the process in a low-oxygen environment by circulating inert gases such as nitrogen, helium, or argon, or by conducting the process under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[0970] As a heating mechanism in the heating process, it is not particularly limited. For example, heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens can be listed.

[0971] <Post-development exposure process>

[0972] The pattern obtained by the developing process (or the washed pattern in the case of the washing process) can also replace the heating process described above or, in addition to the heating process described above, be used for a post-developing exposure process to expose the pattern after the developing process.

[0973] That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for manufacturing the cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.

[0974] In the post-development exposure process, it can promote, for example, the cyclization reaction of polyimide precursors by photo-alkali-generating agents, or the removal of acid-degrading groups by photo-acid-generating agents.

[0975] In the post-development exposure process, it is sufficient for at least a portion of the pattern obtained in the development process to be exposed, but preferably all of the pattern is exposed.

[0976] Based on the exposure energy conversion at the wavelength where the photosensitive compound has sensitivity, the exposure amount in the post-development exposure process is preferably 50–20,000 mJ / cm². 2 More preferably 100–15,000 mJ / cm 2 .

[0977] The post-development exposure process can be performed using the light source described in the above-mentioned exposure process, preferably using broadband light.

[0978] <Metal Layer Formation Process>

[0979] The pattern obtained by the developing process (preferably a pattern for at least one of the heating process and the post-development exposure process) can be used in the metal layer forming process for forming a metal layer on the pattern.

[0980] That is, the method for manufacturing the cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably a pattern for at least one of a heating step and a post-developing exposure step).

[0981] There are no particular limitations on the metal layer; any existing metal can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0982] There are no particular limitations on the method for forming the metal layer, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electroplating can be listed. As a preferred method of plating, electroplating using copper sulfate or copper cyanide plating solutions can be listed.

[0983] The thickness of the metal layer is preferably 0.01 to 50 μm in the thickest part, and more preferably 1 to 10 μm.

[0984] <Uses>

[0985] Examples of applications for manufacturing methods or products to which the present invention can be applied include insulating films for electronic components, interlayer insulating films for rewiring layers, and stress-relief films. Furthermore, examples include patterning of sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or insulating films for mounting purposes as described above, by etching. For applications of these, please refer to, for example, SCIENCE AND TECHNOLOGY CO.,LTD. “High Functionalization and Application Technology of Polyimide”, April 2008, supervised by Masaaki Kakimoto; CMC Technical Library “Fundamentals and Development of Polyimide Materials”, November 2011; and the Japan Polyimide and Aromatic Polymer Symposium / ed., “Latest Polyimide Fundamentals and Applications”, NTS Inc., August 2010.

[0986] The method for manufacturing the cured product of the present invention or the cured product of the present invention can also be used for manufacturing offset printing plates or screen printing plates, etching of shaped parts, manufacturing of protective coatings and dielectric layers in electronics, especially microelectronics, etc.

[0987] (Laminated bodies and methods for manufacturing laminated bodies)

[0988] The laminate of the present invention refers to a structure having multiple layers formed by the cured product of the present invention.

[0989] A laminate is a laminate containing two or more layers formed by a solidified material, or it can be a laminate consisting of three or more layers.

[0990] In the above-described laminate, at least one of the two or more layers formed by the cured material is a layer formed by the cured material of the present invention. From the viewpoint of suppressing the shrinkage of the cured material or the deformation of the cured material accompanying the shrinkage, it is also preferable that all the layers formed by the cured material in the above-described laminate are layers formed by the cured material of the present invention.

[0991] That is, the manufacturing method of the laminate of the present invention preferably includes the manufacturing method of the cured product of the present invention, and more preferably includes the manufacturing method of the cured product of the present invention repeatedly.

[0992] The laminate of the present invention preferably comprises two or more layers formed of a cured material, with a metal layer between any of the aforementioned layers formed of the cured material. The metal layer is preferably formed by the aforementioned metal layer forming process.

[0993] That is, the method for manufacturing the laminate of the present invention preferably includes, between multiple methods for manufacturing cured products, a metal layer forming step in which a metal layer is formed on the layer formed from the cured product. The preferred embodiment of the metal layer forming step is as described above.

[0994] As an example of the aforementioned laminate, a preferred laminate may include at least the following layer structure, which is formed by sequentially stacking three layers: a layer formed by a first cured material, a metal layer, and a layer formed by a second cured material.

[0995] The layers formed by the first cured product and the layers formed by the second cured product are preferably both layers formed by the cured products of the present invention. The resin composition of the present invention used to form the layer formed by the first cured product and the resin composition of the present invention used to form the layer formed by the second cured product may be the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a metal wiring layer such as a rewiring layer.

[0996] <Layering Process>

[0997] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0998] The lamination process includes a series of steps comprising performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step on the surface of a pattern (resin layer) or a metal layer. However, it may also be a process of repeatedly performing at least one of (a) the film formation step, (d) the heating step, and the post-development exposure step. Furthermore, (e) the metal layer formation step may be included after at least one of (d) the heating step and the post-development exposure step. The lamination process may, of course, further appropriately include the aforementioned drying step, etc.

[0999] When a further lamination process is performed after the lamination process, a surface activation treatment process can be performed after the aforementioned exposure process, the aforementioned heating process, or the aforementioned metal layer formation process. Plasma treatment can be cited as an example of a surface activation treatment. Details regarding surface activation treatment will be described later.

[1000] The above-mentioned lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[1001] For example, as in the configuration of resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, the resin layer is preferably configured to have 2 or more layers and 20 or fewer layers, and more preferably configured to have 2 or more layers and 9 or fewer layers.

[1002] The composition, shape, and film thickness of each of the above layers can be the same or different.

[1003] In this invention, particularly after the metal layer is formed, it is preferable to further form a cured product (resin layer) of the resin composition of the present invention by covering the metal layer. Specifically, examples include repeating at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step and post-development exposure step, and (e) metal layer formation step in that order, or repeating at least one of (a) film formation step, (d) heating step and post-development exposure step, and (e) metal layer formation step in that order. By alternately performing the lamination step of the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

[1004] (Surface activation treatment process)

[1005] The preferred method for manufacturing the laminate of the present invention includes a surface activation treatment step of surface activating at least a portion of the metal layer and the resin composition layer.

[1006] The surface activation treatment process is usually performed after the metal layer formation process, but it can also be performed after the development process (preferably after at least one of the heating process and the post-development exposure process) or after the surface activation treatment process of the resin composition layer.

[1007] The surface activation treatment can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. Preferably, the surface activation treatment is performed on at least a portion of the metal layer, and more preferably, on a portion or all of the region of the metal layer on which the resin composition layer is formed. Thus, by performing surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on that surface can be improved.

[1008] Preferably, part or all of the exposed resin composition layer (resin layer) is also surface-activated. In this way, by surface-activating the surface of the resin composition layer, the adhesion to the metal layer or resin layer disposed on the surface-activated surface can be improved. In particular, when the resin composition layer has been cured, such as in the case of negative development, it is less susceptible to damage caused by surface treatment, and adhesion is easily improved.

[1009] Surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[1010] (Semiconductor devices and their manufacturing methods)

[1011] The present invention also discloses a semiconductor device comprising the cured material or laminate of the present invention.

[1012] Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product or the method for manufacturing a laminate of the present invention.

[1013] As a specific example of using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer in a semiconductor device, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and... Figure 1 The records and information contained herein are included in this instruction manual.

[1014] Example

[1015] The following examples provide a more detailed description of the present invention. The materials, amounts, proportions, processing methods, and processing order shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" refer to mass measurements.

[1016] <Resin Synthesis>

[1017] Synthesis of 6-maleimide hexanoyl chloride (M-1)

[1018] In a flask equipped with a thermometer and a calcium chloride tube, 7.92 g (37.5 mmol) of 6-maleimide hexanoic acid was dissolved in 30 g of tetrahydrofuran, and 0.1 g of N,N'-dimethylformamide was added. The mixture was stirred with a magnetic stirrer while cooling to 0 °C. Next, 4.85 g (38.25 mmol) of chloroxal chloride was added dropwise, and the mixture was stirred at 0 °C–10 °C for 1 hour. Then, the temperature was raised to 25 °C and stirred for 2 hours to synthesize 6-maleimide hexanoyl chloride (M-1).

[1019] [Chemical Formula 62]

[1020]

[1021] [Synthesis of M-2 to M-3]

[1022] Compounds represented by the following formulas (M-2) and (M-3) were synthesized by the same method as for 6-maleimide hexanoyl chloride (M-1) described above.

[1023] [Chemical Formula 63]

[1024]

[1025] <Synthesis example AA-1>

[1026] 48.65 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide were mixed in a 1 L flask. 98.21 g (450 mmol) of di-tert-butyl dicarbonate was added dropwise under ice-cold conditions. After the addition was complete, the mixture was stirred at 60 °C for 5 hours. After the reaction was complete and cooled to room temperature, 35 mg of 2,2,6,6-tetramethylpiperidine 1-oxy radical, 68.68 g (450 mmol) of p-chloromethylstyrene, 74.63 g (540 mmol) of potassium carbonate, and 8.96 g (54.0 mmol) of potassium iodide were added, and the mixture was stirred at 60 °C for 3 hours. After the reaction was complete, the mixture was filtered by suction filtration, and the filtrate was added dropwise to 500 mL of water. White crystals precipitated, and the precipitated solid was recovered by suction filtration. The obtained white solid was purified by recrystallization using 1000 mL of acetone at 60 °C. 125 g of the intermediate AA-1a was obtained (yield 85.6%).

[1027] The structure of AA-1a is shown below. According to... 1 H-NMR spectroscopy confirmed the following structure.

[1028] 1 H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6) 8.04-7.94 (s, 2H), 7.

[1029] 75-7.64 (d,2H), 7.56-7.42 (m,8H), 7.27-7.20 (d,2H), 7.19-7.12 (d,2H), 6.79-6.64 (2H),

[1030] 5.89-5.77 (2H), 5.30-5.15 (6H), 1.49-1.43 (s, 18H)

[1031] [Chemical Formula 64]

[1032]

[1033] 75.0 g (115.6 mmol) of (AA-1a) and 500 mL of dichloromethane were mixed in a 1 L flask. After adding 131.8 g (1156 mmol) of trifluoroacetic acid at room temperature, the mixture was stirred at 40 °C for 5 hours. After the reaction was complete, 250 mL of methanol was added dropwise under ice-cold conditions, followed by 117.0 g (1156 mmol) of triethylamine. Pale yellow crystals precipitated, and the precipitated solid was recovered by suction filtration. The solid was washed with 750 mL of methanol to obtain 40.5 g (73% yield) of (AA-1). The structure of AA-1 is shown below. 1 H-NMR spectroscopy confirmed the following structure.

[1034] 1 H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6) 7.53-7.45 (s, 8H), 7.05-6.98 (d, 2H), 6.92-6.85 (d, 2H), 6.79 -6.63(4H),5.89-5.78(d,2H),5.29-5.22(d,2H),5.20-5.13(s,4H),4.92-4.64(4H)

[1035] [Chemical Formula 65]

[1036]

[1037] <Synthetic Examples AA-2, AA-3 and AA-4>

[1038] In synthetic example AA-1, 3,3'-dihydroxybenzidine was appropriately modified; otherwise, AA-2, AA-3, or AA-4 were obtained by the same method as in synthetic example AA-1. The structures of each compound are shown below. 1 H-NMR spectroscopy confirmed the following structure.

[1039] [Chemical Formula 66]

[1040]

[1041] [Synthetic Example SA-1: Synthesis of Polyimide (SA-1)]

[1042] 6.05 g (28.5 mmol) of m-toluidine, 12.78 g (28.5 mmol) of AA-1, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 100 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 26.68 g (51.3 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride was dissolved in 100 g of NMP and added dropwise to the solution over 1 hour at 10°C–25°C. After stirring at 25°C for 60 minutes, 1.87 g (8.55 mmol) of di-tert-butyl dicarbonate was added dropwise, and the mixture was stirred at 45°C for 3 hours. Then, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the reaction was carried out at 80°C for 4 hours. After the reaction was complete, the solution was cooled to 25°C and diluted with 200g of tetrahydrofuran. Next, the reaction solution was added dropwise to a mixture of 1.5L methanol and 0.5L water, and after stirring for 15 minutes, the polyimide resin was filtered. Then, the resin was re-slurryed with 1L water for 30 minutes and filtered again, followed by re-slurrying with 1L methanol and filtering. The resin was then dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in 250g of tetrahydrofuran, and 0.1g of TEMPO and 50g of trifluoroacetic acid were added. The mixture was stirred at 45°C for 4 hours, cooled to below 25°C, and the polyimide resin was precipitated in 2L of methanol with stirring for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day. The dried resin was dissolved in 250 g of tetrahydrofuran and 25 g of water, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SA-1). The obtained polyimide (SA-1) had a weight-average molecular weight of 21,200 and a number-average molecular weight of 7,800. The weight-average molecular weight and number-average molecular weight were determined by gel permeation chromatography (GPC) and were defined as polystyrene equivalents. In this specification, the weight-average molecular weight and number-average molecular weight of the resins obtained in the following synthesis examples were determined using an HLC-8420GPC (manufactured by TOSOH CORPORATION) and by connecting two guard columns, TSK SuperAW-H, TSK SuperAWM-H, and TSK SuperAWM-H, in series. The eluent was determined using a lithium bromide (10 mmol / g) NMP (N-methyl-2-pyrrolidone) solution.Furthermore, a 275nm UV (ultraviolet) detector was used in the GPC measurement. The imidization rate was 99%. Polyimide (SA-1) is a resin having repeating units represented by the following formula SA-1. According to... 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1043] [Chemical Formula 67]

[1044]

[1045] [Synthetic Examples SA-2 to SA-4: Synthesis of Polyimide (SA-2 to SA-4)]

[1046] With appropriate changes to the raw materials, polyimides (SA-2 to SA-4) were synthesized using the same method as in synthesis example SA-1. The polyimides (SA-2 to SA-4) are resins having repeating units represented by the following formulas SA-2 to SA-4. 1 H-NMR spectroscopy determined the structure of each repeating unit. In the following structures, the subscripts in parentheses indicate the molar ratio of each structure. The weight-average molecular weight, number-average molecular weight, and imidization rate of these resins are listed in the table below.

[1047] [Chemical Formula 68]

[1048]

[1049] [Chemical Formula 69]

[1050]

[1051] [Chemical Formula 70]

[1052]

[1053] [Table 1]

[1054]

[1055] [Synthetic Example SA-5: Synthesis of Polyimide (SA-5)]

[1056] 6.05 g (28.5 mmol) of m-toluidine, 12.78 g (28.5 mmol) of AA-1, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 100 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 26.68 g (51.3 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride was dissolved in 100 g of NMP and added dropwise to the solution over 1 hour at 10°C–25°C. After stirring at 25°C for 60 minutes, 1.87 g (8.55 mmol) of di-tert-butyl dicarbonate was added dropwise, and the mixture was stirred at 45°C for 3 hours. Then, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the reaction was carried out at 80°C for 4 hours. After the reaction was completed, the solution was cooled to 25°C and diluted with 200g of tetrahydrofuran. Next, the reaction solution was added dropwise to a mixture of 1.5L methanol and 0.5L water, and after stirring for 15 minutes, the polyimide resin was filtered. Then, the resin was re-slurryed with 1L water for 30 minutes and filtered again, followed by re-slurrying with 1L methanol and filtering. The resin was then dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in 250g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide (SA-5).

[1057] The obtained polyimide (SA-5) has a weight-average molecular weight of 22,500 and a number-average molecular weight of 7,200. The imidization rate is 99%. Polyimide (SA-5) is a resin having repeating units represented by the following formula (SA-5). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1058] [Chemical Formula 71]

[1059]

[1060] [Synthetic Example SA-6: Synthesis of Polyimide (SA-6)]

[1061] With appropriate modifications to the raw materials, polyimide (SA-6) was synthesized using the same method as in synthesis example SA-5. The obtained polyimide (SA-6) had a weight-average molecular weight of 12,600 and a number-average molecular weight of 5,800. 1According to H-NMR measurements, the imidization rate was 98%. Polyimide (SA-6) is a resin having repeating units represented by the following formula (SA-6). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1062] [Chemical Formula 72]

[1063]

[1064] [Synthetic Example SB-1: Synthesis of Polyimide (SB-1)]

[1065] 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 5.14 g (24.2 mmol) of m-toluidine and 10.86 g (24.2 mmol) of AA-1 were dissolved in 80 g of NMP and added dropwise to the solution over 1 hour at 10°C–25°C. After stirring at 25°C for 60 minutes, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the reaction was allowed to proceed at 80°C for 4 hours. After the reaction was complete, the solution was cooled to 25°C and diluted with 200 g of tetrahydrofuran. Next, the reaction solution was added dropwise to 2.0 L of water, and after stirring for 15 minutes, the polyimide resin was filtered. Then, the resin was re-slurryed with 1 L of water for 30 minutes and filtered again, followed by re-slurrying with 1 L of methanol and filtering. The resin was then dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in 250 g of tetrahydrofuran and 20 g of water, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide (SB-1).

[1066] The obtained polyimide (SB-1) has a weight-average molecular weight of 20,500 and a number-average molecular weight of 7,500. According to... 1 According to H-NMR measurements, the imidization rate was 91%. Polyimide (SB-1) is a resin having repeating units represented by the following formula (SB-1). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1067] [Chemical Formula 73]

[1068]

[1069] [Synthetic Examples SB-2, SB-3: Synthesis of Polyimide (SB-2, SB-3)]

[1070] With appropriate changes to the raw materials, polyimides (SB-2, SB-3) were synthesized using the same method as in synthesis example SB-1. Polyimides (SB-2, SB-3) are resins having repeating units represented by the following formulas (SB-2, SB-3). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit. Furthermore, the weight-average molecular weight, number-average molecular weight, and imidization rate of these resins are listed in the table below.

[1071] [Chemical Formula 74]

[1072]

[1073] [Chemical Formula 75]

[1074]

[1075] [Table 2]

[1076]

[1077] [Synthetic Example SB-4: Synthesis of Polyimide (SB-4)]

[1078] 30.00 g (57.64 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)phthalic anhydride was dissolved in 150 g of N-methylpyrrolidone (NMP). Then, while washing with 30 g of NMP, 5.36 g (24.79 mmol) of HAB (3,3'-dihydroxybenzidine, manufactured by WAKAYAMA SEIKA KOGYO CO.,LTD.), 9.13 g (24.79 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl, and 10 g of toluene were added. After stirring for 15 minutes, the mixture was allowed to react at 200 °C for 4 hours under nitrogen atmosphere, and then cooled to 25 °C. Next, 15.3 g (100 mmol) of 4-(chloromethyl)styrene, 19.92 g (144 mmol) of potassium carbonate, 2.39 g (14 mmol) of potassium iodide, and 0.1 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were added. The mixture was reacted at 95°C for 15 hours, then cooled to 25°C, diluted with 200 g of tetrahydrofuran, and filtered through filter paper to remove salts. The reaction solution was then added dropwise to 2.0 L of water and stirred for 1 hour, followed by filtration of the polyimide resin. The resin was then re-slurryed with 1 L of water and filtered, then re-slurryed again with 2 L of methanol and filtered, and finally dried under reduced pressure at 40°C for 8 hours. Next, the dried resin was dissolved in 300g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide (SB-4). The obtained polyimide (SB-4) had a weight-average molecular weight of 18,700 and a number-average molecular weight of 7,300. According to... 1 According to H-NMR measurements, the imidization rate is 90%. Polyimide (SB-4) is a resin having repeating units represented by the following formula (SB-4). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1079] [Chemical Formula 76]

[1080]

[1081] [Synthetic Example SB-5: Synthesis of Polyimide (SB-5)]

[1082] The diamine feedstock was appropriately modified, and 4-(chloromethyl)styrene was appropriately replaced with 3-chloropropyl methacrylate. Otherwise, polyimide (SB-5) was synthesized using the same method as in synthesis example SB-4. The obtained polyimide (SB-5) had a weight-average molecular weight of 14,700 and a number-average molecular weight of 6,300. 1 According to H-NMR measurements, the imidization rate was 89%. Polyimide (SB-5) is a resin having repeating units represented by the following formula (SB-5). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1083] [Chemical Formula 77]

[1084]

[1085] [Synthetic Example SB-6: Synthesis of Polyimide (SB-6)]

[1086] 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride was dissolved in 130 g of N-methylpyrrolidone (NMP). Then, while rinsing with 50 g of NMP, 3.20 g (12.39 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 7.89 g (37.18 mmol) of bi-m-toluidine, and 2.78 g (11.53 mmol) of hexadecylamine were added. The mixture was stirred at 20°C–50°C for 30 minutes, then 10 g of toluene was added, and the mixture was reacted at 200°C for 4 hours under nitrogen atmosphere, followed by cooling to 25°C. Next, a THF solution (37.5 mmol) of the synthesized 6-maleimide hexanoyl chloride (M-1), 6.13 g (77.5 mmol) of pyridine, and 0.10 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were added, and the mixture was reacted at 25°C for 2 hours. The temperature was then raised to 45°C, and the mixture was stirred for another 10 hours. The reaction mixture was then added dropwise to 2.0 L of water, and after stirring for 1 hour, the polyimide resin was filtered. The resin was then re-slurried with 1 L of water and filtered, followed by re-slurrying again with 2 L of methanol and filtering. The resin was then dried under reduced pressure at 40°C for 8 hours. This process was repeated three times in the original text. Next, the dried resin was dissolved in 250g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANOCORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide (SB-6). The obtained polyimide (SB-6) had a weight-average molecular weight of 22,500 and a number-average molecular weight of 8,800. 1 According to H-NMR measurements, the imidization rate was 92%. Polyimide (SB-6) is a resin having repeating units represented by the following formula (SB-6). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1087] [Chemical Formula 78]

[1088]

[1089] [Synthetic Example SB-7: Polyimide (Synthesis of SB-7)]

[1090] With appropriate modifications to the raw materials, polyimide (SB-7) was synthesized using the same method as in synthesis example SB-6. The obtained polyimide (SB-7) had a weight-average molecular weight of 13,500 and a number-average molecular weight of 5,800. 1 According to H-NMR measurements, the imidization rate was 86%. Polyimide (SB-7) is a resin having repeating units represented by the following formula (SB-7). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1091] [Chemical Formula 79]

[1092]

[1093] [Synthetic Example SB-8: Synthesis of Polyimide (SB-8)]

[1094] 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 5.14 g (24.2 mmol) of bitoluidine and 11.87 g (24.2 mmol) of AA-3 were dissolved in 80 g of NMP and added dropwise to the solution over 1 hour at 10°C–25°C. After stirring at 25°C for 60 minutes, 3.35 g (18.5 mmol) of 4-aminophthalic acid was added, and the mixture was stirred at 25°C for 90 minutes. Then, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the reaction was carried out at 80°C for 4 hours. After the reaction was completed, the solution was cooled to 25°C and diluted with 200g of tetrahydrofuran. The reaction mixture was then added dropwise to 2.0L of water and stirred for 15 minutes, followed by filtration of the polyimide resin. Next, the resin was re-slurryed with 1L of water for 30 minutes and filtered, then re-slurryed again with 1L of methanol and filtered, and dried under reduced pressure at 40°C for 10 hours. The dried resin was then dissolved in 250g of tetrahydrofuran and 20g of water, and 40g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SB-8).

[1095] The obtained polyimide (SB-8) has a weight-average molecular weight of 14,600 and a number-average molecular weight of 6,000.

[1096] according to 1 According to H-NMR measurements, the imidization rate was 88%. Polyimide (SB-8) is a resin having repeating units represented by the following formula (SB-8). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1097] [Chemical Formula 80]

[1098]

[1099] [Synthetic Example SB-9: Synthesis of Polyimide (SB-9)]

[1100] 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 8.92 g (24.2 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl and 10.86 g (24.2 mmol) of AA-1 were dissolved in 80 g of NMP and added dropwise to the solution over 1 hour at 10°C–25°C. After stirring at 25°C for 60 minutes, 3.35 g (18.5 mmol) of 4-aminophthalic acid was added, and the mixture was stirred at 25°C for 90 minutes. Then, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the reaction was carried out at 80°C for 4 hours. After the reaction was completed, the mixture was cooled to 25°C, diluted with 250g of tetrahydrofuran, and 50g of methanol was added. The mixture was stirred for 2 hours. Next, the reaction solution was added dropwise to 2.0L of methanol and stirred for 15 minutes. The polyimide resin was then filtered. The resin was then re-slurryed with 1L of water for 30 minutes and filtered again. It was then re-slurryed again with 1L of methanol and filtered, and dried under reduced pressure at 40°C for 10 hours. The dried resin was then dissolved in 250g of tetrahydrofuran and 20g of water, and 40g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SB-9).

[1101] The obtained polyimide (SB-9) has a weight-average molecular weight of 16,200 and a number-average molecular weight of 7,100.

[1102] according to1 According to H-NMR measurements, the imidization rate was 89%. Polyimide (SB-9) is a resin having repeating units represented by the following formula (SB-9). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1103] [Chemical Formula 81]

[1104]

[1105] [Synthetic Example SB-10: Synthesis of Polyimide (SB-10)]

[1106] 30.00 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride was dissolved in 150 g of N-methylpyrrolidone (NMP). Then, while washing with 30 g of NMP, 3.28 g (12.68 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 8.08 g (38.04 mmol) of bi-m-toluidine, and 10 g of toluene were added. After stirring for 1 hour, the mixture was allowed to react at 180 °C for 4 hours under nitrogen atmosphere, and then cooled to 25 °C. Next, 4.33 g (27.89 mmol) of Karenz MOI (Resonac Corporation), 0.1 g of NEOSTANN U-600 (manufactured by NITTOKASEI CO.,LTD), and 0.1 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were added. After reacting at 90°C for 20 hours, the mixture was cooled to 25°C, diluted with 150 g of tetrahydrofuran, and the reaction solution was added dropwise to 2 L of methanol. After stirring for 15 minutes, the polyimide resin was filtered. Then, the resin was re-slurryed with 1 L of water and filtered, followed by re-slurrying again with 1 L of methanol and filtering. The resin was then dried under reduced pressure at 40°C for 8 hours. Next, the dried resin was dissolved in 300g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANOCORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SB-10). The obtained polyimide resin (SB-10) had a weight-average molecular weight of 17,600 and a number-average molecular weight of 7,300. Polyimide (SB-10) is a resin having repeating units represented by the following formula (SB-10). 1H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1107] [Chemical Formula 82]

[1108]

[1109] <Synthesis of Polyimide Precursors>

[1110] [Synthetic Example SP-1: Synthesis of Polyimide (SP-1)]

[1111] 30.00 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride was dissolved in 150 g of N-methylpyrrolidone (NMP). Then, while washing with 30 g of NMP, 5.36 g (24.79 mmol) of HAB (3,3'-dihydroxybenzidine, manufactured by WAKAYAMA SEIKA KOGYO CO.,LTD.), 9.13 g (24.79 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl, 2.51 g (10.38 mmol) of hexadecylamine, and 10 g of toluene were added. After stirring for 15 minutes, the mixture was allowed to react at 200 °C for 4 hours under nitrogen atmosphere and then cooled to 25 °C. Next, 15.3 g (100 mmol) of 4-(chloromethyl)styrene, 19.92 g (144 mmol) of potassium carbonate, 2.39 g (14 mmol) of potassium iodide, and 0.1 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were added, and the mixture was reacted at 95 °C for 15 hours. The mixture was then cooled to 25 °C, diluted with 150 g of tetrahydrofuran, and filtered through filter paper to remove salts. Next, the reaction mixture was added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, stirred for 15 minutes, and then filtered onto the polyimide resin. The resin was then re-slurryed with 1 L of water and filtered, followed by re-slurrying again with 1 L of methanol and filtering. Finally, the resin was dried under reduced pressure at 40 °C for 8 hours. Next, the dried resin was dissolved in 300g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide (SP-1). The obtained polyimide (SP-1) had a weight-average molecular weight of 19,700 and a number-average molecular weight of 8,000. The imidization rate was 90%. Polyimide (SP-1) is a resin having repeating units represented by the following formula SP-1. 1H-NMR spectroscopy determined the structure of the repeating unit. In the following structures, the subscripts in parentheses indicate the molar ratio of each structure.

[1112] [Chemical Formula 83]

[1113]

[1114] [Synthetic Example SP-2: Synthesis of Polyimide Precursor (SP-2)]

[1115] 19.83 g (38.1 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride, 10.12 g (77.8 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 13.40 g (169 mmol) of pyridine, and 70 g of diethylene glycol monomethyl ether were mixed and stirred at 60 °C for 5 hours to produce a diester of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) and glyceryl dimethacrylate. Then, after cooling the mixture to -10 °C, 9.53 g (79.2 mmol) of thionyl chloride was added dropwise over 90 minutes, and the mixture was stirred for 2 hours to obtain a white precipitate of pyridinium hydrochloride. Next, 7.12 g (33.5 mmol) of bi-m-toluidine was dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) and added dropwise over a period of 2 hours. Then, 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 L of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 L of water for 30 minutes, filtered again, and dried at 40°C for 2 days. Next, the dried resin was dissolved in 200 g of tetrahydrofuran, and 50 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added, and the mixture was stirred for 6 hours. Then, the polyimide precursor resin was precipitated in 4 L of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration and dried under reduced pressure at 45°C for two days to obtain polyimide precursor (SP-2). The obtained polyimide precursor (SP-2) had a weight-average molecular weight of 28,600 and a number-average molecular weight of 11,400. The imidization rate was 3%. The polyimide precursor (SP-2) was a resin having repeating units represented by the following formula (SP-2). 1 H-NMR spectroscopy determined the structure of the repeating unit.

[1116] [Chemical Formula 84]

[1117]

[1118] <Comparative Synthesis of Compound A-1>

[1119] In a drying reactor equipped with a flat-bottomed connector featuring a stirrer, condenser, and internal thermometer, 44.43 g (121.3 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 57.29 g (125.0 mmol) of bis(1,3-dioxy-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene were added while removing moisture, along with 492.43 g of γ-butyrolactone. The mixture was stirred at 60 °C for 1.5 hours. Next, 50 mL of toluene was added, and the temperature was raised to 180 °C while introducing nitrogen gas at a flow rate of 200 mL / min. The mixture was stirred for 3 hours and then cooled to room temperature. The obtained polymerization solution was diluted with acetone to prepare a diluent. This diluent was then added dropwise to a water / methanol mixture of 3 / 1, causing a white solid to precipitate. The obtained white solid was recovered and dried under vacuum at 120 °C to obtain 90 g of polymer. Next, 73.86 g (150.0 mmol equivalent of hydroxyl groups) of the polymer obtained above, 21.17 g (150.0 mmol) of ethyl 2-isocyanate acrylate (hereinafter also referred to as AOI, manufactured by SHOWA DENKOK.K.), and 828.26 g of γ-butyrolactone (GBL) were placed in a reaction vessel equipped with a stirrer and a cooling pipe. The temperature was then raised to 120°C while stirring, and the reaction was allowed to proceed for 6 hours. The resulting reaction solution was then diluted with acetone to prepare a diluent. This diluent was then added dropwise to a water / methanol mixture of 2 / 1, causing a white solid to precipitate. The white solid was recovered and dried under vacuum at 40°C, yielding 71.8 g of A-1. The weight-average molecular weight (Mw) of A-1 was 78,500, and the number-average molecular weight (Mn) was 30,200. 1 H-NMR spectroscopy confirmed that the structure of A-1 is represented by the structure shown in equation (A-1), which is the main component. 1 The H-NMR results showed that the cross-linking group introduction rate was 55% and the imidization rate was 99%.

[1120] [Chemical Formula 85]

[1121]

[1122] <Examples and Comparative Examples>

[1123] In each embodiment, the components listed in the table below were mixed to obtain each resin composition. Furthermore, in each comparative example, the components listed in the table below were mixed to obtain each comparative composition.

[1124] Specifically, the content of each component recorded in the table is set to the amount (parts by mass) recorded in the "Amount Added" column of each column of the table.

[1125] The obtained resin composition and the comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm.

[1126] Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

[1127] [Table 3]

[1128]

[1129] [Table 4]

[1130]

[1131] [Resin (containing heterocyclic polymers)]

[1132] •SA-1~SA-6: SA-1~SA-6 synthesized above

[1133] •SB-1~SB-10: SB-1~SB-10 synthesized as described above

[1134] • SP-1~SP-2: SP-1~SP-2 synthesized above

[1135] • A-1: ​​The above-mentioned synthetic product (comparative example)

[1136] SA-1 to SA-6 are compounds corresponding to the heterocyclic polymer A-1 and resin 1 mentioned above.

[1137] SB-1 to SB-10 are compounds corresponding to the heterocyclic polymer A-2 and resin 2 mentioned above.

[1138] [Polymerizing compounds]

[1139] D-1: 1,12-Dodecanediol dimethacrylate (melting point: below 25°C)

[1140] D-2: 1,9-Nonanediol dimethacrylate (melting point: below 25°C)

[1141] D-3: 1,10-Decanediol dimethacrylate (melting point: below 25°C)

[1142] • D-4: SR-209 (manufactured by Sartomer Company, Inc., melting point: below 25°C)

[1143] • D-5: Dipentaerythritol hexaacrylate (ADPH, manufactured by Shin-Nakamura Chemical Co., Ltd., melting point: below 25°C)

[1144] • D-6: Tris(2-Acryloyloxyethyl) isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1145] [Solvent]

[1146] ·DMSO: Dimethyl sulfoxide

[1147] GBL: γ-Butyrolactone

[1148] NMP: N-methylpyrrolidone

[1149] γ-valerolactone

[1150] The table indicates that "DMSO / GBL" was prepared by mixing DMSO and GBL at a ratio (mass ratio) of 80:20.

[1151] [Polymerization initiators (all trade names)]

[1152] • OXE-01: IRGACURE OXE 01 (manufactured by BASF)

[1153] • OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[1154] • OXE-03: IRGACURE OXE 03 (manufactured by BASF)

[1155] • CPI-310B (manufactured by San-Apro Ltd.)

[1156] • BZP: Benzoyl peroxide 75% aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1157] [Migration Inhibitor]

[1158] •E-1~E-7: Compounds with the following structures

[1159] [Chemical Formula 86]

[1160]

[1161] [Metal adhesion modifier]

[1162] • F-1~F-3: Compounds with the following structures

[1163] [Chemical Formula 87]

[1164]

[1165] • F-4: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1166] • F-5: KBM-51073 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1167] • F-6: X-12-1214A (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1168] [Polymerization inhibitor]

[1169] G-1: 1,4-Benzoquinone

[1170] G-2: 4-Methoxyphenol

[1171] G-3: 1,4-Dihydroxybenzene

[1172] • G-4: Compounds with the following structures

[1173] [Chemical Formula 88]

[1174]

[1175] [Metal complex]

[1176] • I-1: TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1177] • I-2: TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1178] • I-3: Compounds with the following structures

[1179] [Chemical Formula 89]

[1180]

[1181] <Evaluation>

[1182] [Resolution Evaluation]

[1183] By spin coating, the resin compositions prepared in each example and comparative example were applied in a layered manner to the surface of a copper thin layer on a resin substrate on which a copper thin layer was formed. After drying at 100°C for 5 minutes to form a resin composition layer with a film thickness of 5 μm, a stepper (FPA-3000 i5 (manufactured by Canon Inc.)) was used with NA=0.50 and 300 mJ / cm². 2 Exposure was performed. A hole pattern mask with hole patterns of 3–20 μm diameter formed in 1 μm increments was exposed at a wavelength of 365 nm. Next, development was performed for 15 seconds using the developer listed in the "Developing Method (Developer)" column of the table, followed by rinsing with PGMEA for 30 seconds, and then heating at a rate of 10 °C / min under nitrogen atmosphere, and heating was performed at the temperature and curing time listed in the "Curing Conditions" column of the table to obtain hole patterns of 3–20 μm. The formed hole patterns were evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Resolution" column of the table. Image analysis using SEM (Scanning Electron Microscopy) was performed, and a residual film percentage at the bottom of the hole was considered resolvable (less than 1%). Generally speaking, the smaller the diameter of the hole pattern, the better the resolution; for example, A or B are preferred. Furthermore, examples not evaluated are recorded as "-" in the "Resolution" column of the table.

[1184] -Evaluation Criteria-

[1185] A: It can distinguish hole patterns up to 3μm in diameter.

[1186] B: It can distinguish hole patterns with a diameter of 5μm, but cannot distinguish hole patterns with a diameter of 3μm.

[1187] C: Unable to distinguish hole patterns with a diameter of 5μm.

[1188] [Evaluation of flatness]

[1189] In each embodiment and comparative example, a resin composition or a comparative composition was applied by spin coating onto a silicon wafer with copper wiring having a 1:1 L / S (line and gap) pattern with a height of 15 μm and a width of 20 μm and a taper angle of 85 degrees, forming a resin composition layer. The silicon wafer with the obtained resin composition layer applied was dried on a hot plate, thereby obtaining a resin composition layer with a uniform thickness of about 20 μm at the gaps of the copper wiring on the silicon wafer.

[1190] Under a nitrogen atmosphere, the above-mentioned resin composition layer was heated at a heating rate of 10°C / min, and heated for the time recorded in the "Curing Time" column of the "Curing Conditions" column of the table at the temperature conditions recorded in the "Temperature" column of the table, to obtain a cured product.

[1191] The depression X (μm) of the cured material in the gaps of the copper wiring was measured using a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation), and evaluated according to the following criteria. The evaluation results are recorded in the "Flatness" column of the table.

[1192] exist Figure 1 The diagram shows a schematic cross-sectional view of a solidified material formed on a silicon wafer with copper wiring. Figure 1 The silicon wafer 16 includes copper wiring 14, and a solidified material 12 is formed on the silicon wafer 16. Here, the solidified material 12 in the region on the silicon wafer 16 where the copper wiring 14 is not formed has a recess 18 of X μm. The width W of the gap portion of the copper wiring is 20 μm, and the cone angle θ of the copper wiring is 85°. The recess 18 can be observed, for example, as the difference between the solidified material at the center of the copper wiring and the total thickness h1 of the copper wiring, and the thickness h2 of the solidified material at the center of the gap portion of the copper wiring.

[1193] The smaller the depression 18(X), the better the flatness, and therefore it is preferred. For example, the evaluation is preferably A, B or C. Furthermore, for examples that are not evaluated, they are recorded as "-" in the "Flatness" column of the table.

[1194] -Evaluation Criteria-

[1195] A: X is below 1μm.

[1196] B: X is greater than 1 μm and less than 2 μm.

[1197] C:X exceeds 2μm and is less than 3μm.

[1198] D:X exceeds 3μm.

[1199] [Evaluation of elongation at break]

[1200] In each embodiment and comparative example, a resin composition layer was formed by spin-coating a photosensitive resin composition or a comparative composition onto a silicon wafer. The silicon wafer with the obtained resin composition layer applied was dried at 100°C for 5 minutes on a hot plate, thereby obtaining a uniform resin composition layer with a thickness of approximately 15 μm on the silicon wafer.

[1201] Using a stepper motor (Nikon NSR 2005 i9C), the entire surface of the obtained resin composition layer was grated at 500 mJ / cm². 2 The exposure energy was used for i-ray exposure.

[1202] Under a nitrogen atmosphere, the exposed resin composition layer (resin layer) was heated at a rate of 10°C / min. After reaching the temperature recorded in the "Temperature" column of the "Curing Conditions" section of the table, it was heated at that temperature for the time recorded in the "Curing Time" column of the "Curing Conditions" section of the table. The cured resin layer (cured film) was immersed in a 4.9% (w / w) hydrofluoric acid aqueous solution and the cured film was peeled off from the silicon wafer. Holes were punched in the peeled cured film using a punching machine to prepare test pieces with a sample width of 3 mm and a sample length of 30 mm. The elongation at break in the longitudinal direction of the obtained test pieces was measured using a tensile testing machine (TENSILON) at a crosshead speed of 300 mm / min, at 25°C and 65% RH (relative humidity), in accordance with JIS-K6251. Each test was performed 5 times, and the arithmetic mean of the elongation at break (elongation at break) of the test pieces was used as the index value.

[1203] Evaluate the above index values ​​according to the evaluation criteria below, and record the evaluation results in the "Elongation at Break" column of the table. It can be said that the higher the above index values, the better the film strength (elongation at break) of the obtained cured film.

[1204] -Evaluation Criteria-

[1205] A: The above indicator value is above 60%.

[1206] B: The above indicator value is above 50% and less than 60%.

[1207] C: The above indicator value is above 40% and less than 50%.

[1208] D: The above indicator value is less than 40%.

[1209] [Evaluation of Insulation Reliability]

[1210] The resin compositions or comparative compositions prepared in each example and comparative example were applied in layers onto a copper substrate using a spin coating method to form resin composition layers or comparative composition layers. The copper substrate with the obtained resin composition layers or comparative composition layers was dried at 100°C for 5 minutes on a hot plate, thereby forming a resin composition layer or comparative composition layer with a uniform thickness of 5 μm on the copper substrate. A stepper (Nikon NSR2005 i9C) was used at 500 mJ / cm². 2Using an exposure energy and a photomask with a non-mask portion forming a square of 100 μm, the resin composition layer or comparative composition layer on a copper substrate was exposed to I-rays. Then, it was developed for 60 seconds with the developer listed in the "Developer" column of the table, and rinsed with propylene glycol monomethyl ether acetate (PGMEA), thereby obtaining a 100 μm square resin layer. Furthermore, under a nitrogen atmosphere and at the temperature listed in the "Curing Temperature (°C)" column of the table, the resin layer (pattern) was formed using a heated oven for the time listed in the "Curing Time (minutes)" column of the table.

[1211] The resin composition layer and copper substrate were subjected to a bath at 100°C and 100% RH for 100 hours. Cross-sectional SEM (scanning microscope) measurements were performed, and the porosity between the copper substrate and the resin layer was evaluated. The porosity was calculated using the following formula.

[1212] Porosity (%) = (Area of ​​voids observed by SEM) / (Total area of ​​resin layer) × 100

[1213] Based on the obtained void area ratio, the evaluation is conducted according to the following evaluation criteria, and the evaluation results are recorded in the "Insulation Reliability" column of the table. It can be said that the smaller the void area ratio, the better the PCT (humid heat) resistance of the cured film; that is, even after a long period of time, voids are less likely to form between the metal layer and the cured material.

[1214] -Evaluation Criteria-

[1215] A: The void area ratio is below 0.2%.

[1216] B: The void area ratio is greater than 0.2% and less than 0.5%.

[1217] C: The void area ratio exceeds 0.5% but is less than 1%.

[1218] D: The porosity exceeds 1%.

[1219] [Evaluation of dielectric loss tangent]

[1220] Resin composition layers were formed by spin-coating the resin compositions or comparative compositions prepared in the various examples and comparative examples onto 12-inch silicon wafers. The silicon wafers with the obtained resin composition layers were dried on a hot plate at 100°C for 5 minutes, thereby forming a resin composition layer with a uniform thickness of 15 μm on the silicon wafer. A stepper (Nikon NSR 2005 i9C) was used at 500 mJ / cm². 2The exposure energy is used to expose the entire surface of the resin composition layer on the silicon wafer, and the exposed resin composition layer (resin layer) is heated in a nitrogen environment at a heating rate of 10°C / min. The temperature is then set at the temperature specified in the "Temperature" column of the "Curing Conditions" section of the table, and the time specified in the "Curing Time" column of the "Curing Conditions" section of the table is recorded, thereby obtaining a cured layer (resin layer) of the resin composition layer.

[1221] The cured layer (resin film) was immersed in a 4.9% (w / w) hydrofluoric acid aqueous solution and then peeled off from the silicon wafer. The dielectric loss tangent (Df) of the film sample was measured at 28 GHz using the resonator perturbation method.

[1222] <Determination Method>

[1223] Split-cylinder resonator (CR-728)

[1224] (Device structure)

[1225] Network Analyzer: N5230A (manufactured by KEYSIGHT)

[1226] (Evaluation Criteria)

[1227] A: The dielectric loss tangent (Df) is less than 0.06.

[1228] B: Dielectric loss tangent (Df) is less than 0.06 to 0.08.

[1229] C: Dielectric loss tangent (Df) is 0.08 or higher.

[1230] <Example 101>

[1231] The resin composition used in Example 1 was applied in a layered manner to the surface of a resin substrate on which a copper thin layer was formed using spin coating. After drying at 100°C for 4 minutes to form a resin composition layer with a film thickness of 20 μm, exposure was performed using a stepper (Nikon Corporation, NSR1505 i6). A spacer mask (a binary mask with a pattern of 1:1 lines and gaps and a linewidth of 10 μm) was exposed at a wavelength of 365 nm. After exposure, the layer was heated at 100°C for 4 minutes. Following the heating, the layer was developed in cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern.

[1232] Next, under nitrogen atmosphere, the temperature was increased at a rate of 10°C / min, and after reaching 230°C, it was maintained at 230°C for 3 hours, thereby forming an interlayer insulating film for the rewiring layer. This interlayer insulating film for the rewiring layer exhibits excellent insulation properties.

[1233] Furthermore, semiconductor devices were fabricated using these rewiring layers with interlayer insulating films, and as a result, they were confirmed to operate without any problems.

[1234] Symbol Explanation

[1235] 12-Curved material, 14-Copper wiring, 16-Silicon wafer, 18-Dent, H-Height of copper wiring, h1-Total thickness of the cured material and copper wiring at the center of the copper wiring, h2-Thickness of the cured material at the center of the gap in the copper wiring, W-Width of the gap in the copper wiring, θ-Cone angle of the copper wiring.

Claims

1. A resin composition comprising: A heterocyclic polymer A-1 having polymerizable groups and optionally protected amino groups; A heterocyclic polymer A-2 having polymerizable groups and structure A, wherein structure A is a structure in which two groups selected from the group consisting of a carboxylic acid ester group and optionally a protected carboxyl group are linked by a linking group with a chain length of 2 to 4; and Polymerization initiator.

2. The resin composition according to claim 1, wherein, The heterocyclic polymer A-2 comprises groups represented by any of the following formulas (S-1) to (S-4). In equations (S-1) to (S-4), R S1 Represents -OH, -O - or -OR S2 R S2 Indicates a protecting group, Cy indicates an aliphatic ring structure, and L represents a protecting group. 1 This indicates a single bond or an aliphatic group with a chain length of 1 or 2, where n represents an integer of 1 or 2, and * indicates a bonding site with other structures.

3. The resin composition according to claim 1 or 2, wherein, The heterocyclic polymer A-1 has two or more of the optionally protected amino groups, and the heterocyclic polymer A-2 has two or more of the structure A.

4. The resin composition according to claim 1 or 2, wherein, The heterocyclic polymer A-1 is a polyimide or a polybenzoxazole.

5. The resin composition according to claim 1 or 2, wherein, The heterocyclic polymer A-1 is a polyimide or a polybenzoxazole, and the heterocyclic polymer A-2 is a polyimide.

6. The resin composition according to claim 1 or 2, wherein, The optionally protected amino group is of the following formula (R T The group represented by ) Formula (R) T In ), T 1 This represents an organic group with a monovalent valence.

7. The resin composition according to claim 1 or 2, wherein, The weight-average molecular weight of the heterocyclic polymer A-1 is less than 26,000, and the weight-average molecular weight of the heterocyclic polymer A-2 is less than 26,000.

8. The resin composition according to claim 1 or 2, wherein, The content of heterocyclic polymer A-1 is 50% to 150% by mass relative to the content of heterocyclic polymer A-2.

9. The resin composition according to claim 1 or 2, further comprising resin C, The resin C is a resin containing repeating units represented by formula (4-1) or formula (4-2) below and not belonging to heterocyclic polymer A-1 and heterocyclic polymer A-2. In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each is an independent hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of them is a monovalent organic group having an olefinic unsaturated bond. In equation (4-2), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Let each independently represent the structure represented by the following formula (R-2), where n and m independently represent integers from 0 to 4, and n+m is 1 or higher. In equation (R-2), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an organic group with a valence of a1+1. 1 The terms represent vinyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, or epoxy, where a1 represents an integer greater than or equal to 1, a2 represents an integer greater than or equal to 1, and * represents X in formula (4-2). 1 Or Y 1 The bonding sites.

10. A resin composition comprising: Resin 1 comprising repeating units represented by the following formula (1-1); Resin 2 comprising repeating units represented by formula (1-2) or formula (1-3) below; and Polymerization initiator, In equation (1-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 W represents an organic group with 4 or more carbon atoms. 1 V represents an organic group with 4 or more carbon atoms. 1 R represents the organic group represented by the following formula (2-1). 1 Each of these groups independently represents a group containing a polymerizable group, where n and m independently represent integers from 0 to 4, and n+m is 1 or higher. In equation (1-2), X 2 Y represents an organic group with 4 or more carbon atoms. 2 W represents an organic group with 4 or more carbon atoms. 2 G represents an organic group with 4 or more carbon atoms. 1 and G 2 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. 2 Each of these groups independently represents a group containing a polymerizable group, where n and m independently represent integers from 0 to 4, and n+m is 1 or higher. In equation (1-3), X 3 Y represents an organic group with 4 or more carbon atoms. 3 W represents an organic group with 4 or more carbon atoms. 3 V represents a single bond or an organic group with 4 or more carbon atoms. 3 R represents the organic group represented by formula (3-1) or formula (3-2) below. 3 Each of these groups independently represents a group containing a polymerizable group, where n and m independently represent integers from 0 to 4, and n+m is 1 or higher. In equation (2-1), Q 1 The symbol represents a hydrogen atom or a group represented by the following formula (2-2), and * represents the W in formula (1-1). 1 The bonding site, In equation (2-2), T 1 The symbol represents a monovalent organic group, and * indicates a bonding site with the nitrogen atom in formula (2-1). In equation (3-1), R C1 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. C2 The substituent is represented by 'a', which represents an integer from 0 to 3, and '*' represents the substituent in equation (1-3). 3 The bonding site, In equation (3-2), R C1 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. C2 The substituent is represented by 'a', which represents an integer from 0 to 9, and '*' represents the substituent in equation (1-3). 3 The bonding sites.

11. The resin composition according to claim 10, wherein, R in equation (1-1) 1 R in equation (1-2) 2 and R in equation (1-3) 3 Let the following formula (R-1) represent the structure. In equation (R-1), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an aromatic group or a cyclic aliphatic group. 1 Indicates a polymerizable group, a1 indicates 1 or more and Z 1 Integers below the largest substitution base, a2 represents integers above 1, and * represents X in equation (1-1). 1 Or Y 1 The bonding sites.

12. The resin composition according to claim 11, wherein, In the formula (R-1) A 1 At least one of them is vinyl.

13. The resin composition according to claim 10, wherein, R in equation (1-1) 1 R in equation (1-2) 2 and R in equation (1-3) 3 It contains maleimide groups.

14. The resin composition according to any one of claims 10 to 13, wherein, G in equation (1-2) 1 and G 2 R in equation (3-1) C1 and R in equation (3-2) C1 Both are -OH or -O - .

15. The resin composition according to any one of claims 10 to 13, wherein, The weight-average molecular weight of resin 1 is below 26,000.

16. The resin composition according to any one of claims 10 to 13, wherein, The weight-average molecular weight of resin 1 is below 16,000.

17. The resin composition according to any one of claims 10 to 13, further comprising resin C, The resin C is a resin that contains repeating units represented by the following formula (4-1) or the following formula (4-2) and does not belong to resin 1 or resin 2. In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each is an independent hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of them is a monovalent organic group having an olefinic unsaturated bond. In equation (4-2), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Let each independently represent the structure represented by the following formula (R-2), where n and m independently represent integers from 0 to 4, and n+m is 1 or higher. In equation (R-2), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an organic group with a valence of a1+1. 1 The terms represent vinyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, or epoxy, where a1 represents an integer greater than or equal to 1, a2 represents an integer greater than or equal to 1, and * represents X in formula (4-2). 1 Or Y 1 The bonding sites.

18. The resin composition according to any one of claims 10 to 13, wherein, The content of resin 1 is 50% to 150% by mass relative to the content of resin 2.

19. The resin composition according to any one of claims 1, 2 and 10 to 13, further comprising a polymerizable compound.

20. The resin composition according to any one of claims 1, 2 and 10 to 13, comprising a solvent having a boiling point of 100°C to 260°C.

21. The resin composition according to claim 20, wherein, The content of the solvent with a boiling point of 100°C to 260°C is 40% by mass or more relative to the total mass of the composition.

22. The resin composition according to claim 20, comprising two or more solvents having a boiling point of 100°C to 260°C.

23. The resin composition according to any one of claims 1, 2 and 10 to 13, used for forming an interlayer insulating film for a rewiring layer.

24. A cured product formed by curing the resin composition according to any one of claims 1, 2 and 10 to 13.

25. A laminate comprising two or more layers formed of the cured material of claim 24, wherein a metal layer is included between any of the layers formed of the cured material.

26. A method for manufacturing a cured material, comprising: The film forming process involves applying the resin composition of any one of claims 1, 2, and 10 to 13 onto a substrate to form a film.

27. The method for manufacturing a cured product according to claim 26, comprising: The exposure process selectively exposes the film; The developing process involves using a developing solution to develop the film and form a pattern.

28. The method for manufacturing a cured product according to claim 26, comprising: The heating process involves heating the membrane at a temperature of 50°C to 450°C.

29. A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in claim 26.

30. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in claim 26.

31. A semiconductor device comprising the cured material of claim 24.

Images