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 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 containing: a resin A; a polymer having a polymerizable group and having two or more amino groups that may be protected; and a compound B having a molecular weight of 2,000 or less, the compound B having a structure A, which is a structure in which two or more groups selected from 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.

Description

TECHNICAL FIELD

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

[0002] Nowadays, resin materials produced from resin compositions containing resins are being effectively utilized in various fields.

[0003] For example, heterocyclic ring-containing polymers such as polyimides are used for various purposes because of their excellent heat resistance and insulating properties, etc. As the above purposes, there are no particular limitations, and if a semiconductor device for mounting is exemplified, the use as a material for an insulating film, a sealing member, or a protective film can be listed. Furthermore, they can also be used as a base film for a flexible substrate, a cover film, etc.

[0004] For example, in the above purposes, heterocyclic ring-containing polymers such as polyimides are used in the form of a resin composition containing a heterocyclic ring-containing polymer or a precursor thereof.

[0005] Such a resin composition is applied to a substrate, for example, by coating, etc. to form a photosensitive film, and then, depending on the need, exposure, development, heating, etc. are performed, whereby a cured product can be formed on the substrate.

[0006] The resin composition can be applied by a known coating method, etc., and thus, it can be said that the adaptability in manufacturing is excellent, for example, the degree of freedom in design, etc. such as the shape, size, application position, etc. of the resin composition to be applied at the time of application. From the viewpoint that such adaptability in manufacturing is excellent in addition to the high performance possessed by heterocyclic ring-containing polymers such as polyimides, the above resin composition is increasingly expected to be applied in industry.

[0007] For example, in Patent Literature 1, a photosensitive resin composition is described, which is characterized by containing a soluble polyimide (A) having a specific structure and a photo-base generator capable of generating an amino group by light irradiation.

[0008] PRIOR ART DOCUMENTS

[0009] PATENT LITERATURE

[0010] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 2007-86763 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] In recent years, in the field of semiconductor devices and the like, miniaturization, high frequency, high integration, and the like of devices are progressing. Along with this, for example, a resin composition used in the formation of a rewiring layer and the like is required to have excellent elongation at break even for a fine pattern, in order to prevent the destruction of the member due to heat shock and the like.

[0013] An object of the present application is to provide a resin composition from which a cured product having excellent elongation at break can be obtained, a cured product obtained by curing the above resin composition, a laminate including the above cured product, a method for producing the above cured product, a method for producing the above laminate, a method for producing a semiconductor device including the method for producing the above cured product, and a semiconductor device including the above cured product.

[0014] Means for solving the technical problem

[0015] Examples of representative embodiments of the present application are shown below.

[0016] <1> A resin composition comprising:

[0017] Resin A having a polymerizable group and having two or more protectable amino groups; and

[0018] Compound B having a structure in which two or more groups selected from a carboxylate group and a protectable carboxyl group are linked by a linking group having a length of 2 to 4 atoms, that is, Structure A, and having a molecular weight of 2,000 or less.

[0019] <2> The resin composition according to <1>, comprising a polyimide or a polybenzoxazole as the above resin A.

[0020] <3> The resin composition according to <1> or <2>, comprising a resin that is a polyimide or a polybenzoxazole and a resin that is a polyimide precursor or a polybenzoxazole precursor as the above resin A.

[0021] <4> The resin composition according to any one of <1> to <3>, comprising a resin including a repeating unit represented by the following formula (1-1) as the above resin A.

[0022] [Chemical Formula 1]

[0023]

[0024] In formula (1-1), X 1 represents an organic group having 4 or more carbon atoms, Y 1 represents an organic group having 4 or more carbon atoms, W 1 represents an organic group having 4 or more carbon atoms, V 1 represents a protectable amino group, R 1Each group represented by formula (R-1) is represented independently, with n and m representing integers from 0 to 4, and n+m being 1 or higher.

[0025] [Chemical Formula 2]

[0026]

[0027] In equation (R-1), L 1 A represents a linking group with a valence of a1+1. 1 The group represents a polymerizable group, a1 represents an integer greater than or equal to 1, and * represents the group with respect to X in equation (1-1). 1 Or Y 1 The bonding sites.

[0028] <5> The resin composition according to <4>, wherein,

[0029] At least one A in equation (R-1) included in equation (1-1) 1 It is vinylphenyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, epoxy, or a group containing them.

[0030] <6> The resin composition according to <4>, wherein,

[0031] At least one A in equation (R-1) included in equation (1-1) 1 It is vinylphenyl.

[0032] <7> The resin composition according to any one of <1> to <3>, wherein,

[0033] The polymerizability of resin A is 0.3–4.0 mmol / g.

[0034] <8> The resin composition according to any one of <4> to <7>, wherein,

[0035] V in equation (1-1) 1 It is the group represented by the following formula (2-1).

[0036] [Chemical Formula 3]

[0037]

[0038] 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.

[0039] [Chemical Formula 4]

[0040]

[0041] In equation (2-2), T 1 The symbol represents a monovalent organic group, and * represents the bonding site with the nitrogen atom in formula (2-1).

[0042] <9> The resin composition according to <8>, wherein,

[0043] In the above equation (2-1), Q 1 The group represented by formula (2-2).

[0044] <10> The resin composition according to any one of <1> to <9>, wherein,

[0045] The aforementioned protected amino groups are groups represented by the following formula (AM-1).

[0046] [Chemical Formula 5]

[0047]

[0048] In formula (AM-1), Q 1 The symbol represents a hydrogen atom or a group represented by the following formula (AM-2), and * indicates a bonding site with other structures.

[0049] [Chemical Formula 6]

[0050]

[0051] In formula (AM-2), T 1 The symbol represents a monovalent organic group, and * indicates the bonding site with the nitrogen atom in formula (AM-1).

[0052] <11> The resin composition according to <10>, wherein,

[0053] In the above formula (AM-1), Q 1 It represents the group represented by formula (AM-2).

[0054] <12> The resin composition according to any one of <1> to <11>, wherein,

[0055] Compound B comprises a structure represented by any of the following formulas (S-1) to (S-4) as a structure containing the above structure A.

[0056] [Chemical Formula 7]

[0057]

[0058] In equations (S-1) to (S-4), R S1 Represents -OH, -O - or -ORS2 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.

[0059] <13> The resin composition according to any one of <1> to <12>, wherein,

[0060] The content of structure A in 1g of compound B is 1-10 mmol / g.

[0061] <14> The resin composition according to any one of <1> to <13>, wherein,

[0062] The compound B mentioned above is the compound represented by the following formula (B-1).

[0063] [Chemical Formula 8]

[0064]

[0065] In equation (B-1), X 3 J represents a tetravalent organic group. 1 and J 2 -O- or -NR can be represented independently. N -, R N R represents a hydrogen atom or a hydrocarbon group. 3 and R 4 Each independently represents a monovalent organic group, G + They can be used to represent hydrogen cations or ammonium cations independently.

[0066] <15> The resin composition according to any one of <1> to <14> further comprises resin C, which is a resin containing repeating units represented by the following formula (4-1) or the following formula (4-2) and not belonging to resin A.

[0067] [Chemical Formula 9]

[0068]

[0069] In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each can be independently a 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.

[0070] [Chemical Formula 10]

[0071]

[0072] 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 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.

[0073] <16> The resin composition according to any one of <1> to <15> contains a solvent with a boiling point of 100 to 260°C at 1 atmosphere.

[0074] <17> The resin composition according to <16>, wherein,

[0075] 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.

[0076] <18> The resin composition according to <16> contains two or more solvents with boiling points of 100 to 260°C.

[0077] <19> The resin composition according to any one of <1> to <18> is used to form an interlayer insulating film for a rewiring layer.

[0078] <20> A cured product, which is a cured product obtained by curing the resin composition described in any one of <1> to <19>.

[0079] <21> A laminate comprising two or more layers formed of the cured material described in <20>, wherein a metal layer is included between any of the layers formed of the cured material.

[0080] <22> A method for manufacturing a cured material, comprising:

[0081] The film forming process involves applying the resin composition described in any one of <1> to <19> onto a substrate to form a film.

[0082] <23> The method for manufacturing the cured product according to <22> includes:

[0083] In the exposure process, the above-mentioned film is selectively exposed; and

[0084] In the developing process, the above film is developed using a developing solution to form a pattern.

[0085] <24> The method for manufacturing a cured product according to <22> or <23> includes:

[0086] The heating process involves heating the membrane at 50–450°C.

[0087] <25> A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in any one of <22> to <24>.

[0088] <26> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in any one of <22> to <24>.

[0089] <27> A semiconductor device comprising the cured material described in <20>.

[0090] Invention Effects

[0091] According to the present invention, a resin composition that yields a cured product with excellent elongation at break 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

[0092] Figure 1 This is a schematic cross-sectional view of a silicon wafer with a solidified material formed on it, where copper wiring has been formed. Detailed Implementation

[0093] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0094] 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.

[0095] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended function of the process can be achieved.

[0096] In this specification, the designations of groups (atomic groups) that do not indicate 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).

[0097] In this specification, unless otherwise stated, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Moreover, examples of light used for 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.

[0098] In this specification, "(meth)acrylate" means "acrylate" and "methacrylate" or either one; "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" or either one; and "(meth)acryloyl" means "acryloyl" and "methacryloyl" or either one.

[0099] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl in the structural formula.

[0100] In this specification, total solids content refers to the total mass of all components of the composition other than the solvent. 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.

[0101] In this specification, unless otherwise stated, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene conversion values. In this specification, for example, an HLC-8220 GPC (manufactured by TOSOH CORPORATION) is used as the column to connect guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) in series, thereby allowing the determination of the weight-average molecular weight (Mw) and number-average molecular weight (Mn). Unless otherwise stated, these molecular weights are determined using NMP (N-methyl-2-pyrrolidone) as the eluent. However, in cases where NMP is unsuitable as an eluent due to low solubility, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise stated, detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm.

[0102] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer among the layers of interest. That is, a third layer or third element can be further inserted between the reference layer and the other layers, and the reference layer does not need to be in contact with the other layers. The direction in which the layers are stacked relative to the substrate layer is called "upper," or, in the case of a resin composition layer, unless otherwise stated, the direction from the substrate toward the resin composition layer is called "upper," and the opposite direction is called "lower." In addition, this setting of up and down directions is for the convenience of explaining this specification, and in practice, the "upper" direction in this specification may also be different from the vertical direction.

[0103] In this specification, unless otherwise stated, each component included in the composition may contain two or more compounds equivalent to that component. Furthermore, unless otherwise stated, the content of each component in the composition refers to the total content of all compounds equivalent to that component.

[0104] Unless otherwise stated, the temperature in this manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH.

[0105] In this specification, the preferred combination of methods is a more preferred method.

[0106] (Resin composition)

[0107] The resin composition of the present invention (hereinafter also simply referred to as "resin composition") contains: resin A, having polymerizable groups and having two or more protected amino groups; and compound B, having a structure A in which two or more groups selected from carboxylic ester groups and protected carboxyl groups are linked by linking groups with a chain length of 2 to 4, and having a molecular weight of 2,000 or less.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative development.

[0112] In this invention, negative development refers to development in which non-exposed areas are removed by development during exposure and development, while positive development refers to development in which exposed areas are removed by development.

[0113] As the above-described exposure method, developer, and developing method, for example, the exposure method described in the exposure step of the description of the method for manufacturing cured material described later, and the developer and developing method described in the developing step can be used.

[0114] According to the resin composition of the present invention, a cured product with excellent elongation at break can be obtained.

[0115] The mechanism by which the above effects are achieved is not yet clear, but the following is a speculation.

[0116] If the required properties of the composition, such as the resin's solubility in solvents and the resolution when used as a photosensitive resin composition, are taken into account, it is necessary to reduce the molecular weight of the resin to a certain extent. However, according to the research of the inventors, reducing the molecular weight of the resin sometimes results in a lower elongation at break of the cured product.

[0117] In this invention, by using resin A and compound B, resin A reacts with compound B during curing to form a resin with a high molecular weight and an imide structure that is typically difficult to use as a composition. Therefore, it is believed that the elongation at break of the resulting cured product is increased.

[0118] Furthermore, it is believed that by setting the molecular weight of resin A to be smaller than that of the final resin, excellent resolution can be achieved during development.

[0119] Furthermore, it is believed that, as described above, since the molecular weight of each resin can be reduced, even when a photosensitive film is formed on a substrate with unevenness, the film's fluidity remains excellent during heating, and the flatness of the photosensitive film is improved.

[0120] This leads to the following situation: since a resin with a large final length is obtained, a cured product with excellent mechanical properties such as elongation at break and a small coefficient of thermal expansion can be obtained.

[0121] Furthermore, it is believed that since a high molecular weight resin is ultimately obtained, a cured product that does not easily form water penetration pathways and has excellent moisture resistance can be obtained.

[0122] Here, Patent Document 1 does not describe a resin composition containing resin A and compound B.

[0123] The components contained in the resin composition of the present invention will be described in detail below.

[0124] <Resin A>

[0125] The resin composition of the present invention contains resin A having polymerizable groups and having two or more protected amino groups.

[0126] Hereinafter, the amino groups present in resin A and the protected amino groups will be collectively referred to as "specific substituent A-1".

[0127] In the resin composition, resin A preferably contains a heterocyclic polymer, more preferably contains polyimide, polybenzoxazole, a polyimide precursor or a polybenzoxazole precursor, and even more preferably contains polyimide or polybenzoxazole, and even more preferably contains polyimide.

[0128] Furthermore, resin containing polyimide or polybenzoxazole and resin that is a polyimide precursor or polybenzoxazole precursor as resin A is also one of the preferred embodiments of the present invention.

[0129] In this specification, polyimide refers to a resin having repeating units containing imide groups within its molecular chain, preferably a resin having repeating units containing imide ring structures within its molecular chain.

[0130] Furthermore, when the polyimide is a linear resin, the polyimide is preferably a resin having repeating units containing imide groups in the main chain, and more preferably a resin having repeating units containing imide ring structures in the main chain.

[0131] In this specification, "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.

[0132] In this specification, the imide group refers to the structure represented by *-C(=O)N(-*)C(=O)-*, where * indicates a bonding site with other structures, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom.

[0133] In this specification, the imide ring structure refers to a ring structure in which both carbon atoms and the nitrogen atom in the aforementioned imide are included as ring-forming atoms. The imide ring structure is preferably a 5-membered ring.

[0134] Polyimide can be a so-called polyamide-imide, which has amide groups in addition to imide groups within its molecular chain. In this specification, the amide group refers to the structure represented by *-C(=O)N(-#)-*, where * indicates a bonding site with other structures, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Furthermore, # indicates a bonding site with other structures, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0135] In this specification, a polyimide precursor refers to a resin that becomes a polyimide by undergoing a change in its chemical structure through external stimulation, preferably a resin that becomes a polyimide by undergoing a change in its chemical structure through heat, and more preferably a resin that becomes a polyimide by forming a ring structure through a ring-closing reaction through heat.

[0136] The preferred manner in which the polyimide is formed is as described above.

[0137] In this specification, polybenzoxazole refers to a resin having repeating units containing a benzoxazole structure within its molecular chain.

[0138] Furthermore, when polybenzoxazole is a linear resin, polybenzoxazole is preferably a resin having repeating units containing a benzoxazole structure in the main chain.

[0139] In this invention, the benzoxazole structure refers to the structure represented by the following formula (PBO-1).

[0140] [Chemical Formula 11]

[0141]

[0142] In formula (PBO-1), * indicates the bonding site with other structures.

[0143] In this specification, a polybenzoxazole precursor refers to a resin that becomes polybenzoxazole by undergoing a change in its chemical structure through external stimulation, preferably a resin that becomes polybenzoxazole by undergoing a change in its chemical structure through heat, and more preferably a resin that becomes polybenzoxazole by forming a ring structure through a ring-closing reaction through heat.

[0144] [polymeric groups]

[0145] Resin A has polymerizable groups.

[0146] 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.

[0147] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0148] Among these, (meth)acryloyl, (meth)acrylamide, vinylphenyl, or maleimide are preferred, with (meth)acryloyl being more preferred from the viewpoint of reactivity. Furthermore, from the viewpoint of reducing dielectric loss tangent, vinylphenyl or maleimide are preferred.

[0149] The content of polymeric groups relative to the total mass of resin A (polymeric group value) is preferably 0.2 to 5.0 mmol / g, more preferably 0.3 to 4.0 mmol / g, and even more preferably 0.4 to 3.0 mmol / g.

[0150] The content of free radical polymerizable groups relative to the total mass of resin A (free radical polymerizable group value) is preferably 0.2 to 5.0 mmol / g, more preferably 0.3 to 4.0 mmol / g, and even more preferably 0.4 to 3.0 mmol / g.

[0151] The content of groups with olefinic unsaturated groups relative to the total mass of resin A (olefinic unsaturated group value) is preferably 0.2 to 5.0 mmol / g, more preferably 0.3 to 4.0 mmol / g, and even more preferably 0.4 to 3.0 mmol / g.

[0152] The content (molar amount) of each group in the resin in the composition can be calculated by the following method.

[0153] Add 1g of the composition to 50g of methanol or water to crystallize, precipitate resin A, and filter. Recover the filtrate, dissolve it in 3.0g of THF (tetrahydrofuran), add it to 50g of methanol or water to crystallize, filter, and dry at 40°C for 20 hours.

[0154] After dissolving 0.1 g of the dried resin A from the above process in 0.9 g of deuterated dimethyl sulfoxide, the solution was then... 1 The H-NMR was used for determination, and the amount of each group was calculated. 1 The cumulative number of H-NMR measurements was set to 640.

[0155] For example, in cases where only vinylphenyl is included as a polymerizable group, benzenesulfonyl anilide is used as the reference substance, and according to... 1 The ratio of the cumulative intensity of the peak near 5-7 ppm derived from vinylphenyl in the H-NMR spectrum to the cumulative intensity of the peak derived from the reference substance, along with the amount of the reference substance and the amount of resin A, allows the calculation of the polymerizable group value in resin A.

[0156] Specifically, 1.00 g of resin and 0.0233 g (0.1 mmol) of benzenesulfonyl aniline were dissolved in 9.0 g of deuterated DMSO, and then... 1 H-NMR (640 times cumulatively). Set the cumulative value of the NH peak of benzenesulfonyl aniline, i.e., the peak near 10.3 ppm, to 0.1, and calculate any one of the cumulative values ​​from vinylphenyl: 4.9–5.5 ppm, 5.5–6.2 ppm, and 6.5–7.0 ppm.

[0157] The units for the above cumulative values ​​are mmol / g.

[0158] Furthermore, the content of specific substituent A-1 and specific substituent A-2 in the resin can also be determined using the same method.

[0159] The acid value of resin A is preferably 0 to 2 mmol / g, more preferably 0 to 0.5 mmol / g, and even more preferably 0 to 0.1 mmol / g.

[0160] Acid value can be determined, for example, by a known titration method using a 0.01 mol / L aqueous sodium hydroxide solution as the titrant.

[0161] Specifically, the acid value can be determined by, for example, the following methods.

[0162] Weigh 0.30g of resin A into a beaker, add 80mL of N-methylpyrrolidone and 5mL of pure water, and dissolve to obtain a solution.

[0163] The acid value of the above solution was determined under the following conditions.

[0164] Automatic titration apparatus: AT-510 (manufactured by KYOTO ELECTRONICS MANUFACTURING CO.,LTD.)

[0165] Titrant: 0.01N (0.01mol / L) sodium hydroxide aqueous solution

[0166] Electrode: C-173 (AT-510 (manufactured by KYOTO ELECTRONICS MANUFACTURING CO.,LTD.))

[0167] Internal electrolyte for electrodes: 3.3 mol / L potassium chloride aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0168] Furthermore, specifically, the determination of amine value can be carried out, for example, by the following methods.

[0169] Weigh 0.30g of resin A into a beaker, add 50mL of diethylene glycol dimethyl ether and 10mL of acetic acid, and dissolve to obtain a solution.

[0170] [Specific substituent A-1]

[0171] The amino group that serves as the specific substituent A-1 can be any one of unsubstituted amino groups (-NH2) or protected amino groups (-N(R)2, where R represents a hydrogen atom or an organic group, and at least one of the two Rs is an organic group. Furthermore, R is preferably a hydrocarbon group.), with unsubstituted amino groups being preferred.

[0172] Furthermore, the protected amino group is preferably a group that generates an amino group through light, heat, acid or alkali.

[0173] Examples of protected amino groups include tert-butoxycarbonylamino, 9-fluorenylmethoxycarbonylamino, and alkoxycarbonylamino, urea, etc., which may have substituents.

[0174] The amino group derived from the protected amino group is preferably an unsubstituted amino group (-NH2).

[0175] Whether a group with a specific substituent A-1 is a group that generates an amino group through light can be confirmed by the following methods.

[0176] Under conditions of 1 atmosphere pressure and 25°C, a 1% by mass N-methylpyrrolidone solution of resin A is exposed to light with wavelengths of 190–800 nm at an exposure illuminance of 25 W / cm². 2 After irradiation for 60 seconds under the conditions, through 1 Methods such as H-NMR were used to confirm whether amino groups were produced.

[0177] When the group that is a 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.

[0178] The heating time for producing alkali is preferably 180 minutes, more preferably 120 minutes, and even more preferably 60 minutes.

[0179] Whether a group with 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 can be confirmed by the following method.

[0180] After exposing a 1% (w / w) N-methylpyrrolidone solution of resin A to heating at X °C for Y hours, the solution was then subjected to... 1 Methods such as H-NMR were used to confirm whether amino groups were produced.

[0181] Whether a group with a specific substituent A-1 is a group that generates an amino group through an acid can be confirmed by the following methods.

[0182] To a 1% by mass N-methylpyrrolidone solution of resin A, 1% by mass methanesulfonic acid was added relative to the solid content of the resin, and the solution was allowed to stand at 25°C for 60 minutes. Then, the solution was...1 Methods such as H-NMR were used to confirm whether amino groups were produced.

[0183] Whether a group with a specific substituent A-1 is a group that generates an amino group through a base can be confirmed by the following method.

[0184] To a 1% by mass N-methylpyrrolidone solution of resin A, add 1% by mass tetrabutylammonium hydroxide and 10% by mass methanol solution relative to the resin solids content, and let stand at 25°C for 60 minutes. Then, [the solution is analyzed by...]. 1 Methods such as H-NMR were used to confirm whether amino groups were produced.

[0185] The specific substituent A-1 is preferably a group represented by the following formula (AM-1).

[0186] [Chemical Formula 12]

[0187]

[0188] In formula (AM-1), Q 1 The symbol represents a hydrogen atom or a group represented by the following formula (AM-2), and * indicates a bonding site with other structures.

[0189] [Chemical Formula 13]

[0190]

[0191] In formula (AM-2), T 1 The symbol represents a monovalent organic group, and * indicates the bonding site with the nitrogen atom in formula (AM-1).

[0192] In formula (AM-2), T 1 Preferably, it is an alkyl group or an alkyl group substituted with a cyclic structure, more preferably a tertiary alkyl group or a methyl group substituted with a cyclic structure, and even more preferably a tert-butyl group or a 9-fluorenylmethyl group.

[0193] The specific substituent A-1 may be present at the end of the side chain of resin A, but is preferably present at the end of the main chain.

[0194] The content of the specific substituent A-1 in resin A 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 0.15 to 0.75 mmol / g.

[0195] The number of specific substituents A-1 in resin A is preferably 2 to 10 per molecule, more preferably 2 to 4, and even more preferably 2.

[0196] [The repeating unit represented by equation (1-1)]

[0197] Resin A preferably contains repeating units represented by the following formula (1-1).

[0198] [Chemical Formula 14]

[0199]

[0200] 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 a protected amino group. 1 Each group represented by formula (R-1) is represented independently, with n and m representing integers from 0 to 4, and n+m being 1 or higher.

[0201] [Chemical Formula 15]

[0202]

[0203] In equation (R-1), L 1 A represents a linking group with a valence of a1+1. 1 The group represents a polymerizable group, a1 represents an integer greater than or equal to 1, and * represents the group with respect to X in equation (1-1). 1 Or Y 1 The bonding sites.

[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 refers to an organic group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the following formulas (V-1) to (V-9), and more preferably, it refers to an organic group that includes a structure obtained 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 a structure containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-4).

[0208] Furthermore, by using organic groups containing structures obtained 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] In particular, by adding an organic group to a structure containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formulas (V-5) to (V-9), the transmittance of ultraviolet light is improved, thereby also achieving effects such as the cured material pattern not easily becoming conical and a wide tolerance for exposure.

[0210] [Chemical Formula 16]

[0211]

[0212] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0213] 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.

[0214] In equation (V-7), R X5 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0215] In equation (V-2), R X1 Each of the components is preferably 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 by a halogen atom. As the halogen atom, F or Cl is preferred, more preferably F.

[0216] In equation (V-3), R X2 and R X3 Each atom is preferably a hydrogen atom.

[0217] 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, an alkyl group or an aryl group, and even more preferably a hydrogen atom.

[0218] When X 1 When X is a group comprising a structure obtained 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). 1In the bonding sites of the four carbonyl groups, n1 represents an integer from 0 to 5, and is more preferably an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0219] [Chemical Formula 17]

[0220]

[0221] When X 1 When X is a group containing a structure obtained 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, and 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 crossing the edge of the ring structure refers to the bond that substitutes for 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 definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0222] [Chemical Formula 18]

[0223]

[0224] When X 1 When X is a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), 1 Preferably, the group is represented by formula (V-3-1) or formula (V-3-2) below. 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 definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0225] [Chemical Formula 19]

[0226]

[0227] When X 1 When X is a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), 1Preferably, 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 represents an integer from 0 to 5. Furthermore, the hydrogen atoms in the following structure can be further substituted with known substituents such as hydrocarbon groups. Preferably, in the structure represented by (V-4-1), none of the hydrogen atoms are substituted.

[0228] [Chemical Formula 20]

[0229]

[0230] When X 1 When X is a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-5), 1 Preferably, it is a group represented by the following formula (V-5-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0231] [Chemical Formula 21]

[0232]

[0233] When X 1 When X is a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), 1 Preferably, it is a group represented by the following formula (V-6-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0234] [Chemical Formula 22]

[0235]

[0236] When X 1 When X is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), 1 Preferably, it is a group represented by the following formula (V-7-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0237] [Chemical Formula 23]

[0238]

[0239] When X 1 When X is a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8), 1 Preferably, it is a group represented by the following formula (V-8-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0240] [Chemical Formula 24]

[0241]

[0242] When X 1 When X is a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9), 1 Preferably, it is a group represented by the following formula (V-9-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0243] [Chemical Formula 25]

[0244]

[0245] In addition, X 1 It can be the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic acid dianhydride as described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0246] And, X 1 Preferably, the structure does not contain imide bonds.

[0247] And, X 1 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0248] In this invention, the carbamate bond refers to *-OC(=O)-NR. N -* represents the key, R N Represents a hydrogen atom or a monovalent organic group, with * indicating the bonding site with a carbon atom. 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.

[0249] In this invention, the urea bond refers to *-NR. N -C(=O)-NR N -* represents the key, R NEach symbol represents a hydrogen atom or a monovalent organic group independently, and * indicates the bonding site with a carbon atom. R N The preferred method is as described above.

[0250] In addition, X 1 Preferably, the structure does not contain ester bonds.

[0251] In this invention, the ester bond refers to the bond represented by *-OC (=O)-*.

[0252] 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.

[0253] And, X 1 X can be the structure represented by the following equation (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 substituent group.

[0254] [Chemical Formula 26]

[0255]

[0256] In equation (X-2), X 2 Each independently represents a trivalent linker, L 3 * indicates a divalent linker, and * indicates a bonding site with other structures.

[0257] In equation (X-2), X 2 Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, or groups formed by linking two or more of them through single bonds or linking groups. Preferably, 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 them through single bonds or linking groups. More preferably, 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] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of them are preferred, and -O-, -S-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of them are more preferred.

[0259] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0260] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, with all hydrogen atoms being preferably replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene, etc.

[0261] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0262] And, X 2 Preferably, the compound is a tricarboxylic acid compound derived from at least one carboxyl group that can be halogenated. Chlorination is preferred as the halogenation method.

[0263] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0264] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-treated.

[0265] Examples of tricarboxylic acid compounds that can be halogenated include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0266] These tricarboxylic acid compounds can be used in one or more forms.

[0267] X 2 Preferably, the structure does not contain an imide structure.

[0268] And, X 2 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0269] Furthermore, X 2 Preferably, the structure does not contain ester bonds.

[0270] 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.

[0271] Specifically, as a tricarboxylic acid compound, it is preferable to be 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.

[0272] 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 formed by the linkage of phthalic acid (or phthalic anhydride) with benzoic acid through single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene oxide.

[0273] These compounds can be compounds with two carboxylic acid anhydrides (e.g., trimellitic anhydride) or compounds with at least one carboxylic acid halide (e.g., trimellitic anhydride chloride).

[0274] In equation (X-2), L 3 Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, or groups formed by linking two or more of them through single bonds or linking groups. Preferably, 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 them through single bonds or linking groups. More preferably, 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.

[0275] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of them are preferred, and -O-, -S-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of them are more preferred.

[0276] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0277] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, with all hydrogen atoms being preferably replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene, etc.

[0278] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0279] And, X 1 X can be the structure 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 substituent group.

[0280] [Chemical Formula 27]

[0281]

[0282] In equation (X-3), X 2 Each independently represents a trivalent linker, L 3 * indicates a divalent linker, and * indicates a bonding site with other structures.

[0283] 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.

[0284] -Y 1 -

[0285] Y 1 The carbon number is 4 or more, preferably 4 to 50, and more preferably 4 to 40.

[0286] In equation (1-1), Y 1 It can be a group that contains a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-9).

[0287] The chemical resistance and flatness of the cured product are improved by adding an organic group to the structure obtained by removing two or more hydrogen atoms from the structure represented by any of the formulas (V-1) to (V-9).

[0288] When Y 1 When Y is a group containing a structure obtained 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 replaced by known substituents such as hydrocarbon groups.

[0289] [Chemical Formula 28]

[0290]

[0291] When Y 1 When Y is a group containing a structure obtained 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, and 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 X1 The preferred configuration is as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0292] [Chemical Formula 29]

[0293]

[0294] When Y 1 When Y is a group containing a structure obtained 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 replaced by known substituents such as hydrocarbon groups.

[0295] [Chemical Formula 30]

[0296]

[0297] When Y 1When Y is a group containing a structure obtained 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 formula (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 represented 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 replaced by known substituents such as hydrocarbon groups.

[0298] [Chemical Formula 31]

[0299]

[0300] When Y 1 When Y is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-5), 1 Preferably, it is a group represented by the following formula (V-5-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0301] [Chemical Formula 32]

[0302]

[0303] When Y 1 When Y is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), 1 Preferably, it is a group represented by the following formula (V-6-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0304] [Chemical Formula 33]

[0305]

[0306] When Y 1 When Y is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), 1 Preferably, it is a group represented by the following formula (V-7-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0307] [Chemical Formula 34]

[0308]

[0309] When Y 1 When Y is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8), 1 Preferably, it is a group represented by the following formula (V-8-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0310] [Chemical Formula 35]

[0311]

[0312] When Y 1 When Y is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9), 1 Preferably, it is a group represented by the following formula (V-9-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0313] [Chemical Formula 36]

[0314]

[0315] In addition, Y 1 It can be the group described in paragraphs 0042 to 0053 of Japanese Patent Application Publication No. 2023-003421.

[0316] Furthermore, Y 1 Preferably, the structure does not contain imide bonds.

[0317] Furthermore, Y 1 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0318] Furthermore, Y 1 Preferably, the structure does not contain ester bonds.

[0319] 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.

[0320] Among these, X in the preferred formula (1-1) 1 and Y 1These are organic groups comprising structures obtained by removing two or more hydrogen atoms from the structures represented by any of the formulas (V-1) to (V-4) described above. Preferred embodiments of these groups are as described above.

[0321] -n and m-

[0322] 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.

[0323] In formula (1-1), n ​​is preferably 1 or 2, and more preferably 2.

[0324] -W 1 -

[0325] 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.

[0326] -V 1 -

[0327] V 1 This indicates an amino group that can be protected. The preferred manner for protecting the amino group is as described above.

[0328] Among these, V 1 Preferably, it represents the organic group represented by the following formula (2-1).

[0329] [Chemical Formula 37]

[0330]

[0331] 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.

[0332] [Chemical Formula 38]

[0333]

[0334] In equation (2-2), T 1 The symbol represents a monovalent organic group, and * represents the bonding site with the nitrogen atom in formula (2-1).

[0335] In equation (2-1), Q 1 Preferably, it is a group represented by formula (2-2).

[0336] In equation (2-2), T 1 The preferred method is the same as T in the above formula (AM-2). 1The preferred method is the same.

[0337] -R 1 -

[0338] R in equation (1-1) 1 It represents the group represented by formula (R-1).

[0339] [Chemical Formula 39]

[0340]

[0341] In equation (R-1), L 1 A represents a linking group with a valence of a1+1. 1 The group represents a polymerizable group, a1 represents an integer greater than or equal to 1, and * represents the group with respect to X in equation (1-1). 1 Or Y 1 The bonding sites.

[0342] In equation (R-1), L 1 Preferably, it is a group represented by the following formula (L-2).

[0343] [Chemical Formula 40]

[0344]

[0345] In equation (L-2), Z 2 Indicates -O-, -NR N -, -C(=O)O-or-C(=O)NR N -, R N Represents a hydrogen atom or a monovalent organic group; when a1 is 1, L x Indicates a single bond or a divalent linkage group; when a1 is 2 or more, L x This represents a linking group with a valence of a1+1, where a1 represents an integer greater than or equal to 1, and * represents a linking group with X in equation (1-1). 1 Or Y 1 Other bonding sites in the structure, # indicates the bonding with A in equation (R-1) 1 The bonding sites.

[0346] In equation (L-2), Z 2 Preferably -O- or -C(=O)O-. And, when Z 2 For -NR N - At that time, R N Preferably, it is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a phenyl group, and even more preferably a hydrogen atom.

[0347] In equation (L-2), when a1 is 1, L xPreferably, 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.

[0348] In equation (L-2), when a1 is 2 or more, L x Preferably, it is a group represented by a hydrocarbon group, a heterocyclic group, or a combination thereof, more preferably a saturated aliphatic hydrocarbon group with 2 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group with 3 to 15 carbon atoms.

[0349] In equation (L-2), a1 has the same meaning as a1 in equation (R-1).

[0350] In equation (R-1), A 1 The preferred method for the polymeric groups in the resin is the same as the preferred method for the polymeric groups in resin A described above.

[0351] Among these, A 1 Preferably, the radical is vinylphenyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, epoxy, or a group containing the like, more preferably maleimide, (meth)acryloyloxy, (meth)acrylamido, or vinylphenyl. In particular, from the viewpoint of reactivity, (meth)acryloyloxy is preferred. Furthermore, from the viewpoint of reducing the dielectric loss tangent of the cured product, maleimide or vinylphenyl is preferred.

[0352] In particular, at least one A in formula (R-1) included in preferred formula (1-1) 1 It is vinylphenyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, epoxy or a group containing them, more preferably maleimide, (meth)acryloyloxy, (meth)acrylamido or vinylphenyl, more preferably vinylphenyl.

[0353] Among these, A in the preferred formula (R-1) 1 It is vinylphenyl and L 1 It is the group represented by formula (L-2-1).

[0354] [Chemical Formula 41]

[0355]

[0356] In equation (L-2-1), L X2 'a1' represents a hydrocarbon group, and 'a1' represents an integer greater than or equal to 1.

[0357] In equation (L-2-1), L X2 Preferably, it contains aliphatic saturated hydrocarbon groups.

[0358] When a1 is 1, L X2Preferably, 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.

[0359] In equation (L-2-1), a1 has the same meaning as a1 in equation (R-1).

[0360] Furthermore, A in the preferred formula (R-1) 1 It is maleimide group and L 1 The group represented by formula (L-2) and L X It is an aromatic group or an aliphatic saturated hydrocarbon group with 4 or more carbon atoms.

[0361] The aromatic group can be any of an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred.

[0362] As an aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 10 carbon atoms is preferred, and an aromatic hydrocarbon group with 6 carbon atoms is more preferred.

[0363] 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, a 5-membered or 6-membered ring containing the aforementioned heteroatoms is preferred. Moreover, the aromatic heterocyclic group can be condensed with other aromatic heterocyclic groups or other aromatic hydrocarbon cyclic groups.

[0364] As an aliphatic saturated hydrocarbon group with 4 or more carbon atoms, it can be any of the structures represented by straight chain, branched chain, cyclic, or combinations thereof.

[0365] 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.

[0366] 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.

[0367] Furthermore, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0368] [The repeating unit represented by equation (4)]

[0369] Resin A may contain repeating units represented by formula (4).

[0370] The repeating unit corresponding to the repeating unit represented by equation (1-1) is considered not to correspond to the repeating unit represented by equation (4).

[0371] [Chemical Formula 42]

[0372]

[0373] In equation (4), R 131 R represents a divalent organic group. 132 It represents a tetravalent organic group.

[0374] R 131 This indicates a divalent organic group. As R... 131 Examples of groups described in paragraphs 0042 to 0053 of Japanese Patent Application Publication No. 2023-003421 may be cited. These descriptions are incorporated into this specification.

[0375] R 132 This indicates a tetravalent organic group. As R... 132 Compounds described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421 may be listed. These descriptions are incorporated into this specification.

[0376] When resin A is polyimide, the content of the repeating unit represented by formula (1-1) relative to the total mass of resin A 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.

[0377] When resin A is polyimide, the total content of the repeating units represented by formula (1-1) and formula (4) relative to the total mass of resin A 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.

[0378] Furthermore, when resin A 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.

[0379] When resin A 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.

[0380] [The repeating unit represented by equation (XA)]

[0381] Resin A can be a resin containing repeating units represented by the following formula (XA).

[0382] [Chemical Formula 43]

[0383]

[0384] In formula (XA), XX1 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).

[0385] 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.

[0386] 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 a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2-, and -C(CH3)2-.

[0387] In formula (XA), R X1 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.

[0388] 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.

[0389] 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.

[0390] In formula (XA), R 123 Hydrogen atoms are preferred.

[0391] [The repeating unit represented by equation (1-4)]

[0392] Resin A preferably contains repeating units represented by the following formulas (1-4).

[0393] [Chemical Formula 44]

[0394]

[0395] In equation (1-4), 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 a protected amino group. 1 Let each of the groups represented by equation (R-1) above be independent, and let n and m be independent integers from 0 to 4. 1 and J 2 Each can be an independent hydrogen atom or a monovalent organic group.

[0396] In equation (1-4), X 1 Y 1 W 1 V 1 R 1 The preferred methods for n and m are the same as those for X in equation (1-1). 1 Y 1 W 1 V 1 R 1 The preferred methods for n and m are the same. Furthermore, in equation (1-4), the method where n and m are 0 is also one of the preferred methods of the present invention.

[0397] In equation (1-4), J 1 and J 2 Each is independently a hydrogen atom or a monovalent organic group, preferably both are monovalent organic groups, and more preferably both are monovalent organic groups having an olefinic unsaturated bond.

[0398] Examples of monovalent organic groups having olefinic unsaturated bonds include those having vinyl, allyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, or maleimide groups, with those having (meth)acryloyloxy being preferred.

[0399] Furthermore, resin A may further include repeating units represented by formula (4-1) described later.

[0400] [The repeating unit represented by equation (1-5)]

[0401] Furthermore, resin A may contain repeating units represented by the following formulas (1-5).

[0402] [Chemical Formula 45]

[0403]

[0404] In equation (1-5), 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).

[0405] In equation (1-5), X X1 Y X1 R X1 n, m, W X1 R 123 and Q 1 The preferred method is the same as X in the above formula (XA). X1 Y X1 R X1 n, m, W X1 R 123 and Q 1 The preferred method is the same.

[0406] The weight-average molecular weight (Mw) of resin A is preferably 3,000 to 100,000.

[0407] 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.

[0408] 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.

[0409] 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 it to such a relatively low molecular weight, resolution can be improved.

[0410] The number average molecular weight (Mn) of resin A is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000.

[0411] The molecular weight dispersion of resin A is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersion is not particularly limited, 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.

[0412] In this specification, the dispersion of molecular weight is a value calculated by weight-average molecular weight / number-average molecular weight.

[0413] When the resin composition contains multiple resins as resin A, the weight-average molecular weight, number-average molecular weight, and dispersibility of at least one resin are preferably within the above-mentioned ranges. The weight-average molecular weight, number-average molecular weight, and dispersibility calculated when the multiple resins are considered as a single resin are also preferably within the above-mentioned ranges.

[0414] When resin A is polyimide, from the viewpoint of the resulting 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, and 100% or less is acceptable.

[0415] Furthermore, when resin A is polyimide, the content of imide structure in resin A 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.

[0416] When resin A is a polyimide precursor, its imidization rate is preferably less than 70%, more preferably 30% or more, and even more preferably 20% or more. The lower limit of the above imidization rate is not particularly limited, as long as it is 0% or more.

[0417] In this specification, the imidization rate is determined, for example, by the following method.

[0418] The infrared absorption spectrum of the resin was measured, and the absorption peak originating from the imide structure, i.e., 1377 cm⁻¹, was determined. -1 The peak intensity P1 near the resin was determined. Next, the resin was heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again, with the peak intensity at 1377 cm⁻¹ calculated. -1 The nearby peak intensity P2. The obtained peak intensities P1 and P2 can be used to determine the imidization rate of a specific resin according to the following formula.

[0419] Imidification rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0420] [Method for manufacturing resin A]

[0421] Resin A can be obtained, for example, by reacting tetracarboxylic dianhydride with diamine at low temperature; by reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamic acid, and then esterifying it using a condensing agent or an alkylating agent; by obtaining an ester compound (e.g., diester) from tetracarboxylic dianhydride and alcohol, and then reacting it in the presence of diamine and a condensing agent; and by obtaining an ester compound (e.g., diester) from tetracarboxylic dianhydride and alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting it with diamine, etc. Of the above manufacturing methods, the following method is more preferred: obtaining an ester compound (e.g., diester) from tetracarboxylic dianhydride and alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting it with diamine.

[0422] 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.

[0423] 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.

[0424] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0425] Furthermore, when a polyimide is desired as resin A, it can be synthesized using the following methods: a method for completely imidizing the resin obtained by the above method using a known imidization reaction; a method for stopping the imidization reaction midway and introducing a portion of imide groups; and a method for introducing a portion of imide groups by mixing the fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0426] In the method for manufacturing resin A, an organic solvent is preferably used during the reaction. The organic solvent can be one type or two or more types.

[0427] As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (Diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0428] In the manufacturing method of resin A, it is preferable to add an alkaline compound during the reaction. The alkaline compound can be one type or two or more types.

[0429] Basic compounds can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0430] -End- Capping Agent-

[0431] In the manufacturing method of resin A, to further improve storage stability, it is preferable to end-cap the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin end of resin A. When end-capping the carboxylic anhydride and anhydride derivative remaining at the resin end, end-capping agents include monools, phenols, thiols, thiophenols, and monoamines. In terms of reactivity and film stability, monools, phenols, and monoamines are more preferred. Preferred monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, 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-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-5-aminonaphthalene. 2-Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different end groups can be introduced by reacting various end-capping agents.

[0432] Furthermore, when capping the amino groups at the resin ends, compounds having functional groups capable of reacting with the amino groups can be used for capping. Preferred capping agents for the amino groups include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides 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, neopentanoyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0433] Furthermore, by bonding a capping material with a specific substituent A-1 to the end of the resin, the specific substituent A-1 can also be introduced into the resin.

[0434] 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).

[0435] [Chemical Formula 46]

[0436]

[0437] In equation (T-1), W 1 V represents an organic group with 4 or more carbon atoms. 1 This indicates an amino group that can be protected.

[0438] 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.

[0439] -Solid precipitation-

[0440] The method for manufacturing resin A 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, and the polymer component is precipitated out, thereby precipitating as a solid and drying it to obtain resin A. To improve purity, the operations of re-dissolving, re-precipitating, and drying resin A can be repeated. The method may further include a step of removing ionic impurities using an ion exchange resin.

[0441] [Specific example]

[0442] Specific examples of resin A include SA-1 to SA-6 in the embodiments described later, but the present invention is not limited thereto.

[0443] 〔content〕

[0444] The content of resin A in the resin composition of the present invention, relative to the total solids content of the resin composition, 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. Furthermore, the content of resin A in the resin composition of the present invention, relative to the total solids content of the resin composition, 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.

[0445] <Other Resins>

[0446] The resin composition of the present invention may contain other resins (hereinafter also referred to as "other resins") that are different from the above-described resin A.

[0447] Other resins that differ from resin A and correspond to polyimide precursors, polyimide, polybenzoxazole precursor, polybenzoxazole, polyamide-imide precursor, polyamide-imide, phenolic resin, polyamide, epoxy resin, polysiloxane, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, amine ester resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins can be listed.

[0448] As other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazole, polyamide-imide precursors, and polyamide-imides, the compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355 are listed. The above descriptions are incorporated herein by reference.

[0449] The following describes resins B and C, which are resins that correspond to other resins.

[0450] <Resin B>

[0451] The photosensitive resin composition of the present invention may further contain resin B, which is a resin having a structure A, i.e., structure A, having two or more groups selected from protected carboxyl groups and carboxylic acid ester groups linked by a linking group with a chain length of 2 to 4.

[0452] Resin B is preferably a resin having a specific substituent A-2, which will be described later. Preferred forms of the specific substituent A-2 are described later.

[0453] Resin B preferably contains repeating units represented by formula (1-2) or formula (1-3) below, and more preferably contains repeating units represented by formula (1-2).

[0454] [Chemical Formula 47]

[0455]

[0456] In equation (1-2), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 2 Let W represent the structure represented by the following equation (R-1) independently. 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 The symbol represents an organic group, where n and m independently represent integers from 0 to 4, and n+m is 1 or higher.

[0457] 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.

[0458] [Chemical Formula 48]

[0459]

[0460] 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.

[0461] In equation (3-2), R C1 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. C2The 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.

[0462] 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.

[0463] 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.

[0464] In equation (1-2), G 1 and G 2 The preferred method and R in the following formula (CA-1) C1 The preferred method is the same.

[0465] 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.

[0466] In equation (1-3), W 3 Preferably, it is a group represented by a single bond or an aliphatic hydrocarbon group, an aromatic group, or a combination thereof.

[0467] In equation (3-1), R C1 R C2 and the preferred method of a and R in the following formula (CA-1) C1 R C2 The preferred method for a is the same.

[0468] In equation (3-2), R C1 R C2 and the preferred method of a and R in the following formula (CA-2) C1 R C2 The preferred method for a is the same.

[0469] Resin B may contain repeating units represented by the above formula (4).

[0470] The content of resin B relative to the total solids content of the photosensitive 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 B is present, the lower limit of the above content is preferably 5% by mass or more, more preferably 10% by mass or more.

[0471] <Resin C>

[0472] The resin composition of the present invention preferably further contains resin C, which is a resin containing repeating units represented by formula (4-1) or formula (4-2) and not belonging to resin A.

[0473] [Chemical Formula 49]

[0474]

[0475] In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each can be independently a 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.

[0476] [Chemical Formula 50]

[0477]

[0478] 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 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.

[0479] 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.

[0480] In equation (4-1), R 1 and R 2 Each is independently a hydrogen atom or a monovalent organic group, preferably both are monovalent organic groups, and more preferably both are monovalent organic groups having an olefinic unsaturated bond.

[0481] Examples of monovalent organic groups having olefinic unsaturated bonds include those having vinyl, allyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, or maleimide groups, with those having (meth)acryloyloxy being preferred.

[0482] 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.

[0483] In equation (4-2), R 1 The preferred method for the polymeric groups in resin A is the same as the preferred method for the polymeric groups in resin A.

[0484] Here, R 1 Preferably, it is a group represented by the above formula (R-1).

[0485] 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.

[0486] When the resin composition of the present invention contains other resins, the content of the 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.

[0487] 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 solid content of the resin composition.

[0488] As a preferred embodiment of the resin composition of the present invention, it is also possible to set the content of other resins to be low. In the above embodiment, 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 still more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, and 0% by mass or more is acceptable.

[0489] 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 above-mentioned range.

[0490] <Compounds with structure A (Compound B)>

[0491] The resin composition of the present invention contains compound B, which has a structure A consisting of two or more groups selected from carboxylic acid ester groups and protected carboxyl groups linked by a linking group with a chain length of 2 to 4, and has a molecular weight of 2,000 or less.

[0492] Hereinafter, the group containing structure A will also be referred to as the specific substituent A-2.

[0493] The carboxylic acid ester group is -C(=O)O - The group represented. The relative cation to the anionic moiety described above is not particularly limited; examples include protons, Na+, etc. + K + Metal cations, ammonium cations, imine cations, etc.

[0494] As a protected carboxyl group in structure A, an unsubstituted carboxyl group is preferred.

[0495] Furthermore, the carboxyl group to be protected is preferably alkoxycarbonyl or aryloxycarbonyl, and more preferably tert-butoxycarbonyl.

[0496] 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 a group generates an amino group. In this method, the part described as amino is replaced with carboxyl group.

[0497] Here, the linking chain length in structure A refers to the minimum number of atoms contained in structure A that exist between two groups selected from the carboxylic acid ester group and the protected carboxyl group contained in structure A.

[0498] Compound B preferably contains a group represented by any of the following formulas (S-1) to (S-4) as a structure containing the above structure A.

[0499] [Chemical Formula 51]

[0500]

[0501] In equations (S-1) to (S-4), R S1 Represents -OH, -O - or -OR S2 R S2Indicates 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.

[0502] In equations (S-1) to (S-4), R S1 Preferably -OH or -O - R S1 -O - The relative cations at that time are not particularly limited, and examples include protons and Na+. + K + Metal cations, ammonium cations, imine cations, etc.

[0503] 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.

[0504] Cy is preferably a cycloalkane structure, and more preferably a cyclohexane ring structure.

[0505] n is preferably 1.

[0506] L 1 Preferably, it is a single bond, methylene, or ethylene, and more preferably a single bond.

[0507] Furthermore, compound B preferably contains a group represented by any one of the following formulas (CA-1) or (CA-2) as a specific substituent A-2.

[0508] [Chemical Formula 52]

[0509]

[0510] 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 sum of a and b is less than 4.

[0511] In equation (CA-2), R C1 Represent -OH and -O independently, respectively. - or -OR C R C R represents an organic group. C2The 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 sum of a and b is less than 10.

[0512] In equation (CA-1), R C1 Preferably -OH or -O - R C1 -O - The relative cations at that time are not particularly limited, and examples include protons and Na+. + K + Metal cations, ammonium cations, imine cations, etc.

[0513] When R C1 For -OR C At that time, R C Preferably alkyl or aryl, more preferably alkyl with 1 to 4 carbon atoms, and even more preferably tert-butyl.

[0514] 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.

[0515] In formula (CA-1), a is preferably 0 or 1.

[0516] In formula (CA-1), b is preferably 1.

[0517] 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.

[0518] Furthermore, compound B preferably has a mesocrystalline framework.

[0519] In this specification, a mesocrystalline framework refers to a structure containing polycyclic aromatic hydrocarbons or two or more aromatic rings, preferably a structure with rigidity and orientation.

[0520] Regarding compound B, as a mesocrystalline framework, a structure in which two or more aromatic rings are connected by single bonds, -O-, -C(=O)O-, or -NHC(=O)- is preferred.

[0521] As an aromatic ring, an aromatic hydrocarbon ring is preferred, a naphthalene ring or a benzene ring is more preferred, and a benzene ring is even more preferred.

[0522] Examples of preferred mesocrystalline frameworks are shown below, but the invention is not limited to these. In the following structures, * indicates bonding sites with other structures.

[0523] [Chemical Formula 53]

[0524]

[0525] The compound B is preferably the compound represented by the following formula (B-1).

[0526] [Chemical Formula 54]

[0527]

[0528] In equation (B-1), X 3 J represents a tetravalent organic group. 1 and J 2 -O- or -NR can be represented independently. N -, R N R represents a hydrogen atom or a hydrocarbon group. 3 and R 4 Each independently represents a monovalent organic group, G + They can be used to represent hydrogen cations or ammonium cations independently.

[0529] In equation (B-1), G + It can dissociate and exist as a cation, or it can react with O in formula (B-1). - Ionic bonding.

[0530] In equation (B-1), X 3 The preferred method is the same as X in equation (1-1) above. 1 The preferred method is the same.

[0531] In equation (B-1), J 1 and J 2 Each is preferably -O-, independently.

[0532] In equation (B-1), when J 1 and J 2 At least one of them is -NR N - At that time, R N Hydrogen atoms are preferred.

[0533] In equation (B-1), R 3 and R 4 Each component is preferably a hydrocarbon group, and more preferably an alkyl group.

[0534] The molecular weight of compound B is preferably 230 to 1,500, more preferably 300 to 1,000.

[0535] The number of structures A in compound B is preferably 2 or more, more preferably 2 to 4, and even more preferably 2.

[0536] The content of structure A in 1g of compound B is preferably 1 to 10 mmol / g, more preferably 1.5 to 9.0 mmol / g, and even more preferably 2.0 to 9.0 mmol / g.

[0537] The content of compound B relative to the total solids content of the resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

[0538] <Compounds with protected amino groups (Compound C)>

[0539] The photosensitive resin composition of the present invention may contain compound C having two or more protected amino groups and a molecular weight of less than 2,000.

[0540] The preferred manner for the protected amino group in compound C is the same as that for the protected amino group in resin A described above.

[0541] For example, protected amino groups include tert-butoxycarbonylamino, 9-fluorenylmethoxycarbonylamino, and alkoxycarbonylamino, urea, etc., which may have substituents.

[0542] The above compound C preferably has an aromatic group.

[0543] Furthermore, the amino group in compound C, or the amino group derived from the protected amino group, is preferably an aromatic amino group.

[0544] In this invention, aromatic amino refers to a structure in which the aromatic ring and the amino group are bonded by a single bond without a linking group.

[0545] Compound C is preferably the compound represented by the following formula (C-1).

[0546] [Chemical Formula 55]

[0547]

[0548] In formula (C-1), L B1 Q represents an n-valent organic group. 1 The symbol represents a hydrogen atom or a group represented by the above formula (2-2), where n represents an integer greater than 2.

[0549] In formula (C-1), L B1 Preferably, it is a hydrocarbon group, a heterocyclic group, or these groups combined with a compound selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N A group formed by bonding at least one of the groups in -. R N The preferred method is as described above.

[0550] Examples of the aforementioned hydrocarbon groups include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds.

[0551] The following records L B1 This is a preferred embodiment, but the invention is not limited thereto. In the following structures, * indicates the bonding site with the nitrogen atom in formula (C-1).

[0552] [Chemical Formula 56]

[0553]

[0554] In equation (C-1), Q 1 The preferred manner of the group represented by formula (2-2) is the same as that of Q in formula (2-1) above. 1 The preferred method is the same as that for the groups represented by formula (2-2).

[0555] In formula (C-1), n ​​is preferably an integer from 2 to 10, more preferably an integer from 2 to 4, even more preferably 2 or 3, and especially preferably 2.

[0556] The molecular weight of compound C is preferably 230 to 1,500, more preferably 300 to 1,000.

[0557] The number of protected amino groups in compound C is preferably 2 or more, more preferably 2 to 4, and even more preferably 2.

[0558] The content of the protected amino group in 1g of compound B is preferably 1 to 10 mmol / g, more preferably 1.5 to 9.0 mmol / g, and even more preferably 2.0 to 7.0 mmol / g.

[0559] The content of compound C relative to the total solids content of the photosensitive resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

[0560] <Polymerizing compounds>

[0561] The resin composition of the present invention preferably contains a polymerizable compound.

[0562] The melting point of the polymerizable compound is preferably below 25°C.

[0563] By setting the melting point below 25°C, the coating film flows easily during drying and heating, thereby improving the flatness of the cured product.

[0564] In particular, from the viewpoint of reducing the dielectric constant of the cured product, as a polymerizable compound, it is preferable to contain 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.

[0565] In this specification, the ClogP value of the compound is based on the following definition.

[0566] The octanol-water partition coefficient (logP value) can usually be determined by the flask shaking 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 or empirical methods instead of actual measurement. Known computational methods include 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)). In this invention, Crippen's fragmentation method is used (J. Chem. Inf. Comput. Sci., 27, 21 (1987)).

[0567] The ClogP value is obtained by calculating the common logarithm logP of the partition coefficient P of 1-octanol and water. Regarding the method or software used in calculating the ClogP value, well-known methods or software can be used; unless otherwise stated, the ClogP program in the system PCModels assembled by Daylight Chemical Information Systems is used in this invention.

[0568] The ClogP value is preferably 4.0 or higher, and more preferably 6.0 or higher.

[0569] Furthermore, the upper limit of the above ClogP value is not particularly limited, but is preferably below 15.0.

[0570] The aromatic ring structure described above can be an aromatic hydrocarbon ring or an aromatic heterocycle, preferably an aromatic hydrocarbon ring, and more preferably containing a benzene ring. Furthermore, from the viewpoint of reducing the dielectric constant of the cured product, a condensation ring such as a fluorene ring is preferred.

[0571] 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.

[0572] Examples of aliphatic ring structures with 6 or more carbon atoms include monocyclic rings such as cyclohexane, bicyclic pentane, and tricyclic rings [5.2.1.0].2,6 [Decane ring and other polycyclic compounds, preferably polycyclic compounds.]

[0573] 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 having 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 even more preferred.

[0574] 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.

[0575] Specific examples of polymeric compounds with a ClogP value of 3.0 or higher include the following compounds, but are not limited to them.

[0576] [Chemical Formula 57]

[0577]

[0578] [Chemical Formula 58]

[0579]

[0580] [Chemical Formula 59]

[0581]

[0582] As polymerizable compounds, examples include polymerizable compounds (free radical crosslinking agents) or other crosslinking agents that have free radical polymerizable groups.

[0583] [Free radical crosslinking agent]

[0584] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0585] 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.

[0586] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0587] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may have three or more olefinic unsaturated bonds.

[0588] As for the above-mentioned compounds having two or more olefinic unsaturated bonds, compounds having 2 to 15 olefinic unsaturated bonds are preferred, compounds having 2 to 10 olefinic unsaturated bonds are more preferred, and compounds having 2 to 6 olefinic unsaturated bonds are even more preferred.

[0589] From the viewpoint of the film strength of the resulting pattern (cured product), the resin composition of the present invention preferably contains a compound having two olefinic unsaturated bonds and the above-mentioned compound having three or more olefinic unsaturated bonds.

[0590] 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.

[0591] 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 polyvalent amine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or thioalkyl groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Moreover, 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, and substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are even more preferred. Furthermore, as other examples, compounds that can replace the aforementioned unsaturated carboxylic acids, such as unsaturated phosphonic acids, vinylbenzene derivatives like styrene, vinyl ethers, allyl ethers, etc., can 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.

[0592] The free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at normal pressure. Examples of compounds having a boiling point of 100°C or higher at normal pressure include those described in paragraph 0203 of International Publication No. 2021 / 112189. This information is included in this specification.

[0593] Other preferred free radical crosslinking agents besides those mentioned above include free radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0594] As free radical crosslinking agents, preferred are dinepentylenetetroxide triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)), dinepentylenetetroxide penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A-DPH (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)) and their structures in which the (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. They can also use their oligomer types.

[0595] Commercially available free radical crosslinking agents include, for example, tetrafunctional acrylates SR-494 having four ethoxide chains, difunctional methacrylates SR-209, 231, and 239 having four ethoxide chains (all manufactured by Sartomer Company, Inc.), hexafunctional acrylates DPCA-60 having six pentylene oxide chains, trifunctional acrylates TPA-330 having three isobutyrite chains (all manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (all manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, and UA-7200 (all manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and DPHA-40H (Nippon Kayaku Co., Ltd.). Manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOFCORPORATION.), etc.

[0596] As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, and urethane compounds having an ethylene oxide backbone 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 free radical crosslinking agents.

[0597] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. Free radical crosslinking agents with acid groups are preferably esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and more preferably free radical crosslinking agents that have acid groups by reacting the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. Particularly preferred are compounds in which the aliphatic polyhydroxy compound, having an acid group by reacting the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, is a pentaerythritol or dipentaerythritol. Commercially available examples include, for instance, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO.,LTD.

[0598] 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. If 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 acid value was determined according to the description in JIS K 0070:1992.

[0599] As a free radical crosslinking agent, a free radical crosslinking agent having at least one selected from urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is preferred.

[0600] Furthermore, as a free radical crosslinking agent, the aforementioned crosslinking agent U or a free radical crosslinking agent having an isocyanuric ring structure is preferred, and a free radical crosslinking agent having a urea bond or an isocyanuric ring structure is more preferred.

[0601] The presence of crosslinking agent U in the resin composition can sometimes improve chemical resistance, resolution, and other properties.

[0602] The mechanism by which the above effects are achieved is not yet clear, but it is believed that, for example, during curing by heating, a portion of the crosslinking agent U thermally decomposes to produce amines, which in turn promote the cyclization of cyclized resin precursors such as polyimide precursors.

[0603] The crosslinking agent U may have only one urea bond or a carbamate bond, or it may have more than one urea bond and more than one carbamate bond, or it may have no carbamate bond but have more than two urea bonds, or it may have no urea bond but have more than two carbamate bonds.

[0604] The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0605] When the crosslinking agent U does not have urethane bonds, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0606] When the crosslinking agent U does not have urea bonds, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0607] The free radical polymerizable groups in the crosslinking agent U are not particularly limited, and may include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0608] When the crosslinking agent U has more than two free radical polymerizable groups, the structures of each free radical polymerizable group can be the same or different.

[0609] The number of free radical polymerizable groups in the crosslinking agent U can be only 1 or more than 2, preferably 1 to 10, more preferably 1 to 6, and especially preferably 1 to 4.

[0610] The free radical polymerizable group value (mass of compound per mole of free radical polymerizable groups) in crosslinking agent U is preferably 150-400 g / mol.

[0611] From the viewpoint of the chemical resistance of the cured product, the lower limit of the free radical polymerizability group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more.

[0612] From the viewpoint of reproducibility, the upper limit of the above-mentioned free radical polymerizability group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, and especially preferably 300 g / mol or less.

[0613] Among these, the polymerizability value of crosslinking agent U is preferably 210–400 g / mol, more preferably 220–400 g / mol.

[0614] The crosslinking agent U is preferably represented by, for example, the structure of the following formula (U-1).

[0615] [Chemical Formula 60]

[0616]

[0617] In equation (U-1), R U1 A is a hydrogen atom or a monovalent organic group, and A is -O- or -NR. N -, R N Z is a hydrogen atom or a monovalent organic group. U1 Z is an m-valent organic group. U2 X is an organic group with a valence of n+1, X is a free radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 1.

[0618] R U1 Preferably, it is a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0619] R N Preferably, it is a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0620] Z U1 Preferably, the radicals are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, or -NR. N - or groups formed by two or more of them, more preferably hydrocarbon groups or hydrocarbon groups and groups selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - A group formed by bonding at least one of the groups in -.

[0621] The aforementioned hydrocarbon group is preferably a hydrocarbon group with 20 or fewer carbon atoms, more preferably a hydrocarbon group with 18 or fewer carbon atoms, and even more preferably a hydrocarbon group with 16 or fewer carbon atoms. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds. N It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.

[0622] Z U2Preferably, the radicals are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, or -NR. N - or groups formed by two or more of them, more preferably hydrocarbon groups or hydrocarbon groups and groups selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - A group formed by bonding at least one of the groups in -.

[0623] As the aforementioned hydrocarbon group, examples of those in Z can be listed. U1 For groups that are the same as those listed, the preferred method is also the same.

[0624] X is not particularly limited and may include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0625] n is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, even more preferably 1 or 2, and especially preferably 1.

[0626] m is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0627] The crosslinking agent U preferably has at least one of hydroxyl, alkoxide, amide and cyano groups.

[0628] From the viewpoint of the chemical resistance of the obtained cured film, the hydroxyl group can be an alcoholic hydroxyl group or a phenolic hydroxyl group, preferably an alcoholic hydroxyl group.

[0629] From the viewpoint of the chemical resistance of the obtained cured film, alkene oxides with 2 to 20 carbon atoms are preferred, alkene oxides with 2 to 10 carbon atoms are more preferred, alkene oxides with 2 to 4 carbon atoms are even more preferred, ethylene or propylene oxide is even more preferred, and ethylene is particularly preferred.

[0630] The alkene oxide can be included in the crosslinking agent U as a polyalkene oxide. In this case, the number of repetitions of the alkene oxide is preferably 2 to 10, more preferably 2 to 6.

[0631] The amide group refers to -C(=O)-NR N - The key it represents. R N As described above, when the crosslinking agent U has an amide group, the crosslinking agent U can use the amide group as, for example, RC(=O)-NR. N -* indicates the group or *-C(=O)-NR NThe group represented by -R is included. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0632] The crosslinking agent U may have two or more structures selected from hydroxyl, alkoxy (polyalkoxy when constituting polyalkoxy), amide and cyano groups in the molecule, and preferably has only one structure in the molecule.

[0633] The aforementioned hydroxyl, alkeneoxy, amide, and cyano groups can be present at any position in the crosslinking agent U. From the viewpoint of drug resistance, it is also preferred that at least one of the aforementioned hydroxyl, alkeneoxy, amide, and cyano groups in the crosslinking agent U is linked to at least one free radical polymerizable group contained in the crosslinking agent U through a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1").

[0634] In particular, when the crosslinking agent U contains only one free radical polymerizable group, it is preferable that the free radical polymerizable group contained in the crosslinking agent U is linked to at least one of the groups selected from hydroxyl, alkeneoxy, amide and cyano groups through a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").

[0635] When the crosslinking agent U contains an alkene group (or a polyalkene group if constituting a polyalkene group) and has the aforementioned linking group L2-1 or L2-2, the structure bonded to the alkene group (or a polyalkene group if constituting a polyalkene group) on the side opposite to linking group L2-1 or L2-2 is not particularly limited, and is preferably a group represented by a hydrocarbon group, a free radical polymerizable group, or a combination thereof. As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, more preferably a hydrocarbon group with 18 or fewer carbon atoms, and even more preferably a hydrocarbon group with 16 or fewer carbon atoms. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds. Furthermore, the preferred manner for the free radical polymerizable group is the same as the preferred manner for the free radical polymerizable group in the aforementioned crosslinking agent U.

[0636] When the crosslinking agent U contains an amide group and has the aforementioned linking group L2-1 or L2-2, the structure on the side of the amide group opposite to the linking group L2-1 or L2-2 is not particularly limited, and is preferably a group represented by a hydrocarbon group, a free radical polymerizable group, or a combination thereof. As the aforementioned hydrocarbon group, it is preferably a hydrocarbon group with 20 or fewer carbon atoms, more preferably a hydrocarbon group with 18 or fewer carbon atoms, and even more preferably a hydrocarbon group with 16 or fewer carbon atoms. Furthermore, examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds. The preferred manner for the free radical polymerizable group is the same as the preferred manner for the free radical polymerizable group in the crosslinking agent U. Furthermore, in the above manner, the carbon atom side of the amide group may be bonded to the linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or L2-2.

[0637] Of these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, the crosslinking agent U having hydroxyl groups is preferred.

[0638] From the viewpoint of compatibility with resin A, crosslinking agent U preferably contains aromatic groups.

[0639] The aromatic groups mentioned above are preferably directly bonded to the urea bonds or urethane bonds contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.

[0640] The aromatic group can be an aromatic hydrocarbon group or an aromatic heterocyclic group, or it can be a structure that forms a condensation ring, preferably an aromatic hydrocarbon group.

[0641] As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group with 6 to 20 carbon atoms is more preferred, and a group formed by removing 2 or more hydrogen atoms from the benzene ring structure is even more preferred.

[0642] As the aforementioned aromatic heterocyclic group, a 5-membered or 6-membered aromatic heterocyclic group is preferred. Examples of aromatic heterocycles in such aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetraazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings can be further condensed with other rings such as indole and benzimidazole.

[0643] Nitrogen, oxygen, or sulfur atoms are preferred as heteroatoms contained in the aforementioned aromatic heterocyclic groups.

[0644] The aforementioned aromatic groups are preferably included, for example, in a linking group that links two or more free radical polymerizable groups and contains a urea bond or a urethane bond, or in a linking group that links at least one of the above-mentioned groups selected from hydroxyl, alkoxy, amide, and cyano groups to at least one free radical polymerizable group contained in the crosslinking agent U.

[0645] The number of atoms (linking chain length) between the urea bond or urethane bond in the crosslinking agent U and the free radical polymerizable group is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.

[0646] When the crosslinking agent U contains two or more urea bonds or urethane bonds, contains two or more free radical polymerizable groups, or contains two or more urea bonds or urethane bonds and two or more free radical polymerizable groups, the smallest number of atoms (linking chain length) between the urea bonds or urethane bonds and the free radical polymerizable groups is within the above range.

[0647] In this specification, "the number of atoms (linkage chain length) between the urea bond or urethane bond and the polymerizable group" refers to the shortest (minimum number of atoms) atomic chain in the path that links the two atoms or groups of atoms that are the linking objects. For example, in the structure represented by the following formula, the number of atoms (linkage chain length) between the urea bond and the free radical polymerizable group (methacryloyloxy) is 2.

[0648] [Chemical Formula 61]

[0649]

[0650] [Axis of symmetry]

[0651] The crosslinking agent U is preferably a compound without a symmetry axis.

[0652] Crosslinking agent U lacks a symmetry axis, meaning it does not possess an axis that allows it to produce molecules identical to the original molecule by rotating the entire compound; thus, it is a compound that is left-right asymmetrical. Furthermore, when representing the structural formula of crosslinking agent U on paper, "crosslinking agent U lacks a symmetry axis" means that its structural formula cannot be represented in a form with a symmetry axis.

[0653] It is believed that because the crosslinking agent U does not have a symmetry axis, the aggregation of crosslinking agents U in the composite film is suppressed.

[0654] [Molecular weight]

[0655] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0656] The method of manufacturing crosslinking agent U is not particularly limited. For example, it can be obtained by reacting a compound having a free radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxyl or an amino group.

[0657] The following are specific examples of crosslinking agent U, but crosslinking agent U is not limited to these.

[0658] [Chemical Formula 62]

[0659]

[0660] [Chemical Formula 63]

[0661]

[0662] [Chemical Formula 64]

[0663]

[0664] As a free radical crosslinking agent with an isocyanuric ring structure, it is preferably a compound having 2 or 3 free radical polymerizable groups, more preferably a compound having 3.

[0665] Furthermore, examples of free radical crosslinking agents having an isocyanuric ring structure include triisocyanurate (2-acryloyloxyethyl ester), triisocyanurate (2-methacryloyloxyethyl ester), EO isocyanurate (ethylene oxide) modified diacrylate, EO isocyanurate modified triacrylate, and compounds with the following structures, but are not limited to these. In the following structures, n independently represents an integer from 1 to 20, and R represents a divalent linking group.

[0666] [Chemical Formula 65]

[0667]

[0668] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses difunctional methacrylates or acrylates.

[0669] 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, neopentyl glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, and 3-methyl-1,5-pentanediol can be used. Diacrylates, 1,6-hexanediol diacrylates, 1,6-hexanediol dimethacrylates, dimethylol-tricyclodecane diacrylates, dimethylol-tricyclodecane dimethacrylates, bisphenol A EO (ethylene oxide) adduct diacrylates, bisphenol A EO adduct dimethacrylates, bisphenol A PO (propylene oxide) adduct diacrylates, bisphenol A PO adduct dimethacrylates, 2-hydroxy-3-acryloyloxypropyl methacrylates, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. These can be mixed in two or more as needed.

[0670] Additionally, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of approximately 200 for the polyethylene glycol chain.

[0671] 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 a 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 with a boiling point of 100°C or higher at atmospheric pressure are also preferred.

[0672] In addition, as free radical crosslinking agents with two or more functions, examples include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0673] 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.

[0674] A single free radical crosslinking agent can be used alone, or two or more can be used in combination. When two or more are used together, their combined dosage is preferably within the range mentioned above.

[0675] [Other crosslinking agents]

[0676] The resin composition of the present invention preferably also contains other crosslinking agents that are different from the free radical crosslinking agents described above.

[0677] 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 the photosensitive acid generator or photobase 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.

[0678] 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.

[0679] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0680] [Polymerization initiator]

[0681] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator can be a thermal polymerization initiator or a photopolymerization initiator, and a photopolymerization initiator is particularly preferred.

[0682] 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 sensitive to light in the ultraviolet to visible regions is preferred. Furthermore, it can also be an active agent that reacts with a photoexcited sensitizer to generate active free radicals.

[0683] The photoradical polymerization initiator preferably contains at least one initiator having a wavelength range 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. The molar absorptivity of a compound can be measured using known methods. For example, it is preferably determined using a UV-Vis spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0684] 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, azido compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For detailed information on these compounds, 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 are examples of peroxide-based photopolymerization initiators described in Japanese Patent Application Publication No. 2014-130173 (paragraphs 0065 to 0111), Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol.19, No.3, 2019, international publication No. 2018 / 221177, international publication No. 2018 / 110179, Japanese Patent Application Publication No. 2019-043864, Japanese Patent Application Publication No. 2019-044030, and Japanese Patent Application Publication No. 2019-167313, which are incorporated into this specification.

[0685] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) may also be preferred.

[0686] 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.

[0687] 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.

[0688] 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.

[0689] As an aminoacetophenone-based initiator, an acylphosphine oxide-based initiator, or a metallocene compound, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 may preferably be used. This content is incorporated herein by reference.

[0690] Oxime compounds are more preferably used as photoradical polymerization initiators. By using oxime compounds, exposure tolerance can be further improved more effectively. Oxime compounds are preferred because they offer a wide exposure tolerance (exposure margin) and also act as photocuring accelerators.

[0691] 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.

[0692] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))butane-2-one, 3-(acetoxy(imino))butane-2-one, 3-(propionyloxy(imino))butane-2-one, 2-(acetoxy(imino))pentane-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butane-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one, etc. In resin compositions, oxime compounds are particularly preferred as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have an intramolecular linking group >C=NOC(=O)-.

[0693] [Chemical Formula 66]

[0694]

[0695] 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 Electronic Materials CO.,LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Furthermore, oxime compounds with the following structures can also be used.

[0696] [Chemical Formula 67]

[0697]

[0698] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring, oxime compounds having at least one benzene ring forming a naphthalene ring skeleton, and oxime compounds having fluorine atoms can also be used.

[0699] Furthermore, it is also possible to use oxime compounds with nitro groups, oxime compounds with benzofuran skeletons, and oxime compounds with hydroxyl substituents bonded to a carbazole skeleton as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359. These contents are incorporated in this specification.

[0700] Furthermore, as a photopolymerization initiator, compounds described in paragraphs 0113 to 0117 of Japanese Patent Application Publication No. 2023-058585 can also be used. This description is incorporated in the specification of this application.

[0701] 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 contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range.

[0702] In addition, since photopolymerization initiators sometimes also function as thermal polymerization initiators, crosslinking based on photopolymerization initiators can sometimes be further promoted by heating in ovens, heating plates, etc.

[0703] [Sensitizer]

[0704] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The electronically excited sensitizer then comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., and undergoes electron transfer, energy transfer, and heating. Consequently, the thermal free radical polymerization initiator or photofree radical polymerization initiator undergoes a chemical change and decomposes, generating free radicals, acids, or bases.

[0705] As usable sensitizers, compounds such as benzophenone, mifepristone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethyl, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0706] Examples of sensitizers include mifepristone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylenepropyl dihydroindone, and p-dimethylaminophenylenepropyl dihydroindone. Aminophenylmethylene dihydroindone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethyl 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-toluenediethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0707] Furthermore, other sensitizing pigments can be used.

[0708] 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.

[0709] 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 alone, or two or more may be used in combination.

[0710] [Chain transfer agent]

[0711] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferably used.

[0712] Furthermore, the chain transfer agent can also use compounds described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0713] When the resin composition contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids of the resin composition is 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. There may be only one type of chain transfer agent or two or more types. When there are two or more types of chain transfer agents, their total content is preferably within the above-mentioned range.

[0714] Furthermore, the polymerization initiator can be a photoacid generator. Preferably, it is a photoacid generator that generates free radicals.

[0715] Specifically, the preferred compound is one that absorbs light to decompose and generate free radicals, and extracts hydrogen from the solvent or the acid-generating agent itself to generate an acid.

[0716] Examples of photoacid generators include quinone diazide compounds, oxime sulfonate compounds, organohalides, organoborates, disulfones, and onium salts, with onium salts being preferred.

[0717] Examples of onium salts include diazonium salts, phosphonium salts, sulfonium salts, and sulfonium salts.

[0718] 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.

[0719] 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 cation and anion molecules that are different molecules, 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.

[0720] [Sulfur]

[0721] In this invention, sulfonium salt refers to a salt of sulfonium cation and anion.

[0722] -sulfonium cation-

[0723] As a sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.

[0724] Furthermore, the preferred cation as a sulfonium cation is the cation represented by the following formula (103).

[0725] [Chemical Formula 68]

[0726]

[0727] In equation (103), R 8 ~R 10 Each hydrocarbon group can be represented independently.

[0728] 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.

[0729] 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, alkyl or alkoxy is preferred as a substituent, branched alkyl or alkoxy is more preferred, and branched alkyl or alkoxy with 3 to 10 carbon atoms or alkoxy with 1 to 10 carbon atoms is even more preferred.

[0730] 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.

[0731] -Anion-

[0732] 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.

[0733] [Salt]

[0734] In this invention, sulfonium salt refers to a salt of sulfonium cation and anion. Examples of anions include those identical to the anions in the aforementioned sulfonium salts, and the preferred embodiments are also the same.

[0735] -Morphine cation-

[0736] As a ferrophosphate cation, a diarylferrophosphate cation is preferred.

[0737] Furthermore, the preferred cation is the one represented by the following formula (104).

[0738] [Chemical Formula 69]

[0739]

[0740] In equation (104), R 11 and R 12 Each hydrocarbon group can be represented independently.

[0741] 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.

[0742] 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, alkyl or alkoxy is preferred as a substituent, branched alkyl or alkoxy is more preferred, and branched alkyl or alkoxy with 3 to 10 carbon atoms or alkoxy with 1 to 10 carbon atoms is even more preferred.

[0743] R 11 and R 12 The groups can be the same or different groups, but from the point of view of synthetic suitability, the same groups are preferred.

[0744] [phosphorus salt]

[0745] In this invention, a phosphonium salt refers to a salt of a phosphonium cation and anion. Examples of anions include those identical to the anions in the sulfonium salts described above, and the preferred embodiments are also the same.

[0746] -phosphonium cation-

[0747] As a phosphonium cation, a quaternary phosphonium cation is preferred, and examples include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations.

[0748] Furthermore, the preferred cation is the one represented by the following formula (105).

[0749] [Chemical Formula 70]

[0750]

[0751] In equation (105), R 13 ~R 16 Each can be used to represent a hydrogen atom or a hydrocarbon group independently.

[0752] 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.

[0753] 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, alkyl or alkoxy is preferred as a substituent, branched alkyl or alkoxy is more preferred, and branched alkyl or alkoxy with 3 to 10 carbon atoms or alkoxy with 1 to 10 carbon atoms is even more preferred.

[0754] 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.

[0755] The content of the photoacid generator relative to the total solid 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.

[0756] A photoacid generator can be used alone or in combination. When multiple generators are used in combination, the total dosage is preferably within the range mentioned above.

[0757] Furthermore, in order to impart photosensitivity to the desired light source, it is preferable to use it in combination with a sensitizer.

[0758] Furthermore, the resin composition of the present invention containing two or more polymerization initiators is also one of the preferred embodiments of the present invention.

[0759] 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.

[0760] By including photopolymerization initiators and thermal polymerization initiators (described later), exposure-based patterning can be achieved, and free radical polymerization is easily carried out during curing via the heating process described later, sometimes improving properties such as chemical resistance.

[0761] As the ratio of the photopolymerization initiator and the thermal polymerization initiator (described later), the content of the thermal polymerization initiator relative to the total content of the photopolymerization initiator and the thermal polymerization initiator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass.

[0762] By incorporating photoradical polymerization initiators and photoacid generators, performance characteristics such as resolution can sometimes be improved.

[0763] As the ratio of the photopolymerization initiator and the photoacid generator, the content of the photoacid generator relative to the total content of the photopolymerization initiator and the photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass.

[0764] [Thermal polymerization initiator]

[0765] 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 and 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.

[0766] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are included in this specification, can be cited as thermal free radical polymerization initiators.

[0767] 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 only one type or may contain two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0768] <Alkali-generating agents>

[0769] The resin composition of the present invention may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of generating alkali through physical or chemical action. Preferred alkali-generating agents include thermal alkali-generating agents and photo-alkali-generating agents.

[0770] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains an alkali-generating agent. By containing a thermal alkali-generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, thereby improving the mechanical properties and chemical resistance of the cured product, and improving the performance of, for example, the interlayer insulating film used as a rewiring layer in semiconductor packaging.

[0771] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from a base-generating agent include, for instance, secondary and tertiary amines.

[0772] The base-generating agent is not particularly limited, and known base-generating agents can be used. Examples of known base-generating agents include, for instance, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imine salts, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0773] Specific compounds that can be listed as nonionic base generators include those represented by formulas (B1), (B2), or (B3).

[0774] [Chemical Formula 71]

[0775]

[0776] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3 Each of these can be used independently to represent an organic group, halogen atom, or hydrogen atom that does not possess a tertiary amine structure. Specifically, Rb... 1 and Rb 2 It will not simultaneously become a hydrogen atom. Furthermore, Rb 1 、Rb 2 and Rb 3None of them contain a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of the trivalent nitrogen atom are covalently bonded to the carbon atoms of the hydrocarbon group. Therefore, when the carbon atom bonded to the trivalent nitrogen atom is the carbon atom constituting the carbonyl group, i.e., when it forms an amide group together with the nitrogen atom, it is not a tertiary amine structure.

[0777] In equations (B1) and (B2), Rb is preferred. 1 、Rb 2 and Rb 3 At least one of the rings contains a cyclic structure, more preferably at least two rings. The cyclic structure can be any of a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring formed by the condensation of two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0778] More specifically, Rb 1 and Rb 2 Preferably, the atoms are hydrogen atoms, alkyl groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), alkenyl groups (preferably 2-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), or aralkyl groups (preferably 7-25 carbon atoms, more preferably 7-19, and even more preferably 7-12). These groups may have substituents. Rb 1 With Rb 2 They can bond together to form rings. Preferably, the formed rings are nitrogen-containing heterocycles of 4 to 7 members. Rb 1 and Rb 2 Preferably, it is a straight-chain, branched, or cyclic alkyl group that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), more preferably a cycloalkyl group that may have substituents (preferably 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), and even more preferably a cyclohexyl group that may have substituents.

[0779] As Rb 3Examples of such compounds include alkyl groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), alkenyl groups (preferably 2-24 carbon atoms, more preferably 2-12, and even more preferably 2-6), aralkyl groups (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12), aryl-alkenyl groups (preferably 8-24 carbon atoms, more preferably 8-20, and even more preferably 8-16), alkoxy groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryloxy groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-12), or arylalkoxy groups (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12). Among these, cycloalkyl (preferably 3-24 carbon atoms, more preferably 3-18, and even more preferably 3-12), aryl, and arylalkoxy are preferred. Rb 3 It can further have substituents.

[0780] The compound represented by formula (B1) is preferably the compound represented by formula (B1-1) or formula (B1-2) below.

[0781] [Chemical Formula 72]

[0782]

[0783] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 respectively with Rb in equation (B1) 1 and Rb 2 They have the same meaning.

[0784] Rb 13 The alkyl group (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), alkenyl group (preferably 2-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl group (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-12), or aralkyl group (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12) may have substituents. Rb 13 Preferably, it is an aryl alkyl group.

[0785] Rb 33 and Rb 34Each of the following is independently composed of hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen atoms.

[0786] Rb 35 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), and preferably aryl.

[0787] The compound represented by formula (B1-1) is preferably the compound represented by formula (B1-1a).

[0788] [Chemical Formula 73]

[0789]

[0790] Rb 11 and Rb 12 Rb in equation (B1-1) 11 and Rb 12 They have the same meaning.

[0791] Rb 15 and Rb 16 The atom is a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

[0792] Rb 17 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), or aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), wherein aryl is preferred.

[0793] [Chemical Formula 74]

[0794]

[0795] In formula (B3), L represents a divalent hydrocarbon group with saturated hydrocarbon groups on the path of the linking chain connecting adjacent oxygen and carbon atoms, and the number of atoms on the linking chain path is 3 or more. Furthermore, R... N1 and R N2 Each can be used to represent a monovalent organic group independently.

[0796] In this specification, a "linking chain" refers to the shortest (minimum number of atoms) atomic chain that connects two atoms or groups of atoms along a path that links them. For example, in the compound represented by the following formula, L is composed of phenylene ethylene and has ethylene as a saturated hydrocarbon group, the linking chain consists of 4 carbon atoms, and the number of atoms along the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "linking chain length") is 4.

[0797] [Chemical Formula 75]

[0798]

[0799] The number of carbon atoms in L of formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and especially preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of accelerating the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and especially preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds as base generating agents include, for example, compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0800] Furthermore, the alkali generating agent preferably comprises a compound represented by the following formula (N1).

[0801] [Chemical Formula 76]

[0802]

[0803] In equation (N1), R N1 and R N2 Each independently represents a monovalent organic group, R C1 The symbol represents a hydrogen atom or a protecting group, and L represents a divalent linker.

[0804] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0805] In equation (N1), R N1 and R N2 Preferably, each group independently represents a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10), specifically, aliphatic hydrocarbon groups (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or aromatic hydrocarbon groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), preferably aliphatic hydrocarbon groups. As R N1 and R N2 If an aliphatic hydrocarbon group is used, the resulting base will have high basicity, which is preferred. Furthermore, the aliphatic and aromatic hydrocarbon groups can have substituents, and the aliphatic and aromatic hydrocarbon groups can also have oxygen atoms in the aliphatic hydrocarbon chain, the aromatic ring, or the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0806] As a component of R N1 and R N2 The aliphatic hydrocarbon group can be exemplified by straight-chain or branched chain alkyl groups, cyclic alkyl groups, groups comprising combinations of chain alkyl and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. The number of carbon atoms in the straight-chain or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and even more preferably 3 to 12. Examples of straight-chain or branched chain alkyl groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, etc.

[0807] The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0808] The number of carbon atoms in the group comprising a combination of chain alkyl and cyclic alkyl groups is preferably 4 to 24, more preferably 4 to 18, and even more preferably 4 to 12. Examples of groups comprising a combination of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0809] The alkyl group having oxygen atoms in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched.

[0810] In terms of increasing the boiling point of the alkali produced by the subsequent decomposition, R N1 and R N2 Preferably, it is an alkyl group having 5 to 12 carbon atoms. In formulations where adhesion with metal (e.g., copper) layers is important, it is preferred to have a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms.

[0811] R N1 and R N2 They can link together to form a ring structure. The ring structure can contain oxygen atoms, etc., within the chain. Furthermore, R... N1 and R N2 The formed ring structure can be a monocyclic ring or a condensed ring, preferably a monocyclic ring. Preferably, the formed ring structure is a 5-membered or 6-membered ring containing the nitrogen atom in formula (N1). Examples include pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, pyrazoleidine rings, piperidine rings, piperazine rings, and morpholine rings. Pyrroleline rings, pyrrolidine rings, piperidine rings, piperazine rings, and morpholine rings are particularly preferred.

[0812] R C1 It represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0813] As a protecting group, it is preferred to be a protecting group that decomposes by the action of acid or base, and protecting groups that decompose by acid are preferably listed.

[0814] Specific examples of protecting groups include chain-like or cyclic alkyl groups or chain-like or cyclic alkyl groups having oxygen atoms in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, etc. Examples of chain-like alkyl groups having oxygen atoms in the chain include alkoxyalkyl groups, preferably methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxetyl, tetrahydrofuranyl, tetrahydropyranyl (THP), etc.

[0815] In formula (N1), the divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have substituents, or may have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that can have oxygen atoms in the chain, further preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a group comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that can have oxygen atoms in the chain, and even more preferably a divalent aliphatic hydrocarbon group that can have oxygen atoms in the chain. These groups may not have oxygen atoms.

[0816] The number of carbon atoms in the divalent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and even more preferably 2 to 6. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The number of carbon atoms in the group comprising a combination of divalent aliphatic hydrocarbon group and divalent aromatic hydrocarbon group (e.g., arylene alkyl group) is preferably 7 to 22, more preferably 7 to 18, and even more preferably 7 to 10.

[0817] Specifically, the linking group L is preferably a straight-chain or branched chain alkylene, a cyclic alkylene, a group comprising a combination of chain alkylene and cyclic alkylene, an alkylene with an oxygen atom in the chain, a straight-chain or branched chain alkenyl, a cyclic alkenyl, an aryl, or an arylalkylene.

[0818] The linear or branched alkylene groups preferably have 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4.

[0819] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6.

[0820] The number of carbon atoms in the group comprising a combination of chain alkylene and cyclic alkylene is preferably 4 to 24, more preferably 4 to 12, and even more preferably 4 to 6.

[0821] The alkylene group containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. The number of carbon atoms in the alkylene group containing oxygen atoms in the chain is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0822] The number of carbon atoms in the linear or branched chain-like alkenyl groups is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds in the linear or branched chain-like alkenyl groups is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0823] The number of carbon atoms in the cyclic alkenyl group is preferably 3 to 12, more preferably 3 to 6. The number of C=C bonds in the cyclic alkenyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

[0824] The number of carbon atoms in the arylene group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10.

[0825] The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11.

[0826] Preferably, the compounds are chain-like alkylene, cyclic alkylene, alkylene with oxygen atoms in the chain, chain-like alkenyl, arylene, and arylalkylene; more preferably, 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and ethoxyethylene (especially 1,2-ethoxy-1,2-ethylene).

[0827] The following compounds can be listed as base-generating agents, but are not limited to these.

[0828] [Chemical Formula 77]

[0829]

[0830] [Chemical Formula 78]

[0831]

[0832] The molecular weight of the nonionic alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0833] Specific preferred compounds for generating ionic bases include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0834] Specific examples of ammonium salts include the following compounds, but are not limited to these.

[0835] [Chemical Formula 79]

[0836]

[0837] Specific examples of imine salts include the following compounds, but are not limited to these.

[0838] [Chemical Formula 80]

[0839]

[0840] Furthermore, from the viewpoint of storage stability and the generation of alkali through deprotection during curing, an amine with an amino group protected by a tert-butoxycarbonyl group is preferred as an alkali generating agent.

[0841] Examples of amine compounds protected by the tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, and α-[2-(methylamino)ethyl]benzylethanolamine. Alcohols, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanol bis(3-amino) Compounds containing amino acids and their derivatives whose amino groups are protected by a tert-butoxycarbonyl group, but not limited to these.

[0842] When the resin composition contains an alkali-generating agent, the content of the alkali-generating agent relative to 100 parts by weight of resin in the resin composition is preferably 0.1 to 50 parts by weight. The lower limit is more preferably 0.3 parts by weight or more, and even more preferably 0.5 parts by weight or more. The upper limit is more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less, and particularly preferably 4 parts by weight or less.

[0843] One or more alkali-generating agents can be used. When two or more are used, the total dosage is preferably within the range mentioned above.

[0844] <Solvent>

[0845] The resin composition of the present invention preferably contains a solvent.

[0846] 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.

[0847] Examples of preferred 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, alkyl 3-alkoxypropionic acid). 2-Alkoxypropionic acid alkyl esters (e.g., methyl 2-alkoxypropionic acid, ethyl 2-alkoxypropionic acid, propyl 2-alkoxypropionic acid, etc. (e.g., methyl 2-methoxypropionic acid, ethyl 2-methoxypropionic acid, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionic acid, ethyl 2-ethoxypropionic acid)), methyl 2-alkoxy-2-methylpropionic acid and ethyl 2-alkoxy-2-methylpropionic acid (e.g., methyl 2-methoxy-2-methylpropionic acid, ethyl 2-ethoxy-2-methylpropionic acid, 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.

[0848] Examples of ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol 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.

[0849] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0850] Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0851] As a sulfoxide, dimethyl sulfoxide is preferably listed, for example.

[0852] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0853] Examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolium ketone.

[0854] 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, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

[0855] From the perspective of improving the properties of the coating surface, it is preferable to mix two or more solvents.

[0856] In this invention, the solvent is preferably selected from one of the following: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic 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, or a mixed solvent consisting of two or more of these solvents. Particularly preferred combinations are those of dimethyl sulfoxide and γ-butyrolactone, dimethyl sulfoxide and γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone and ethyl lactate. Further addition of approximately 1 to 10% by mass relative to the total mass of these solvent combinations is also a preferred embodiment of the invention.

[0857] In particular, from the viewpoint of the storage stability of the resin composition, the inclusion of 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 taking into account the solubility of components such as resin A contained in the resin composition.

[0858] 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.

[0859] Furthermore, the resin composition of the present invention preferably contains a solvent with a boiling point of 50°C to 300°C at 1 atmosphere, and more preferably contains a solvent with a boiling point of 100°C to 260°C. In the present invention, the boiling point of the solvent is the boiling point at 1 atmosphere.

[0860] Based on this method, it is believed that cured products with excellent solvent removal and high resolution can be obtained.

[0861] 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.

[0862] Furthermore, the resin composition of the present invention preferably contains two or more solvents with a boiling point of 100 to 260°C, more preferably contains two or more solvents with a boiling point of 150 to 250°C, and even more preferably contains two or more solvents with a boiling point of 180 to 230°C.

[0863] Furthermore, the content of solvents with boiling points of 100–260°C relative to the total mass of the composition 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 contained, their total amount is preferably within the above-mentioned range.

[0864] 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 coating thickness and coating method. When two or more solvents are contained, their total content is preferably within the above range.

[0865] <Metal Adhesion Modifier>

[0866] 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.

[0867] [Silane coupling agent]

[0868] 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, the contents of 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 formula, Me represents methyl and Et represents ethyl. Furthermore, the following R can represent structures derived from the end-capping isocyanate group. As end-capping agents, they 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 setting 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.).

[0869] [Chemical Formula 81]

[0870]

[0871] [Chemical Formula 82]

[0872]

[0873] 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-acryloyloxypropyltrimeth ...methoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysil 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)isocyanurate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0874] Furthermore, as a silane coupling agent, compounds of oligomer type having multiple alkoxysilane groups can also be used.

[0875] Examples of this type of oligomer include compounds containing repeating units represented by the formula (S-1) below.

[0876] [Chemical Formula 83]

[0877]

[0878] 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.

[0879] 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 groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl groups), (meth)acrylamido groups, (meth)acryloyloxy groups, etc., preferably vinylphenyl, (meth)acrylamido, or (meth)acryloyloxy groups, more preferably vinylphenyl or (meth)acryloyloxy groups, and even more preferably (meth)acryloyloxy groups.

[0880] R S2 Preferably, it is alkoxy, more preferably methoxy or ethoxy.

[0881] n represents an integer from 0 to 2, preferably 1.

[0882] Among them, the repeating units represented by multiple formulas (S-1) contained in the oligomer type compounds can have the same structure.

[0883] Among the multiple repeating units represented by formula (S-1) contained in the oligomer type compound, preferably 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.

[0884] As for this type of oligomer compound, commercially available products can be used, such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0885] [Aluminum-based adhesive additives]

[0886] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and diisopropyl acetoacetate aluminum.

[0887] 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 included in this specification.

[0888] The content of the metal adhesion modifier relative to the mass of resin A100 is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass. 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 can be only one type or two or more types. When two or more types are used, their total content is preferably within the above range.

[0889] <Migration Inhibitor>

[0890] The resin composition of the present invention preferably further contains a migration inhibitor. By containing 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.

[0891] 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, pyrazine ring, piperidine ring, piperazine ring, morpholine 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.

[0892] Among these, the resin composition of the present invention preferably contains an azole compound.

[0893] 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. These structures, such as benzimidazole and benzotriazole, can form polycyclic rings with other ring structures through condensation or other processes.

[0894] Furthermore, as a compound having an azole structure, it is preferred to have a group directly bonded to the azole structure as represented by the following formula (R-1) or the following formula (R-2).

[0895] [Chemical Formula 84]

[0896]

[0897] In equation (R-1), R 1* indicates a monovalent organic group, and * indicates the bonding site with the azole structure.

[0898] In equation (R-2), R 2 R represents a hydrogen atom or a monovalent organic group. 3 * indicates a monovalent organic group, and * indicates the bonding site with the azole structure.

[0899] In equation (R-1), R 1 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by a bond of at least one of the groups in - R N As stated above.

[0900] As the aforementioned hydrocarbon group, it is preferred to use a group represented by an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.

[0901] 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.

[0902] 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 -

[0903] 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.

[0904] In equation (R-2), R 2 Hydrogen atoms are preferred.

[0905] When R 2 When R is a monovalent organic group, 2 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by a bond of at least one type of base in - R N As stated above.

[0906] As the aforementioned hydrocarbon group, it is preferred to use a group represented by an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.

[0907] And, when 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.

[0908] When R 2 When R is a monovalent organic group, 2 The bonding site between the nitrogen atom in formula (R-2) and the nitrogen atom is preferably a hydrocarbon group or -C(=O)-.

[0909] In equation (R-2), R 3 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group represented by a bond of at least one of the groups in - R N It represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom.

[0910] As the aforementioned hydrocarbon group, it is preferred to use a group represented by an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.

[0911] And, when 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.

[0912] 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)-.

[0913] 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.

[0914] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[0915] Other migration inhibitors may include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are included in this specification.

[0916] The following compounds can be listed as specific examples of migration inhibitors.

[0917] [Chemical Formula 85]

[0918]

[0919] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition 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.

[0920] 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 mentioned above.

[0921] <Light Absorber>

[0922] The resin composition of the present invention preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.

[0923] 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.

[0924] In particular, from the viewpoint of improving adhesion to the substrate, the resin composition of the present invention preferably further contains 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.

[0925] <Polymerization Inhibitor>

[0926] 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.

[0927] 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-diacrylbicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. This content is included in this specification.

[0928] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid 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.

[0929] The polymerization inhibitor can be one type or two or more types. When there are two or more polymerization inhibitors, their total number is preferably within the range mentioned above.

[0930] <Other Additives>

[0931] The resin composition of the present invention may contain various additives as needed within the range 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, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other additives (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the film properties and other properties can be adjusted. Regarding these components, for example, reference can be made to paragraphs 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are incorporated, their total content is preferably set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0932] [surfactants]

[0933] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0934] By including a surfactant in the resin composition of this invention, the liquid properties (especially flowability) of the coating liquid composition can be further improved, and the uniformity of the coating thickness or the liquid-saving properties can be further improved. That is, when using a coating liquid containing a surfactant to form a film, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and enhancing the coatability of the coated surface. Therefore, it is possible to form a more uniform film with smaller thickness deviations.

[0935] As fluorinated surfactants, compounds described in paragraph 0328 of International Publication No. 2021 / 112189, the contents of which are incorporated herein by reference, may be listed.

[0936] As a fluorinated surfactant, it is also preferable to use a fluorinated polymeric compound comprising repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or propoxy groups), for example, the following compounds can be listed.

[0937] [Chemical Formula 86]

[0938]

[0939] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0940] Regarding fluorinated surfactants, fluorinated polymers with olefinically unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Furthermore, commercially available products include, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DICCorporation.

[0941] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniformity of coating thickness or liquid saving, and also have good solubility in the composition.

[0942] As silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants, the compounds described in paragraphs 0329 to 0334 of International Publication No. 2021 / 112189 are listed respectively, and this content is incorporated into this specification.

[0943] A single surfactant can be used, or two or more surfactants can be used in combination.

[0944] The content of surfactant relative to the total solids content of the composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass.

[0945] [Inorganic particles]

[0946] 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.

[0947] 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.

[0948] 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.).

[0949] When the above measurements are difficult to perform, measurements can also be made using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0950] [Organotitanium compounds]

[0951] By incorporating organotitanium compounds into the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0952] As usable organotitanium compounds, examples include compounds in which organic groups are bonded to titanium atoms via covalent or ionic bonds.

[0953] Specific examples of organotitanium compounds are shown in I) to VII) below:

[0954] I) Chelated titanium compounds: From the viewpoint of good storage stability of the resin composition and the ability to obtain good cured patterns, chelated titanium 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(tetramethylheptyl ester)diisopropoxy titanium, bis(ethyl acetoacetate)diisopropoxy titanium, etc.

[0955] 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, tetrastearoxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc.

[0956] III) Titanium decene compounds: such as pentamethylcyclopentadienetrimethoxytitanium, 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.

[0957] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecyl benzenesulfonate) isopropoxy titanium, etc.

[0958] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0959] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0960] VII) Titanate coupling agents: such as isopropyltris(2-dodecylbenzenesulfonyl)titanate, etc.

[0961] From the viewpoint of better drug resistance, at least one compound selected from the above-mentioned I) chelated titanium compound, II) tetraalkoxy titanium compound and III) dicaprocene compound is preferred as the organotitanium compound. In particular, 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 are preferred.

[0962] Furthermore, as an organotitanium compound or a substitute for an organotitanium compound, it is preferred to contain a compound represented by the following formula (T-1).

[0963] [Chemical Formula 87]

[0964]

[0965] 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 R is independently substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted phenoxy. 12 R is a substituted or unsubstituted hydrocarbon group. 2 R are groups that independently contain the structure represented by the following formula (T-2). 3 X are groups that independently contain the structure represented by the following formula (T-2). A Each can be an oxygen atom or a sulfur atom, independently.

[0966] [Chemical Formula 88]

[0967]

[0968] 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.

[0969] In formula (T-1), from the viewpoint of the storage stability of the composition, M is preferably titanium.

[0970] In equation (T-1), the setting of l1 and l2 to 0 is also one of the preferred embodiments of the present invention.

[0971] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0972] In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1.

[0973] In formula (T-1), it is also preferred that l1 and l2 are 0 and m is 0, 2 or 4.

[0974] In equation (T-1), from the viewpoint of the stability of a specific metal complex, R 11 Preferably, it is a substituted or unsubstituted cyclopentadiene ligand.

[0975] 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.

[0976] In equation (T-1), R 12 Preferably, it is a hydrocarbon group with 1 to 20 carbon atoms, and more preferably a hydrocarbon group with 2 to 10 carbon atoms.

[0977] As R 12 The hydrocarbon group in the hydrocarbon group can be any one of aliphatic hydrocarbon group or aromatic hydrocarbon group, preferably an aromatic hydrocarbon group.

[0978] As an aliphatic hydrocarbon group, it can be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, preferably a saturated aliphatic hydrocarbon group.

[0979] 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.

[0980] 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.

[0981] 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.

[0982] In equation (T-1), m is 2 or more, when it contains more than 2 R. 2 At that time, the two or more R 2 The structures can be the same or different.

[0983] In equation (T-1), n ​​is 2 or more, when it contains more than 2 R 3 At that time, the two or more R 3 The structures can be the same or different.

[0984] In equation (T-2), X 1 ~X 3-C(-*)= or -N= can be represented independently, preferably at least one of them is -C(-*)=, more preferably at least two of them are -C(-*)=.

[0985] 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.

[0986] When an organotitanium compound is present, its content relative to parts by weight of resin A100 is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. When the content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0987] When an organotitanium compound is present, its content relative to parts by weight of resin A100 is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight. When the content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0988] 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.

[0989] <Characteristics of the Resin Composition>

[0990] The viscosity of the resin composition of the present invention can be adjusted by the concentration of the solid components in the resin composition. From the viewpoint of coating film thickness, 1000 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. Within the above range, a highly uniform coating film is easily obtained. For 1,000 mm... 2 If the thickness is above / s, it is easy to coat with the film thickness required for reinsertion insulation, for example, if it is 12,000 mm. 2 When the speed is below / s, a coating film with excellent surface finish can be obtained.

[0991] When a cured material with a film thickness of 10 μm is formed using the resin composition of the present invention, the transmittance of the cured material to light with a wavelength of 365 nm is preferably 10% or more, more preferably 20% or more, and even more preferably 25% or more.

[0992] The upper limit of the aforementioned transmittance is not specifically limited and can be 100%.

[0993] The cured product described above can be obtained, for example, by coating the resin composition of the present invention onto a silicon wafer, drying it at 100°C for 5 minutes, and then passing it through an i-ray at 500 mJ / cm². 2 After full-area exposure at the specified exposure energy, the temperature was increased at a rate of 10°C / min under a nitrogen atmosphere and heated at 230°C for 180 minutes.

[0994] <Restrictions on the Contents of Resin Compositions>

[0995] 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.

[0996] Methods for maintaining moisture content include adjusting humidity during storage and reducing the porosity of the container during storage.

[0997] 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 exclude metals contained as complexes of organic compounds and metals. When multiple metals are contained, the total amount of these metals is preferably within the above-mentioned range.

[0998] Furthermore, as a method to reduce metal impurities accidentally included 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 with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0999] Regarding the resin composition of the present invention, from the viewpoint of wiring corrosion resistance, considering its use as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. The amount present as 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.

[1000] Methods for adjusting the content of halogen atoms include, preferably, ion exchange treatment.

[1001] 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 formed of six different resins or bottles with a seven-layered structure formed of six different resins are also preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[1002] <Cure of Resin Composition>

[1003] By curing the resin composition of the present invention, a cured resin composition can be obtained.

[1004] The cured product of the present invention is a cured product obtained by curing a resin composition.

[1005] 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. Through patterning of the resin composition, the shape of the cured product can also be selected according to applications such as forming a protective film on a wall surface, forming conductive through-holes, adjusting resistance, electrostatic capacitance or internal stress, or imparting heat dissipation. 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.

[1006] The shrinkage rate of the resin composition of the present invention during curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, which can be calculated according to the following formula.

[1007] Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[1008] <Characteristics of cured resin compositions>

[1009] 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.

[1010] 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.

[1011] 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.

[1012] <Preparation of Resin Compositions>

[1013] 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 by conventionally known methods.

[1014] Examples of mixing methods include mixing based on stirring blades, mixing based on ball mills, and mixing by rotating a tank.

[1015] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[1016] For the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration is preferably performed using a filter. Regarding the filter pore size, it 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 a filter pre-cleaned with an organic solvent. In the 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. For example, a connection method can be described as follows: using an HDPE filter with a 1 μm pore size as the first stage and an HDPE filter with a 0.2 μm pore size as the second stage, connecting them in series. Furthermore, various materials can be filtered multiple times. Multiple filtrations can be performed as circulating filtration. Pressure filtration can also be performed. When pressure filtration is performed, 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.

[1017] Besides using filters for filtration, adsorption materials can also be used to remove impurities. Furthermore, filtration and impurity removal using adsorption materials can 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.

[1018] After filtration, the resin composition filled in the bottle can be placed under reduced pressure to perform a degassing process.

[1019] (Method for manufacturing solidified products)

[1020] 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.

[1021] The method for manufacturing the cured material more preferably includes the above-described film forming step, an exposure step for selectively exposing the film formed by the film forming step, and a development step for developing the film exposed by the exposure step using a developing solution to form a pattern.

[1022] The method for manufacturing the cured material is particularly preferably 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.

[1023] Furthermore, the method for manufacturing the cured material preferably includes the above-mentioned film formation step and the step of heating the above-mentioned film.

[1024] The following is a detailed explanation of each process.

[1025] <Membrane Formation Process>

[1026] The resin composition of the present invention can be used in a film forming process in which it is applied to a substrate to form a film.

[1027] 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.

[1028] [Substrate]

[1029] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any substrate formed of metal and substrates with metal layers formed by plating or vapor deposition); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). Semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred.

[1030] Layers such as a sealing layer or an oxide layer formed of hexamethyldisilazane (HMDS) can be provided on the surface of these substrates.

[1031] The shape of the substrate is not particularly limited; it can be circular or rectangular.

[1032] Regarding the dimensions of the substrate, if it is circular, the diameter is preferably 100–450 mm, more preferably 200–450 mm. If it is rectangular, the length of the shorter side is preferably 100–1000 mm, more preferably 200–700 mm.

[1033] As a substrate, a plate-like material can be used, preferably a panel-like substrate (substrate).

[1034] 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.

[1035] As a method for applying a resin composition to a substrate, coating is preferred.

[1036] 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 both 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, and inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, and inkjet coating are preferred. When using spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for approximately 10 seconds to 3 minutes.

[1037] Furthermore, it is also possible to apply a method for transferring a coating film, which has been pre-applied to a temporary support by the above-described application method, onto a substrate.

[1038] 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.

[1039] Furthermore, a process for removing excess film from the ends of the substrate can be performed. Examples of such processes include edge bead rinsing (EBR) and back rinsing.

[1040] 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 the wettability of the substrate, and then the resin composition is applied.

[1041] <Drying Process>

[1042] After the film formation process (layer formation process), the above-mentioned film can be supplied to a process for drying the formed film (layer) (drying process) to remove the solvent.

[1043] 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.

[1044] The drying process described above is preferably performed after the film formation process and before the exposure process.

[1045] The membrane drying temperature in the drying process is preferably 50–150°C, more preferably 70–130°C, and even more preferably 90–110°C. Furthermore, drying can be performed under reduced pressure. The drying time can be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[1046] <Exposure Process>

[1047] The above-mentioned film can be used in an exposure process for selective exposure of the film.

[1048] The method for manufacturing a cured material may include an exposure process that selectively exposes a film formed by a film forming process.

[1049] Selective exposure refers to exposing a portion of a film. Furthermore, selective exposure creates exposed areas (exposed areas) and unexposed areas (non-exposed areas) on the film.

[1050] 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 / cm², calculated in terms of exposure energy at a wavelength of 365 nm. 2 More preferably 200–8,000 mJ / cm 2 .

[1051] The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[1052] Regarding the exposure wavelength, in relation to the light source, the following can be listed: (1) semiconductor lasers (wavelengths 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, i-rays, etc.), (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. Regarding the resin composition of the present invention, exposure based on high-pressure mercury lamps is preferred, and from the viewpoint of exposure sensitivity, exposure based on i-rays is more preferred.

[1053] The exposure method is not particularly limited, as long as it is a method of exposing at least a portion of the film formed by the resin composition of the present invention, such as exposure using a photomask, exposure based on laser direct imaging, etc.

[1054] <Post-exposure heating process>

[1055] The above-mentioned film can be used in the post-exposure heating process (post-exposure heating process).

[1056] 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.

[1057] The post-exposure heating process can be performed after the exposure process and before the development process.

[1058] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[1059] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[1060] Regarding the heating rate in the post-exposure heating process, from the initial heating temperature to the maximum heating temperature, it is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[1061] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[1062] As a heating method in the post-exposure heating process, it is not particularly limited and can use known heating plates, ovens, infrared heaters, etc.

[1063] Furthermore, during heating, it is preferable to conduct the process in an atmosphere with low oxygen concentration by introducing inert gases such as nitrogen, helium, or argon.

[1064] <Developing Process>

[1065] The exposed film can be used in the developing process to form a pattern by developing with a developing solution.

[1066] That is, the method for manufacturing the cured material 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.

[1067] By developing the film, one of the exposed and unexposed portions is removed to form a pattern.

[1068] 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.

[1069] [Developing solution]

[1070] Developers used in the developing process include alkaline aqueous solutions and developer solutions containing organic solvents.

[1071] When the developer is an alkaline aqueous solution, the alkaline compounds that may be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred alkaline 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, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium 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.

[1072] 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 in this specification. Furthermore, as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., may also be preferably listed; as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., may also be preferably listed.

[1073] When the developer contains an organic solvent, one or more organic solvents may be used. In this invention, a developer containing at least one selected from cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferred, more preferably a developer containing at least one selected from cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide, and especially preferably a developer containing cyclopentanone.

[1074] 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 can be 100% by mass.

[1075] Developer may also contain other ingredients.

[1076] Other components include, for example, well-known surfactants or well-known defoamers.

[1077] [Method for supplying developer]

[1078] 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; examples include direct spray nozzles, spray nozzles, and mist nozzles.

[1079] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, a method of supplying developer using a direct spray 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 developer using a spray nozzle is more preferred.

[1080] Furthermore, the following steps can be adopted: after continuously supplying developer with a direct-jet nozzle, rotating the substrate to remove developer from the substrate, rotating and drying, and then continuously supplying developer with a direct-jet nozzle again, rotating the substrate to remove developer from the substrate, or repeating this step multiple times.

[1081] 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 substantially static state, using ultrasound or the like to vibrate the developer on the substrate, and combining these methods.

[1082] 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 limited, but is preferably 10 to 45°C, more preferably 18°C ​​to 30°C.

[1083] In the developing process, the pattern can be further cleaned (rinsed) using a rinsing solution after treatment with the developing solution. Alternatively, the rinsing solution can be supplied before the developing solution in contact with the pattern has completely dried.

[1084] [Rinse solution]

[1085] 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.

[1086] As for the organic solvents that are present in the rinsing solution, the same organic solvents as those exemplified when the developing solution contains organic solvents can be listed.

[1087] The organic solvent contained in the rinsing solution is preferably an organic solvent that is different from the organic solvent contained in the developing solution, and more preferably an organic solvent that has a lower solubility in the pattern compared to the organic solvent contained in the developing solution.

[1088] 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.

[1089] 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 can be 100% by mass relative to the total mass of the rinsing solution.

[1090] The rinsing solution may also contain other ingredients.

[1091] Other components include, for example, well-known surfactants or well-known defoamers.

[1092] [Method for supplying flushing fluid]

[1093] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the rinsing liquid. The following methods are available: immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by swirling immersion, supplying the rinsing liquid to the substrate with a spray head, and continuously supplying the rinsing liquid to the substrate through a mechanism such as a direct spray nozzle.

[1094] From the perspectives of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, methods for supplying rinsing fluid include spray nozzles, direct spray nozzles, and mist nozzles. A continuous supply method using a mist nozzle is preferred. From the perspective of the penetrability of the rinsing fluid to the image area, a mist nozzle supply method is even more preferred. There are no particular limitations on the type of nozzle; examples include direct spray nozzles, spray nozzles, and mist nozzles.

[1095] That is, the rinsing process is preferably a process of supplying or continuously supplying rinsing liquid to the exposed film using a direct spray nozzle, and more preferably a process of supplying rinsing liquid through a spray nozzle.

[1096] 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.

[1097] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution is not particularly limited, but is preferably 10 to 45°C, more preferably 18°C ​​to 30°C.

[1098] <Heating Process>

[1099] The pattern obtained by the developing process (or the washed pattern if a rinsing process is performed) can be used in a heating process for heating the pattern obtained by the developing process described above.

[1100] 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.

[1101] Furthermore, the method for manufacturing the cured product of the present invention may 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.

[1102] In the heating process, resins such as polyimide precursors are cyclized to form resins such as polyimide.

[1103] Furthermore, crosslinking of unreacted crosslinking groups in resin A or a crosslinking agent other than resin A is also performed.

[1104] 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.

[1105] When the resin composition contains a resin corresponding to the polyimide precursor, the heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by heating and by the action of an alkali or the like generated from the alkali generating agent.

[1106] In the heating process, heating is preferably carried out from the initial temperature to the maximum heating temperature at a heating rate of 1 to 12°C / min. More preferably, the heating rate is 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the heating rate to 1°C / min or more, productivity can be ensured while preventing excessive evaporation of acid or solvent; by setting the heating rate to 12°C / min or less, residual stress in the cured material can be mitigated.

[1107] Furthermore, when using 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.

[1108] 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 process begins when the material is heated to 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, the temperature of the dried film (layer) is preferred; for example, it is preferable to start heating from a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the resin composition.

[1109] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[1110] In particular, when forming a multilayer 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.

[1111] 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.

[1112] Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at a rate of 3°C / min and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at a rate of 2°C / min and holding at 180°C for 120 minutes. Furthermore, it is preferable to perform the treatment while irradiating with ultraviolet light, as described in U.S. Patent No. 9,159,547. This pretreatment process can improve the properties of the membrane. The pretreatment process can be performed in a short time of approximately 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process can be a two-stage or more process; for example, a first-stage pretreatment process can be performed in the range of 100–150°C, followed by a second-stage pretreatment process in the range of 150–200°C.

[1113] Furthermore, cooling can be performed after heating, and the preferred cooling rate at this time is 1 to 5°C / minute.

[1114] Regarding the heating process, from the viewpoint of preventing the decomposition of resin A, it is preferable to carry it under reduced pressure by introducing inactive gases such as nitrogen, helium, or argon, thereby creating an atmosphere with a low oxygen concentration. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[1115] The heating method used in the heating process is not particularly limited; for example, heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens can be listed.

[1116] <Post-development exposure process>

[1117] The pattern obtained by the developing process (or the washed pattern when the washing process is performed) can replace the heating process described above, or other than the heating process described above, and be used in a post-development exposure process to expose the pattern after the developing process.

[1118] 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.

[1119] In the post-development exposure process, reactions such as cyclization of polyimide precursors by exposure to photoalkali generating agents and removal of acid-decomposing groups by exposure to photoacid generating agents can be promoted.

[1120] 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, preferably all of the pattern is exposed.

[1121] Regarding the exposure amount in the post-development exposure process, calculated based on the exposure energy at the wavelength where the photosensitive compound has sensitivity, it is preferably 50–20,000 mJ / cm². 2 More preferably 100–15,000 mJ / cm 2 .

[1122] Regarding the post-development exposure process, for example, the light source used in the above-mentioned exposure process can be used, preferably broadband light.

[1123] <Metal Layer Formation Process>

[1124] The pattern obtained by the developing process (preferably a pattern obtained by at least one of the heating process and the exposure process after developing) can also be used in the metal layer forming process of forming a metal layer on the pattern.

[1125] 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 obtained by at least one of a heating step and a post-developing exposure step).

[1126] As a metal layer, it is not particularly limited and can use existing metal types, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[1127] The method for forming the metal layer is not particularly limited, 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 vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electroplating can be listed. As a preferred method of plating, electroplating using copper sulfate plating solution or copper cyanide plating solution can be listed.

[1128] The thickness of the metal layer, measured in the thickest part, is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

[1129] <Uses>

[1130] 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. Other applications include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), or patterns formed by etching on insulating films used for mounting purposes as described above. For these applications, references can be made to Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimides,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and the Japan Polyimide & Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[1131] 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, for etching molded parts, and for manufacturing protective coatings and dielectric layers in electronics, especially microelectronics.

[1132] (Laminated bodies and methods for manufacturing laminated bodies)

[1133] The laminate of the present invention refers to a structure having multiple layers formed by the cured product of the present invention.

[1134] 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.

[1135] Of the two or more layers formed by the cured material included in the above-mentioned laminate, at least one layer is 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 that accompanies the shrinkage, it is even more preferable that all the layers formed by the cured material included in the above-mentioned laminate are formed by the cured material of the present invention.

[1136] That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

[1137] The laminate of the present invention preferably comprises two or more layers formed of a cured material, and a metal layer is included between any of the layers formed of the cured material. The metal layer is preferably formed by the aforementioned metal layer forming process.

[1138] That is, the method for manufacturing the laminate of the present invention preferably includes a metal layer forming step between multiple methods for manufacturing cured products, wherein a metal layer is formed on the layer formed by the cured product. The preferred embodiment of the metal layer forming step is as described above.

[1139] As an example of the aforementioned laminate, a laminate structure comprising at least three layers sequentially stacked: a layer formed by a first cured material, a metal layer, and a layer formed by a second cured material can be preferred.

[1140] Both the layer formed by the first cured product and the layer formed by the second cured product are preferably layers formed by the cured product 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 can be the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[1141] <Layering Process>

[1142] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[1143] The lamination process includes a series of steps that sequentially perform 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 the pattern (resin layer) or metal layer. However, it may be possible to repeat at least one of (a) the film formation step and (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. Of course, the lamination process may appropriately further include the aforementioned drying step, etc.

[1144] When a further lamination process is performed after the lamination process, a surface activation treatment process may 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 surface activation treatment. Details regarding surface activation treatment will be described later.

[1145] The above-mentioned layering process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[1146] For example, a structure with 2 or more but less than 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure with 2 or more but less than 9 layers is even more preferred.

[1147] The composition, shape, and film thickness of each of the above layers can be the same or different.

[1148] In this invention, it is particularly preferred that a cured product (resin layer) of the resin composition of the present invention is further formed after the metal layer is formed to cover 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 sequence, 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 sequence. 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.

[1149] (Surface activation treatment process)

[1150] The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the above-mentioned metal layer and resin composition layer.

[1151] The surface activation treatment process is usually performed after the metal layer formation process, but the metal layer formation process can also be performed after the surface activation treatment process of the resin composition layer after the above-mentioned development process (preferably after at least one of the heating process and the post-development exposure process).

[1152] 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, surface activation treatment is performed on at least a portion of the metal layer, and more preferably on a portion or all of the area on the metal layer where 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 its surface can be improved.

[1153] Preferably, part or all of the exposed resin composition layer (resin layer) is also subjected to surface activation treatment. In this way, by performing surface activation treatment on 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 is cured, such as during negative development, it is less likely to be damaged by surface treatment, and adhesion is easily improved.

[1154] Surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189, which is incorporated herein by reference.

[1155] (Semiconductor devices and their manufacturing methods)

[1156] The present invention also discloses a semiconductor device comprising the cured material or laminate of the present invention.

[1157] 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.

[1158] 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.

[1159] Example

[1160] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing contents, processing order, etc., shown in the following examples can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise stated, "parts" and "%" are based on mass.

[1161] <Synthesis of dianhydride (AH-1)>

[1162] In a flask equipped with a stirrer and a condenser, 38.9 g (185 mmol) of trimellitic anhydride chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.10 g of N,N'-dimethylaminopyridine (DMAP), and 15.0 g of pyridine were dissolved in 100 g of tetrahydrofuran (THF) and 20 g of N-methylpyrrolidone, and the solution was cooled to -10°C to 0°C. Next, 12.35 g (90 mmol) of the Q-1 synthesized above was dissolved in 60 mL of tetrahydrofuran and 40 g of N-methylpyrrolidone (NMP). The solution was added dropwise over 1 hour with stirring for 1 hour, then the temperature was raised to 25°C and stirred for 24 hours. Next, the reaction solution was transferred to a separatory funnel, diluted with 4 L of ethyl acetate, washed twice with 500 mL of 1 N (mol / L) hydrochloric acid aqueous solution, washed three times with 500 mL of saturated sodium bicarbonate aqueous solution, and washed with 500 mL of saturated saline solution. After drying with sodium sulfate, it was filtered through filter paper, and the solvent was removed using an evaporator to obtain crystals. The crystals obtained above were then transferred to a flask, 200 mL of acetic anhydride was added, and the mixture was stirred at 80 °C for 3 hours. After cooling to 25 °C, it was filtered, rinsed with 500 mL of hexane, and dried under vacuum at 40 °C for 1 day to obtain 21 g of dianhydride AH-1. 1 H-NMR confirmed that AH-1 is a compound with the structure represented by the formula AH-1.

[1163] [Chemical Formula 89]

[1164]

[1165] <Synthesis of dianhydrides (AH-2 to AH-5)>

[1166] With appropriate changes to the raw materials, AH-2 to AH-5 were synthesized using the same method as AH-1. Through 1 H-NMR confirmed that AH-2 to AH-5 are compounds with structures represented by the formulas AH-2 to AH-5 respectively.

[1167] [Chemical Formula 90]

[1168]

[1169] <Synthesis of BC-1>

[1170] 6.20 g (20 mmol) of 4,4'-oxophthalic anhydride, 4.93 g (41 mmol) of diethylene glycol monomethyl ether, 3.16 g (40 mmol) of pyridine, and 44.5 g of tetrahydrofuran were weighed into a flask and stirred at 60 °C for 4 hours, then cooled to 25 °C. The reaction mixture was then transferred to a separatory funnel, diluted with 500 mL of ethyl acetate, washed twice each with 300 mL of 1N hydrochloric acid, 200 mL of water, and 300 mL of saturated saline solution, and dried over sodium sulfate. The organic layer was then transferred to a grate flask, and the solvent was removed using an evaporator to obtain 10 g of BC-1 (a mixture of isomers).

[1171] from 1 ¹H-NMR spectroscopy confirmed that BC-1 is a compound with the structure represented by the formula BC-1. BC-1 is a mixture of isomers of the following structure.

[1172] [Chemical Formula 91]

[1173]

[1174] <Synthesis of BC-2 to BC-5>

[1175] With appropriate changes to the raw materials, BC-2 to BC-5 were synthesized using the same method as BC-1. Through 1 H-NMR confirmed that BC-2 to BC-5 are compounds with structures represented by the formulas BC-2 to BC-5 respectively.

[1176] [Chemical Formula 92]

[1177]

[1178] [Chemical Formula 93]

[1179]

[1180] <Synthesis of BC-6>

[1181] 10.41 g (20 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride, 1.80 g (100 mmol) of pure water, 1.58 g (20 mmol) of pyridine, and 60.0 g of tetrahydrofuran were weighed into a flask and stirred at 60 °C for 4 hours, then cooled to 25 °C. The reaction mixture was then transferred to a grate flask, and the solvent was removed using an evaporator to obtain 11 g of BC-6.

[1182] from 1 H-NMR spectroscopy confirmed that BC-6 is a compound with the structure represented by the formula BC-6.

[1183] [Chemical Formula 94]

[1184]

[1185] <Synthesis of BC-7 to BC-9>

[1186] The raw materials were appropriately changed, and BC-7 to BC-9 were synthesized using the same method as BC-6.

[1187] [Chemical Formula 95]

[1188]

[1189] <Synthesis of BC-10>

[1190] 6.20 g (20 mmol) of 4,4'-oxophthalic anhydride, 2.50 g (40 mmol) of cis-octahydroisoindole, and 50.0 g of tetrahydrofuran were weighed into a flask and stirred at 60 °C for 4 hours, then cooled to 25 °C. The reaction mixture was then transferred to a gai flask, and the solvent was removed using an evaporator to obtain 8 g of BC-10.

[1191] from 1 ¹H-NMR spectroscopy confirmed that BC-10 is a compound with the structure represented by the formula BC-10. BC-10 is a mixture of isomers with the following structure.

[1192] [Chemical Formula 96]

[1193]

[1194] <Synthesis of BC-11~12>

[1195] With appropriate changes to the raw materials, BC-11 to BC-12 were synthesized using the same method as BC-10. Through 1 H-NMR confirmed that BC-11 to BC-12 are compounds with structures represented by the formulas BC-11 to BC-12.

[1196] [Chemical Formula 97]

[1197]

[1198] <Synthesis of 6-maleimide hexanoyl chloride (M-1)>

[1199] 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 oxaloyl 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 the mixture was stirred for 2 hours to synthesize 6-maleimide hexanoyl chloride (M-1).

[1200] [Chemical Formula 98]

[1201]

[1202] <Synthesis example AA-1>

[1203] 48.65 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide were mixed in a flask. 98.21 g (450 mmol) of di-tert-butyl dicarbonate was added dropwise under ice bath 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. Since white crystals precipitated, the precipitated solid was recovered by suction filtration. The resulting 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%).

[1204] The structure of AA-1a is shown below. (Through...) 1 H-NMR spectroscopy confirmed the following structure.

[1205] [Chemical Formula 99]

[1206]

[1207] 75.0 g (115.6 mmol) of (AA-1a) was mixed with 500 mL of dichloromethane in a 1 L flask.

[1208] 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 bath conditions, followed by 117.0 g (1156 mmol) of triethylamine. Since pale yellow crystals precipitated, the precipitated solid was recovered by suction filtration. Resuspension washing with 750 mL of methanol yielded 40.5 g of (AA-1) (73% yield). The structure of AA-1 is shown below. 1 H-NMR spectroscopy confirmed the following structure.

[1209] [Chemical Formula 100]

[1210]

[1211] <Synthesis examples AA-2, AA-3, AA-4>

[1212] In synthetic example AA-1, 3,3'-dihydroxybenzidine was appropriately modified; otherwise, AA-2, AA-3, and AA-4 were obtained by the same method. The structures of each compound are shown below. 1 H-NMR spectroscopy confirmed the following structure.

[1213] [Chemical Formula 101]

[1214]

[1215] <Synthetic Example SA-1: Synthesis of Polyimide (SA-1)>

[1216] A solution was prepared by dissolving 6.05 g (28.5 mmol) of m-Tolidine, 12.78 g (28.5 mmol) of AA-1, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical in 100 g of N-methylpyrrolidone (NMP). 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. The reaction mixture was then added dropwise to a mixture of 1.5L methanol and 0.5L water, stirred for 15 minutes, and the polyimide resin was filtered. Next, 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. The dried resin was then dissolved in 250g of tetrahydrofuran, and 0.1g of TEMPO, 50g of trifluoroacetic acid, and 15g of water 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 precipitate was obtained by filtration and dried under reduced pressure at 45°C for 1 day. Next, the dried resin was dissolved in 250g of tetrahydrofuran and 25g of water. 40g of ion exchange resin (MB-1: manufactured by ORGANOCORPORATION) was added and stirred for 4 hours. After filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 liters 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 imidization rate was 99%. Polyimide (SA-1) is a resin having repeating units represented by the following formula SA-1. 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.

[1217] [Chemical Formula 102]

[1218]

[1219] <Synthetic Examples SA-2 to SA-4: Synthesis of Polyimides (SA-2) to (SA-4)>

[1220] With appropriate changes to the raw materials, polyimides (SA-2) to (SA-4) were synthesized using the same method as SA-1. 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.

[1221] [Chemical Formula 103]

[1222]

[1223] [Chemical Formula 104]

[1224]

[1225] [Table 1]

[1226]

[1227] <Synthetic Example SA-5: Synthesis of Polyimide (SA-5)>

[1228] A solution was prepared by dissolving 6.05 g (28.5 mmol) of m-Tolidine, 12.78 g (28.5 mmol) of AA-1, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical in 100 g of N-methylpyrrolidone (NMP). 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, stirred for 15 minutes, and then the polyimide resin was filtered. The resin was then 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. The dried resin was then dissolved in 250g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANOCORPORATION) was added and stirred for 4 hours. After filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The precipitate was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SA-5).

[1229] 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 each repeating unit. In the following structures, the subscripts in parentheses indicate the molar ratio of each structure.

[1230] [Chemical Formula 105]

[1231]

[1232] <Synthetic Example SA-6: Synthesis of Polyimide (SA-6)>

[1233] With appropriate changes to the raw materials, polyimide (SA-6) was synthesized using the same method as in synthesis example SA-5.

[1234] The weight-average molecular weight of polyimide (SA-6) is 12,600, and the number-average molecular weight is 5,800. According to...1 The H-NMR results showed an imidization rate of 98%. Polyimide (SA-6) is a resin having repeating units represented by the formula SA-5. 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.

[1235] [Chemical Formula 106]

[1236]

[1237] <Synthetic Example MA-1: Synthesis of End-Capping Agent (MA-1)>

[1238] 23.02 g (100 mmol) of 4-amino-4'-nitrodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 mL of dimethylformamide were mixed in a flask. 22.91 g (105 mmol) of di-tert-butyl dicarbonate (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise under ice bath conditions. After the addition was complete, the mixture was stirred at 60 °C for 5 hours. After the reaction was complete, the mixture was cooled to room temperature, diluted in 800 mL of ethyl acetate, and transferred to a separatory funnel. The mixture was then washed three times with 300 mL of saturated sodium bicarbonate aqueous solution and once with 300 mL of saturated brine, dried over 100 g of sodium sulfate, the solvent was removed using an evaporator, and the mixture was dried under vacuum at 45 °C for 24 hours to obtain 27.2 g of MA-1. 1 H-NMR confirmed the following structure.

[1239] [Chemical Formula 107]

[1240]

[1241] <Synthetic Example MB-1: Synthesis of End-Capping Agent (MB-1)>

[1242] 240 mL of isopropanol, 60 mL of pure water, 11.27 g of ammonium chloride, 5.75 g of acetic acid, and 55.7 g of reduced iron were mixed in a flask and stirred at 20°C–30°C. Next, 25 g of the synthesized MA-1 was added, and the mixture was stirred for 1 hour. The temperature was then raised to 80°C and stirred for 4 hours. The mixture was filtered through a diatomaceous earth-lined funnel (Nutsche), and the filtrate was dissolved in 800 mL of ethyl acetate. The solution was transferred to a separatory funnel, washed three times with 300 mL of saturated sodium bicarbonate solution, and once with 300 mL of saturated saline solution. The solution was then dried with 100 g of sodium sulfate, the solvent was removed using an evaporator, and the solution was vacuum dried at 45°C for 24 hours to obtain 20.1 g of MB-1.

[1243] pass 1 H-NMR confirmed the following structure.

[1244] [Chemical Formula 108]

[1245]

[1246] <Synthetic Example PB-1: Synthesis of Polyimide Precursor (PB-1)>

[1247] 7.42 g (34.0 mmol) of pyromellitic anhydride, 17.7 g (34.0 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diglyme were mixed and stirred at 60 °C for 5 hours to prepare a diester of pyromellitic anhydride and 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) with 2-hydroxyethyl methacrylate. Next, the mixture was cooled to -20°C, and 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours to obtain a white precipitate of pyridinium hydrochloride.

[1248] Next, a solution obtained by dissolving 12.0 g (56.4 mmol) of meta-toluidine in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. Then, 3.80 g of the end-capping agent (MB-1) synthesized above was dissolved in 30.0 g of NMP, and the mixture was stirred for another 2 hours. Next, the polyimide precursor was precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The mixture was filtered to obtain the polyimide precursor, stirred again in 4 L of water for 30 minutes, and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 °C for 2 days to obtain polyimide precursor (PB-1). The obtained polyimide precursor (PB-1) had a weight-average molecular weight of 21,800 and a number-average molecular weight of 8,100. The imidization rate was 8%. 1 H-NMR confirmed that the polyimide precursor (PB-1) was a resin having two repeating units represented by the following formula (PB-1).

[1249] [Chemical Formula 109]

[1250]

[1251] <Synthetic Example SA-7: Synthesis of Polyimide (SA-7)>

[1252] 31.23 g (60.0 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride was dissolved in 100 g of NMP. Next, 5.48 g (25.8 mmol) of meta-toluidine and 5.58 g (25.8 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl were dissolved in 100 g of N-methylpyrrolidone (NMP) and added dropwise to the solution over 1 hour at 10°C–25°C. After stirring for 60 minutes, 3.60 g (12.0 mmol) of MB-1 was added, and the mixture was stirred for 2 hours at 10°C–25°C. Then, 28.4 g of pyridine and 15.3 g of acetic anhydride were added, and the reaction was carried out at 80°C for 4 hours. After the reaction was complete, the mixture was cooled to 25°C. Next, 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical and 14.2 (62 mmol) of the synthesized M-1 were added, and the mixture was stirred at 10°C–25°C for 24 hours. Then, after dilution with 200 g of tetrahydrofuran, the reaction mixture was added dropwise to a mixture of 1.5 L of methanol and 0.5 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was re-slurried with 1 L of water for 30 minutes and filtered, then re-slurried again with 1 L of methanol and filtered, and dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added, and the mixture was stirred for 4 hours. 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-7).

[1253] The obtained polyimide (SA-7) has a weight-average molecular weight of 18,500 and a number-average molecular weight of 7,000. The imidization rate is 97%. Polyimide (SA-7) is a resin having repeating units represented by the following formula SA-7. 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.

[1254] [Chemical Formula 110]

[1255]

[1256] <Synthetic Example SB-1: Synthesis of Polyimide (SB-1)>

[1257] A solution was prepared by dissolving 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 in 120 g of N-methylpyrrolidone (NMP). Next, 5.14 g (24.2 mmol) of meta-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 a temperature of 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 carried out at 80°C for 4 hours. After the reaction was completed, the solution was cooled to 25°C and diluted with 200 g of tetrahydrofuran. Next, the reaction solution was added dropwise to 2.0 liters of water, stirred for 15 minutes, and then the polyimide resin was filtered. The resin was then re-slurryed with 1 liter of water for 30 minutes and filtered again, followed by re-slurrying with 1 liter of methanol and filtration. The resin was then dried under reduced pressure at 40°C for 10 hours. The dried resin was then 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 and stirred for 4 hours. After filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 liters 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-1).

[1258] The obtained polyimide (SB-1) has a weight-average molecular weight of 20,500 and a number-average molecular weight of 7,500.

[1259] according to 1 The H-NMR results showed that the imidization rate was 91%.

[1260] [Chemical Formula 111]

[1261]

[1262] <Synthetic Example SP-1: Synthesis of Polyimide Precursor (SP-1)>

[1263] 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 (manufactured by Wakayama Energy Chemical Industry Trade Corporation), 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, nitrogen was introduced, and the reaction was carried out at 200 °C for 4 hours, followed by cooling 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. After reacting at 95°C for 15 hours, the mixture was cooled to 25°C, diluted with 150 g of tetrahydrofuran, and the salts in the reaction solution were filtered off using filter paper. Then, the reaction solution was added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered off. The resin was then re-slurried 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 ORGANO CORPORATION) was added and stirred for 4 hours. After filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 liters 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 (SP-1). The obtained polyimide resin SP-1 has a weight-average molecular weight of 19,700 and a number-average molecular weight of 8,000.

[1264] [Chemical Formula 112]

[1265]

[1266] <Synthetic Example SP-5: Synthesis of Polyimide Precursor (SP-5)>

[1267] The raw materials were appropriately changed, and the polyimide precursor (SP-5) was synthesized using the same method as in synthesis example SP-1.

[1268] SP-5 has a weight-average molecular weight of 20,100 and a number-average molecular weight of 8,400.

[1269] [Chemical Formula 113]

[1270]

[1271] <Synthetic Example PA-1: Synthesis of Polyimide Precursor (PA-1)>

[1272] 7.42 g (34.0 mmol) of pyromellitic anhydride, 17.7 g (34.0 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diglyme were mixed and stirred at 60 °C for 5 hours to prepare a diester of pyromellitic anhydride and 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) with 2-hydroxyethyl methacrylate. The mixture was then cooled to -20 °C, and 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours to obtain a white precipitate of pyridinium hydrochloride.

[1273] Next, a solution obtained by dissolving 12.0 g (56.4 mmol) of meta-toluidine in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. Then, a mixture of 30.0 g of NMP and 10.0 g of water was added, and the mixture was stirred for 2 hours. Next, the polyimide precursor was precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The mixture was filtered to obtain the polyimide precursor, and then stirred again in 4 L of water for 30 minutes and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 °C for 2 days to obtain polyimide precursor (PA-1). The obtained polyimide precursor (PA-1) had a weight-average molecular weight of 16,200 and a number-average molecular weight of 7,000. The imidization rate was 3%. 1 H-NMR confirmed that the polyimide precursor (PA-1) was a resin having two repeating units represented by the following formula (PA-1).

[1274] [Chemical Formula 114]

[1275]

[1276] <Comparative Synthesis of Compound A-1>

[1277] In a drying reactor equipped with a stirrer, condenser, and a flat-bottomed connector with an 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-dioxo-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 h. Next, 50 mL of toluene was added, and the temperature was raised to 180 °C while nitrogen was bubbled through at a flow rate of 200 mL / min. The mixture was stirred for 3 h and then cooled to room temperature. The resulting 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 resulting white solid was recovered and dried under vacuum at 120 °C to obtain 90 g of polymer.

[1278] Next, 73.86 g (150.0 mmol in hydroxyl content), 21.17 g (150.0 mmol) of ethyl 2-isocyanate (hereinafter referred to as AOI, manufactured by Showa Denko KK), and 828.26 g of γ-butyrolactone (GBL) were added to 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 carried out for 6 hours. The resulting reaction solution was then diluted with acetone to prepare a diluent, which was then added dropwise to a water / methanol mixture of 2 / 1, causing a white solid to precipitate. The resulting white solid was recovered and dried under vacuum at 40°C to obtain 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 represented by the following formula (A-1) is the main component in the structure of A-1. 1 The H-NMR results showed that the cross-linking group introduction rate was 55% and the imidization rate was 99%.

[1279] [Chemical Formula 115]

[1280]

[1281] <Examples and Comparative Examples>

[1282] 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.

[1283] 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 in the table.

[1284] The obtained resin composition and the comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm.

[1285] Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

[1286] [Table 2]

[1287]

[1288] [Table 3]

[1289]

[1290] The detailed information of each component recorded in the table is as follows.

[1291] [Resin A]

[1292] •SA-1~SA-7: SA-1~SA-7 synthesized above

[1293] •PB-1: PB-1 synthesized in the above process

[1294] [Other resins]

[1295] •SB-1: SB-1 synthesized in the above process

[1296] •SP-1, SP-5: SP-1 and SP-5 synthesized above

[1297] •PA-1: PA-1 synthesized above

[1298] •A-1: A-1 synthesized in the above process

[1299] [Compound B]

[1300] •BC-1~BC-12: BC-1~BC-12 synthesized above

[1301] •BC-13: 3,3',4,4'-Biphenyltetracarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1302] [Polymerization initiators (all trade names)]

[1303] •C-1: IRGACURE OXE 01 (manufactured by BASF)

[1304] •C-2: IRGACURE OXE 02 (manufactured by BASF)

[1305] •C-3: IRGACURE OXE 03 (manufactured by BASF)

[1306] •C-4: Irgcue 784 (manufactured by BASF)

[1307] •C-5: CPI-310B (manufactured by San-Apro Ltd.)

[1308] •C-6: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1309] [Solvent]

[1310] •DMSO: Dimethyl sulfoxide

[1311] •GBL: γ-Butyrolactone

[1312] •NMP: N-methylpyrrolidone

[1313] •γ-valerolactone

[1314] •MDMPA: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.)

[1315] The entry for “DMSO / GBL” in the table indicates that a solvent was used to obtain the solvent by mixing DMSO and GBL at a mixing ratio (mass ratio) of DMSO:GBL=80:20.

[1316] [Polymerizing compounds (all trade names)]

[1317] •D-1: 1,12-Dodecanediol dimethacrylate (melting point: below 25°C)

[1318] •D-2: 1,9-Nonadiol diacrylate (melting point: below 25°C)

[1319] •D-3: 1,10-Decanediol diacrylate (melting point: below 25°C)

[1320] •D-4: SR-209 (manufactured by Sartomer Company, Inc., melting point: below 25°C)

[1321] •D-5: ADPH: Dipentadiene tetraol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., melting point: below 25°C)

[1322] •D-6: Tris(2-acryloyloxyethyl) isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1323] [Migration Inhibitor]

[1324] •E-1~E-7: Compounds with the following structures

[1325] [Chemical Formula 116]

[1326]

[1327] [Metal adhesion modifier]

[1328] •F-1~F-3: Compounds with the following structures

[1329] [Chemical Formula 117]

[1330]

[1331] •F-4: X-12-1293 (...

Claims

1. A resin composition comprising: Resin A, having polymerizable groups and having two or more optionally protected amino groups; and Compound B has a structure consisting of two or more groups selected from carboxylic acid ester groups and optionally protected carboxyl groups linked by a linking group with a chain length of 2 to 4, i.e., structure A, and a molecular weight of less than 2000.

2. The resin composition according to claim 1, wherein the resin A contains polyimide or polybenzoxazole.

3. The resin composition according to claim 1 or 2, wherein the resin A comprises a resin that is a polyimide or a polybenzoxazole and a resin that is a polyimide precursor or a polybenzoxazole precursor.

4. The resin composition according to claim 1 or 2, wherein the resin comprises a resin containing repeating units represented by the following formula (1-1) as resin A, 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 indicates that the protected amino group is optional. 1 Each group represented by formula (R-1) is represented independently, with n and m representing integers from 0 to 4, and n+m being 1 or higher. In equation (R-1), L 1 A represents a linking group with a valence of a1+1. 1 The group represents a polymerizable group, a1 represents an integer greater than or equal to 1, and * represents the group with respect to X in equation (1-1). 1 Or Y 1 The bonding sites.

5. The resin composition according to claim 4, wherein, At least one A in equation (R-1) included in equation (1-1) 1 It is vinylphenyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, epoxy, or a group containing them.

6. The resin composition according to claim 4, wherein, At least one A in equation (R-1) included in equation (1-1) 1 It is vinylphenyl.

7. The resin composition according to claim 4, wherein, The polymerizable group value of the resin A is 0.3 mmol / g to 4.0 mmol / g.

8. The resin composition according to claim 4, wherein, V in equation (1-1) 1 The group represented by the following formula (2-1) 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 * represents the bonding site with the nitrogen atom in formula (2-1).

9. The resin composition according to claim 8, wherein, In the above equation (2-1), Q 1 The group represented by formula (2-2).

10. The resin composition according to claim 1 or 2, wherein, The optionally protected amino group is a group represented by the following formula (AM-1). In formula (AM-1), Q 1 The symbol represents a hydrogen atom or a group represented by the following formula (AM-2), and * indicates a bonding site with other structures. In formula (AM-2), T 1 The symbol represents a monovalent organic group, and * indicates the bonding site with the nitrogen atom in formula (AM-1).

11. The resin composition according to claim 10, wherein, In the formula (AM-1), Q 1 It represents the group represented by formula (AM-2).

12. The resin composition according to claim 1 or 2, wherein, Compound B contains a structure represented by any of the following formulas (S-1) to (S-4) as a structure comprising said structure A. 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.

13. The resin composition according to claim 1 or 2, wherein, The content of structure A in 1g of compound B is 1mmol / g to 10mmol / g.

14. The resin composition according to claim 1 or 2, wherein, The compound B is a compound represented by the following formula (B-1). In equation (B-1), X 3 J represents a tetravalent organic group. 1 and J 2 -O- or -NR can be represented independently. N -, R N R represents a hydrogen atom or a hydrocarbon group. 3 and R 4 Each independently represents a monovalent organic group, G + They can be used to represent hydrogen cations or ammonium cations independently.

15. The resin composition according to claim 1 or 2, further comprising resin C, said resin C being a resin containing repeating units represented by formula (4-1) or formula (4-2) below and not belonging to resin A. In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each can be independently a hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of them is a monovalent organic group with 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 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.

16. The resin composition according to claim 1 or 2, wherein it contains a solvent having a boiling point of 100°C to 260°C at 1 atmosphere.

17. The resin composition according to claim 16, 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.

18. The resin composition according to claim 16, wherein it contains two or more solvents having a boiling point of 100°C to 260°C.

19. The resin composition according to claim 1 or 2, used for forming an interlayer insulating film for a rewiring layer.

20. A cured product, which is a cured product obtained by curing the resin composition of claim 1 or 2.

21. A laminate comprising two or more layers formed of the cured material of claim 20, wherein a metal layer is included between any of the layers formed of the cured material.

22. A method for manufacturing a cured material, comprising: The film forming process involves applying the resin composition of claim 1 or 2 onto a substrate to form a film.

23. The method for manufacturing a cured product according to claim 22, comprising: The exposure process involves selectively exposing the film. and In the developing process, the film is developed using a developing solution to form a pattern.

24. The method for manufacturing a cured product according to claim 22, comprising: The heating process involves heating the membrane at a temperature of 50°C to 450°C.

25. A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in claim 22.

26. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in claim 22.

27. A semiconductor device comprising the cured material of claim 20.

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