Method for producing polyimide precursor or polyamideimide precursor, method for producing resin composition, resin composition, polyimide precursor or polyamideimide precursor, transfer film, cured product, layered product, method for producing cured product, method for producing layered product, method for producing semiconductor device, and semiconductor device

Abstract

This method for producing a polyimide precursor or polyamideimide precursor includes in the stated order: (A) a step for reacting an acid anhydride derivative and a triazine chloride compound represented by general formula (1) disclosed in the description in the presence of a tertiary amine to produce a compound represented by general formula (2) disclosed in the description or a compound represented by general formula (3) disclosed in the description; and (B) a step for reacting the compound represented by general formula (2) disclosed in the description or the compound represented by general formula (3) disclosed in the description with a compound having two or more amino groups.

Description

Method for producing polyimide precursors or polyamideimide precursors, method for producing resin compositions, resin compositions, polyimide precursors or polyamideimide precursors, transfer films, cured products, laminates, methods for producing cured products, methods for producing laminates, methods for producing semiconductor devices, and semiconductor devices

[0001] The present invention relates to a method for producing a polyimide precursor or polyamideimide precursor, a method for producing a resin composition, a resin composition, a polyimide precursor or polyamideimide precursor, a transfer film, 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.

[0002] Polyimides and other resins are used in a variety of fields. These resins are used, for example, in semiconductor devices and the aerospace industry. As for methods for synthesizing polyimide precursors, which are the basis of polyimides, methods using thionyl chloride (Patent Document 1) and methods using N,N'-dicyclohexylcarbodiimide (DCC) are known. Furthermore, as described in Patent Document 2, a method for producing polyimide precursors using 4-(4,6-dialkoxy-1,3,5-triazine-2-yl)-4-alkylmorpholinium halide is also known.

[0003] International Publication No. 2015 / 052885, Japanese Patent Publication No. 2011-174020

[0004] However, conventional techniques for producing polyimide precursors or polyamide-imide precursors sometimes resulted in the generation of impurities or unwanted imidation, leaving room for improvement. There was also a need to synthesize various polyimide precursors or polyamide-imide precursors. This invention was made in view of these circumstances and aims to provide a method for producing polyimide precursors or polyamide-imide precursors that suppresses the generation of impurities and suppresses imidation, and a method for producing a resin composition including the method for producing polyimide precursors or polyamide-imide precursors. Furthermore, this invention aims to provide polyimide precursors or polyamide-imide precursors with reduced impurities and suppressed imidation, as well as a resin composition using the same, a transfer film, 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.

[0005] Examples of typical embodiments of the present invention are shown below.

[0006] [1] A method for producing a polyimide precursor or polyamideimide precursor, comprising the steps of: (A) reacting an acid anhydride derivative with a triazine chloride compound represented by the following general formula (1) in the presence of a tertiary amine to produce a compound represented by the following general formula (2) or a compound represented by the following general formula (3); and (B) reacting the compound represented by the above general formula (2) or a compound represented by the above general formula (3) with a compound having two or more amino groups.

[0007]

[0008]

[0009] In general formula (1), R １ ~R ２ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. In general formula (2), A １ and A ２ Each of these is independently an oxygen atom or -NR Ｚ Represents -. R ｚ X represents a hydrogen atom or a monovalent organic group. １represents a tetravalent organic group. R ３ ~R ６ each independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxy group. R ７ , R ８ each independently represents a hydrogen atom or a monovalent organic group. In general formula (3), A ３ represents an oxygen atom or -NR Ｚ -. R ｚ represents a hydrogen atom or a monovalent organic group. X ２ represents a trivalent group. R ９ ~R １２ each independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxy group. R １３ represents a hydrogen atom or a monovalent organic group.

[0010] [2] The method for producing a polyimide precursor or a polyamideimide precursor according to [1], wherein at least one of R ７ and R ８ in the general formula (2) has a polymerizable functional group. [3] The method for producing a polyimide precursor or a polyamideimide precursor according to [1] or [2], wherein the above step (A) and the above step (B) are carried out in one pot.

[0011] [4] The method for producing a polyimide precursor or a polyamideimide precursor according to any one of [1] to [3], wherein in the above step (A), the relationship between the content A of the triazine chloride compound and the content B of the tertiary amine on a molar basis is A≥B. [5] The method for producing a polyimide precursor or a polyamideimide precursor according to any one of [1] to [4], wherein the above step (B) is carried out in a hydroxy group-containing organic solvent.

[0012] [6] The method for producing a polyimide precursor or a polyamideimide precursor according to [5], wherein the hydroxy group-containing organic solvent is a hydroxy acid ester, a hydroxy ether, or an alkylene glycol solvent. [7] The method for producing a polyimide precursor or a polyamideimide precursor according to [5] or [6], wherein the hydroxy group-containing organic solvent is ethyl lactate or propylene glycol monomethyl ether.

[0013] [8] A method for producing a polyimide precursor or polyamideimide precursor according to any one of [1] to [7], wherein the polyimide precursor or polyamideimide precursor has a structure represented by the following general formula (N).

[0014]

[0015] In general formula (N), Y １１ *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position.

[0016] [9] A method for producing a polyimide precursor or polyamideimide precursor according to any one of [1] to [7], wherein the polyimide precursor or polyamideimide precursor has a structure represented by the following general formula (N2).

[0017]

[0018] In general formula (N2), Y １３ This represents a divalent linking group containing an aliphatic group.

[0019]

[10] A method for producing a polyimide precursor or polyamideimide precursor according to any one of [1] to [9], wherein the polyimide precursor or polyamideimide precursor comprises a structure represented by the following general formula (11).

[0020]

[0021] In general formula (11), R １５ and R １６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. * indicates the bond position.

[0022]

[11] A method for producing a polyimide precursor or polyamideimide precursor according to any one of [1] to

[10] , wherein the polyimide precursor or polyamideimide precursor contains 10 ppm to 10,000 ppm of a compound represented by the following general formula (12).

[0023]

[0024] In general formula (12), R １７ and R １８ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group.

[0025]

[12] A method for producing a polyimide precursor or polyamideimide precursor according to any one of [1] to

[11] , wherein the amide solvent content in the polyimide precursor or polyamideimide precursor is 100 ppm or less.

[0026]

[13] A method for producing a resin composition by mixing (1) a polyimide precursor or polyamideimide precursor produced by any one of the methods in [1] to

[12] , (2) a solvent, and (3) a polymerizable compound.

[0027]

[14] (11) A polyimide precursor or polyamideimide precursor having a repeating unit represented by the following general formula (23) or the following general formula (24) (2) A solvent (3) A resin composition comprising a polymerizable compound.

[0028]

[0029] In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

[0030]

[15] R in the above general formula (23) ２３ and R ２４ At least one of the groups has an ethylenically unsaturated bond, or the R of the general formula (24) above. ２５ The resin composition according to

[14] , wherein the group having an ethylenically unsaturated bond is a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group.

[0031]

[17] (12) A polyimide precursor or polyamideimide precursor having a structure represented by the following general formula (11), wherein the imidization rate of the polyimide precursor or polyamideimide precursor is less than 15%. (2) A solvent. (3) A resin composition containing a polymerizable compound.

[0032]

[0033] In general formula (11), R １５ and R １６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. * indicates the bond position.

[0034]

[18] (13) A polyimide precursor or polyamideimide precursor containing 10 ppm to 10,000 ppm of a compound represented by the following general formula (12), wherein the imidization rate of the polyimide precursor or polyamideimide precursor is less than 15%. (2) A solvent. (3) A resin composition containing a polymerizable compound.

[0035]

[0036] In general formula (12), R １７ and R １８ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group.

[0037]

[19] A resin composition according to any one of

[14] to

[18] , further comprising (4) a polymerization initiator.

[0038]

[20] A transfer film comprising: a support film; and a composition layer comprising: (11) a polyimide precursor or polyamideimide precursor having repeating units represented by the following general formula (23) or the following general formula (24); and (3) a resin composition comprising a polymerizable compound.

[0039]

[0040] In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

[0041]

[21] The transfer film according to

[20] , wherein the amide solvent content in the resin composition is 100 ppm or less.

[0042]

[22] A cured product obtained by curing the resin composition described in any one of items

[14] to

[19] .

[0043]

[23] A laminate comprising two or more layers made of the cured product described in

[22] , wherein a metal layer is included between any of the layers made of the cured product.

[24] A method for producing a cured product, comprising a film-forming step of applying the resin composition described in any one of

[14] to

[19] onto a substrate to form a film.

[0044]

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

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

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

[24] or

[25] .

[27] A semiconductor device comprising the cured product according to

[22] .

[0045]

[28] A polyimide precursor or polyamideimide precursor having a repeating unit represented by the following general formula (23) or the following general formula (24).

[0046]

[0047] In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

[0048] A polyimide precursor or polyamide-imide precursor containing a structure represented by the following general formula (11), wherein the imidization rate of the polyimide precursor or polyamide-imide precursor is less than 15%.

[0049]

[0050] In the general formula (11), R １５ and R １６ each independently represent a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxy group. * represents the bonding position.

[0051]

[30] A polyimide precursor or polyamide-imide precursor containing 10 ppm or more and 10,000 ppm or less of a compound represented by the following general formula (12), wherein the imidization rate of the polyimide precursor or polyamide-imide precursor is less than 15%.

[0052]

[0053] In the general formula (12), R １７ and R １８ each independently represent a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxy group.

[0054]

[31] The polyimide precursor or polyamide-imide precursor according to

[28] , wherein R ２３ , R ２４ each independently represent a group represented by the following general formula (4A).

[0055]

[0056] In the general formula (4A), A represents a (q + 1)-valent organic group, L represents an oxygen atom, or N(R ４６ )(R ４７ )(R ４６ , R ４７ each independently represent a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group), and R ４３ to R ４５Each independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, q represents an integer of 1 to 4. * represents the bonding position.

[0057]

[32] R in the general formula (23) above ２３ , R ２４ Each independently represents a group represented by the following general formula (4), the polyimide precursor or polyamide-imide precursor according to

[28] .

[0058]

[0059] In the general formula (4), A represents a (q + 1)-valent organic group, and R ４３ to R ４５ Each independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, q represents an integer of 1 to 4. * represents the bonding position.

[0060]

[33] The polyimide precursor or polyamide-imide precursor according to

[32] , wherein R in the general formula (4) is a hydrogen atom. ４５

[0061] According to the present invention, there can be provided a method for producing a polyimide precursor or a polyamide-imide precursor in which the generation of impurities is suppressed and imidization is suppressed, and a method for producing a curable resin composition including the method for producing a polyimide precursor or a polyamide-imide precursor. Further, according to the present invention, there can be provided a polyimide precursor or a polyamide-imide precursor in which impurities are reduced and imidization is suppressed, and a resin composition, a transfer film, a cured product, and a laminate using the same.

[0062] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substitution or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Furthermore, examples of light used for exposure include the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV), X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate," or either of them; "(meth)acrylic" means both "acrylic" and "methacrylic," or either of them; and "(meth)acryloyl" means both "acryloyl" and "methacryloyl," or either of them. In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of the components of the composition excluding the solvent. Also in this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer (sometimes referred to as a "resin layer"), the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH. In this specification, “organic group” means a group containing at least one carbon atom. In this specification, “preferred embodiment” means “more preferred embodiment.”

[0063] [Method for Producing Polyimide Precursors or Polyamideimide Precursors] First, the method for producing polyimide precursors or polyamideimide precursors of the present invention will be described. The method for producing polyimide precursors or polyamideimide precursors of the present invention comprises, in this order: (A) a step of reacting an acid anhydride derivative with a triazine chloride compound represented by the following general formula (1) in the presence of a tertiary amine to produce a compound represented by the following general formula (2) or a compound represented by the following general formula (3) (hereinafter also referred to as "step 1"), and (B) a step of reacting the compound represented by the above general formula (2) or a compound represented by the above general formula (3) with a compound having two or more amino groups (hereinafter also referred to as "step 2").

[0064]

[0065]

[0066] In general formula (1), R １ ~R ２ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. In general formula (2), A １ and A ２ Each is independently an oxygen atom or -NR Ｚ Represents -. R ｚ X represents a hydrogen atom or a monovalent organic group. １ R represents a tetravalent organic group. ３ ~R ６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. ７ , R ８ Each of these independently represents a hydrogen atom or a monovalent organic group. In general formula (3), A ３ is an oxygen atom or -NR Ｚ Represents -. R ｚ X represents a hydrogen atom or a monovalent organic group. ２ R represents a trivalent group. ９ ~R １２Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. １３ represents a hydrogen atom or a monovalent organic group.

[0067] The present invention provides a method for producing a polyimide precursor or polyamide-imide precursor that suppresses impurities and reduces imidation. The mechanism by which the present invention achieves the above effects is not yet clear, but the inventors have the following hypothesis. However, the present invention is not limited in any way by the following hypothesis. As described above, a known method for synthesizing a polyimide precursor or polyamide-imide precursor is to use thionyl chloride. When thionyl chloride is used in this way, acidic impurities containing sulfur atoms and highly polar by-products tend to be generated. The present invention provides a method for producing a polyimide precursor or polyamide-imide precursor that, in step 1, uses a triazine chloride compound represented by the above general formula (1) and a tertiary amine, thereby reducing the sulfur atom content in the polyimide precursor or polyamide-imide precursor.

[0068] Furthermore, as mentioned above, known methods for synthesizing polyimide precursors or polyamideimide precursors include a method using N,N'-dicyclohexylcarbodiimide (DCC) and a method using 4-(4,6-dialkoxy-1,3,5-triazine-2-yl)-4-alkylmorpholinium halide. However, these methods require the addition of basic compounds under reaction conditions, which tends to increase the basicity under reaction conditions, and thus some of the resulting polyimide precursors or polyamideimide precursors tend to undergo unintended cyclization. The method for producing polyimide precursors or polyamideimide precursors of the present invention uses a triazine chloride compound represented by the above general formula (1), allowing the reaction to proceed without using an excess of basic compounds. This prevents an excessive increase in the basicity of the reaction system, thus suppressing unintended imidization.

[0069] The present invention provides a polyimide precursor or polyamide-imide precursor, and a resin composition using the same, in which impurities are reduced and imidation is suppressed. When forming a coated film using the above-mentioned polyimide precursor or polyamide-imide precursor composition (resin composition), the resin composition can be applied uniformly (excellent in-plane uniformity). As described above, the polyimide precursor or polyamide-imide precursor obtained by the method for producing the polyimide precursor or polyamide-imide precursor of the present invention has suppressed imidation. Generally, in the production of a polyimide precursor or polyamide-imide precursor, if unintended imidation progresses, or if the so-called imidation rate is high, the number of imide rings with different polarities increases, which tends to worsen the compatibility with the constituent units of the polyimide precursor or polyamide-imide precursor. In addition, aggregation of imide rings may occur, making it easy to form a physical gel, which is thought to result in poor coatability. However, in the polyimide precursor or polyamide-imide precursor of the present invention, imidation is suppressed to a low level, so the resin composition can be applied uniformly, and excellent in-plane uniformity is considered to be achieved. Furthermore, when a film formed using a resin-containing composition (resin composition) is used in semiconductor devices, it is required to have the following excellent PCT characteristics. The Pressure Cooker Test (PCT) is a well-known test method for environmental reliability testing of electronic equipment. In such tests, it is required that the wiring does not corrode and that the resin film is less prone to abnormalities and foreign matter (also known as having excellent "PCT properties"). The polyimide precursor obtained by the method for producing the polyimide precursor or polyamide-imide precursor of the present invention has reduced impurities (sulfur atoms), and therefore, when a film is formed using a resin composition containing the polyimide precursor or polyamide-imide precursor, it is considered to have excellent PCT properties. When the polyimide precursor or polyamide-imide precursor obtained in this way is applied to a resin composition, it is considered that a film can be formed that has excellent in-plane uniformity in the coated film after application, as well as excellent PCT properties.

[0070] The steps included in the method for producing the polyimide precursor or polyamideimide precursor of the present invention will be described in detail below. [(A) A step in which an acid anhydride derivative and a triazine chloride compound represented by general formula (1) are reacted in the presence of a tertiary amine to produce a compound represented by general formula (2) or a compound represented by general formula (3) (hereinafter also referred to as "step 1" or "step (A)")]

[0071]

[0072]

[0073] In general formula (1), R １ ~R ２ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. In general formula (2), A １ and A ２ Each of these is independently an oxygen atom or -NR Ｚ Represents -. R ｚ X represents a hydrogen atom or a monovalent organic group. １ R represents a tetravalent organic group. ３ ~R ６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. ７ , R ８ Each of these independently represents a hydrogen atom or a monovalent organic group. In general formula (3), A ３ is an oxygen atom or -NR Ｚ Represents -. R ｚ X represents a hydrogen atom or a monovalent organic group. ２ R represents a trivalent group. ９ ~R １２ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. １３ represents a hydrogen atom or a monovalent organic group.

[0074] (Acid anhydride derivatives) Acid anhydride derivatives are compounds having a carboxyl group derived from acid anhydrides, although they are not particularly limited. Acid anhydrides are not particularly limited, but examples include tetracarboxylic dianhydrides. Tetracarboxylic dianhydrides are preferably represented by the following formula (O).

[0075]

[0076] In formula (O), R １１５ R represents a tetravalent organic group. １１５ The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6). In formula (5) or formula (6), * independently represents a bonding site with another structure.

[0077]

[0078] In formula (5), R １１２ The linking group is a single bond or a divalent linking group, preferably a single bond or a C1-C10 aliphatic hydrocarbon group, -O-, -CO-, and -NHCO-, which may be substituted with a fluorine atom, and a group selected from combinations thereof, and more preferably a single bond or a group selected from a C1-C3 alkylene group, -O-, and -CO-, which may be substituted with a fluorine atom, and -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ It is even more preferable that the group is a divalent group selected from the group consisting of -, -O-, and -CO-.

[0079] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (4,4'-biphthalic acid dianhydride) (BPDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride. Examples include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

[0080] Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0081] Furthermore, examples of acid anhydrides include the anhydrides of tricarboxylic acid compounds. Specifically, these are compounds in which two carboxyl groups of a tricarboxylic acid compound have been converted into anhydrides. In this invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound.

[0082] Specifically, preferred tricarboxylic acid compounds include, for example, a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred tricarboxylic acid compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0083] 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-naphthalentricarboxylic acid, and phthalic acid (or phthalic anhydride) and benzoic acid with a single bond, -O-, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -SO ２ - Or, compounds linked by phenylene groups. Examples of tricarboxylic acid compounds in which the two carboxyl groups have been converted to anhydrides include trimellitic anhydride and hemimellitic anhydride.

[0084] Acid anhydrides may be used individually or in combination of two or more.

[0085] In one preferred embodiment, the acid anhydride derivative can be a compound represented by the following general formula (Q) or a compound represented by the general formula (R).

[0086]

[0087] In general formula (Q), A １ and A ２ Each of these is independently an oxygen atom or -NR Ｚ Represents -. R ｚ X represents a hydrogen atom or a monovalent organic group. １ R represents a tetravalent organic group. ７ , R ８ Each of these independently represents a hydrogen atom or a monovalent organic group. In general formula (R), A３ is an oxygen atom or -NR Ｚ Represents -. R ｚ X represents a hydrogen atom or a monovalent organic group. ２ R represents a trivalent group. １３ represents a hydrogen atom or a monovalent organic group.

[0088] In general formula (Q), A １ A ２ , R Ｚ , X １ , R ７ , and R ８ In the general formula (2) described below, A １ A ２ , R Ｚ , X １ , R ７ , and R ８ The same applies, and the preferred range is also the same. In general formula (R), A ３ , R Ｚ , X ２ , and R １３ In the general formula (3) described below, A ３ , R Ｚ , X ２ , and R １３ The same applies to the preferred range.

[0089] In addition, as a preferred embodiment, the acid anhydride derivative can be a compound represented by the following general formula (S) or a compound represented by the general formula (T).

[0090]

[0091] In general formulas (S) and (T), Rx independently represents a monovalent organic group.

[0092] The monovalent organic group is not particularly limited, but examples include alkyl groups having 1 to 10 carbon atoms. The alkyl group may have substituents. The substituents are not particularly limited, but examples include (meth)acryloyloxy groups and (meth)acrylamide groups.

[0093] In a preferred embodiment, the acid anhydride derivative is preferably a compound obtained by the reaction of an acid anhydride with an alcohol. Any known alcohol can be used. Furthermore, the reaction is not particularly limited and can be carried out under known conditions.

[0094] The acid anhydride derivative may be used individually or in combination of two or more.

[0095] (Triazine chloride compounds represented by general formula (1))

[0096]

[0097] In general formula (1), R １ ~R ２ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. The alkyl group in the alkoxy group may be linear or branched, and an alkyl group having 1 to 10 carbon atoms is preferred. Specifically, examples of alkyl groups in the alkoxy group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. The alkyl group in the alkoxy group is preferably a methyl group, an ethyl group, or an n-propyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. The alkoxy group may further have substituents. The substituents are not particularly limited, but examples include an aryl group and a (meth)acryloyloxy group.

[0098] The aryl group in the aryloxy group may be monocyclic or polycyclic, and an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of the aryl group in the aryloxy group include a phenyl group, a naphthyl group, and the like. The aryloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups.

[0099] The aralkyl group in the aralkyloxy group can be an aralkyl group having 7 to 11 carbon atoms. Specifically, the aralkyl group in the aralkyloxy group can be a benzyl group, etc. The aralkyloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups, etc.

[0100] Specific examples of triazine chloride compounds represented by general formula (1) (hereinafter also simply referred to as "triazine chloride compounds") are shown below, but the present invention is not limited to these.

[0101]

[0102] The triazine chloride compound represented by general formula (1) may be used alone or in combination of two or more types. Since it is preferable to use the triazine chloride compound in excess of the carboxyl groups of the acid anhydride derivative, the amount used is preferably 1 to 4 equivalents, more preferably 1.1 to 3 equivalents, and even more preferably 1.2 to 1.7 equivalents.

[0103] (Tertiary amines) Examples of tertiary amines include trialkylamines (e.g., triethylamine, trimethylamine, N-methyldiethylamine), N-alkylmorpholines (e.g., N-methylmorpholine, N-ethylmorpholine, N-isobutylmorpholine), pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine, 1,8-diazabicyclo[5.4.0]-7-undensene, and 1,4-diazabicyclo[2.2.2]octane (DABCO), among which triethylamine, N-methylmorpholine, and pyridine are preferred. In a preferred embodiment, from the viewpoint of reactivity, the pKa of the tertiary amine is preferably 6 to 13, more preferably 6.5 to 12, and particularly preferably 7 to 11. Preferred tertiary amines include trialkylamines such as triethylamine (pKa = 10.7), and N-alkylmorpholines such as N-methylmorpholine (pKa = 7.4) and N-ethylmorpholine (pKa = 7.6).

[0104] The tertiary amine may be used individually or in combination of two or more. The amount of tertiary amine used is usually 1 to 6 moles, preferably 2 to 5 moles, relative to 1 mole of carboxyl groups (or the total amount if there are multiple) of the acid anhydride derivative used in the reaction.

[0105] In step (A), it is preferable that the relationship between the content A of the triazine chloride compound and the content B of the tertiary amine on a molar basis is A ≥ B.

[0106] Step 1 is preferably carried out in the presence of a solvent. The solvent is typically an organic solvent. There may be one or more organic solvents. The organic solvent that can be used in this reaction is preferably a good solvent for acid anhydride derivatives, triazine chloride compounds, tertiary amines, and the resulting polyimide precursor. Examples of organic solvents include diethylene glycol dimethyl ether (also called diglyclyme), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone. Examples of organic solvents include hydroxyl group-containing organic solvents. Examples of hydroxyl group-containing organic solvents include hydroxy acid ester solvents, hydroxy ether solvents, and alkylene glycol solvents. Examples of hydroxy acid ester solvents include methyl lactate, ethyl lactate, butyl lactate, and methyl 2-hydroxyisobutyrate. Examples of hydroxyether-based solvents include ethylene glycol monoethyl ether and propylene glycol monomethyl ether (PGME). Examples of alkylene glycol-based solvents include ethylene glycol, diethylene glycol, or propylene glycol. In a preferred embodiment, the hydroxyl group-containing organic solvent is preferably ethyl lactate or propylene glycol monomethyl ether.

[0107] In step 1, the method for reacting the acid anhydride derivative and the triazine chloride compound in the presence of a tertiary amine involves adding the triazine chloride compound little by little to a solution in which the acid anhydride derivative is dissolved / dispersed, taking care to avoid exothermic reactions. Then, a tertiary amine solution dissolved in a solvent, or a liquid tertiary amine, is added dropwise, taking care to avoid exothermic reactions. The temperature is not particularly limited, but for example, it can be -15°C to 30°C. The reaction time is also not particularly limited, but for example, it can be 10 minutes to 4 hours. The reaction vessel may also be stirred. Furthermore, in the compound represented by general formula (2), -C(=O)-A １ -R ７ , -C(=O)-A ２ -R ８ In introducing such a structure, compounds for introducing such a structure can be used as appropriate. Known reaction conditions can be used. In addition, in the compound represented by general formula (3), -C(=O)-A ３ -R １３ In introducing such a structure, compounds can be used as appropriate. Known reaction conditions can be used.

[0108] In step 1, a compound represented by the following general formula (2) or a compound represented by the following general formula (3) is produced.

[0109]

[0110] In general formula (2), A １ and A ２ Each of these is independently an oxygen atom or -NR Ｚ Represents -. R ｚ X represents a hydrogen atom or a monovalent organic group. １ R represents a tetravalent organic group. ３ ~R ６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. ７ , R ８ Each of these independently represents a hydrogen atom or a monovalent organic group. In general formula (3), A ３ is an oxygen atom or -NR Ｚ Represents -. R ｚX represents a hydrogen atom or a monovalent organic group. ２ R represents a trivalent group. ９ ~R １２ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. １３ represents a hydrogen atom or a monovalent organic group.

[0111] A １ and A ２ Each is independently an oxygen atom or -NR ｚ R represents a negative sign, and an oxygen atom is preferred. ｚ X represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred. １ R in equation (O) １１５ This is synonymous with the same thing, and the preferred range is also similar.

[0112] R ３ ~R ６ The alkyl group in the alkoxy group may be linear or branched, and an alkyl group having 1 to 10 carbon atoms is preferred. Specifically, examples of alkyl groups in the alkoxy group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups. The alkyl group in the alkoxy group is preferably a methyl, ethyl, or n-propyl group, more preferably a methyl or ethyl group, and even more preferably a methyl group. The alkoxy group may further have substituents. The substituents are not particularly limited, but examples include aryl groups and (meth)acryloyloxy groups.

[0113] The aryl group in the aryloxy group may be monocyclic or polycyclic, and an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of the aryl group in the aryloxy group include a phenyl group, a naphthyl group, and the like. The aryloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups.

[0114] The aralkyl group in the aralkyloxy group can be an aralkyl group having 7 to 11 carbon atoms. Specifically, the aralkyl group in the aralkyloxy group can be a benzyl group, etc. The aralkyloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups, etc.

[0115] A ３ is an oxygen atom or -NR ｚ R represents a negative sign, and an oxygen atom is preferred. ｚ represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred.

[0116] X ２ X represents a trivalent group, preferably a trivalent organic group. ２ Examples of these groups include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these groups by single bonds or linking groups. Preferably, these groups include linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these groups by single bonds or linking groups. More preferably, these groups include aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. Examples of the linking groups include -O-, -S-, -C(=O)-, and -S(=O). ２-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are preferred, and -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are more preferred. As for the 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. As for the halogenated alkylene group, halogenated alkylene groups having 1 to 20 carbon atoms are preferred, halogenated alkylene groups having 1 to 10 carbon atoms are more preferred, and halogenated alkylene groups having 1 to 4 carbon atoms are even more preferred. Furthermore, as for the halogen atom in the halogenated alkylene group, examples include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include the (ditrifluoromethyl)methylene group. The above arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0117] Also, X ２ It is preferable that it be derived from the anhydride of a tricarboxylic acid compound. The tricarboxylic acid compound is as described above.

[0118] R ９ ~R １２The alkyl group in the alkoxy group may be linear or branched, and an alkyl group having 1 to 10 carbon atoms is preferred. Specifically, examples of alkyl groups in the alkoxy group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups. The alkyl group in the alkoxy group is preferably a methyl, ethyl, or n-propyl group, more preferably a methyl or ethyl group, and even more preferably a methyl group. The alkoxy group may further have substituents. The substituents are not particularly limited, but examples include aryl groups and (meth)acryloyloxy groups.

[0119] The aryl group in the aryloxy group may be monocyclic or polycyclic, and an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of the aryl group in the aryloxy group include a phenyl group, a naphthyl group, and the like. The aryloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups.

[0120] The aralkyl group in the aralkyloxy group can be an aralkyl group having 7 to 11 carbon atoms. Specifically, the aralkyl group in the aralkyloxy group can be a benzyl group, etc. The aralkyloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups, etc.

[0121] R ７ , R ８ , and R １３ Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes an alkyl group (linear, branched, or cyclic), an alkenyl group (linear or branched), an aromatic group, or a polyalkylene oxy group. The number of carbon atoms in the monovalent organic group is not particularly limited, but is, for example, 1 to 30. ７ and R ８ It is preferable that at least one of them has a polymerizable functional group. ７ and R ８It is more preferable that both have polymerizable functional groups. Examples of polymerizable functional groups include groups having ethylenically unsaturated bonds. In one preferred embodiment, R １３ It is preferable that it has a polymerizable functional group, and more preferably that it has a group having an ethylenically unsaturated bond. In addition, as a preferred embodiment, R ７ and R ８ It is more preferable that at least one of the groups has a group having an ethylenically unsaturated bond, and both groups have a group having an ethylenically unsaturated bond. ７ and R ８ It is also preferable that at least one of the groups has two or more ethylenically unsaturated bonds.

[0122] Groups having an ethylenically unsaturated bond are polymerizable groups, and radical polymerizable groups. Examples of groups having an ethylenically 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 group), (meth)acrylamide groups, (meth)acryloyloxy groups, groups represented by the following general formula (4A), and groups represented by the following general formula (4). In a preferred embodiment, the group having an ethylenically unsaturated bond is preferably a vinyl group, allyl group, isoallyl group, 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group, (meth)acrylamide group, or (meth)acryloyloxy group. In a preferred embodiment, the group having an ethylenically unsaturated bond is preferably a group represented by the general formula (4A) or a group represented by the general formula (4), and more preferably a group represented by the following general formula (4).

[0123]

[0124] In general formula (4A), A represents an organic group with a (q+1) valency, and L represents an oxygen atom, or N(R) ４６ ) (Caution ４７ ) (Caution ４６ , R ４７ Each of these independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and R ４３ ~R ４５Each of these independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and q represents an integer from 1 to 4. * indicates the bond position.

[0125]

[0126] In general formula (4), A represents an organic group with (q+1) valence, and R ４３ ~R ４５ Each of the symbols independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and q represents an integer from 1 to 4. * indicates the bond position.

[0127] In general formulas (4A) and (4), A represents an organic group with a (q+1) valency. The divalent linking group when q is 1 is described below. Examples of divalent linking groups include alkylene groups with 2 to 12 carbon atoms, and -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or a polyalkylene oxy group. Examples of divalent linking groups include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH ２ CH(OH)CH ２ -Polyalkylene oxy groups are examples, including alkylene groups such as ethylene groups and propylene groups, and -CH ２ CH(OH)CH ２ -, cyclohexyl groups and polyalkylene oxy groups are more preferred, and alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. A (q+1) valent organic group (q is 2 or more) is a group obtained by removing (q-1) hydrogen atoms from a divalent linking group.

[0128] In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be random, have blocks, or have alternating patterns. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, even more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, etc. Furthermore, the number of alkylene oxy groups contained in the polyalkylene oxy group (the number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred configurations for the number of repeating ethylene oxy groups in these groups are as described above.

[0129] In general formulas (4A) and (4), R ４３ ~R ４５ Each of these independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group. ４３ ~R４５ The aliphatic hydrocarbon group is not particularly limited, but examples include alkyl groups. Examples of alkyl groups include methyl groups and ethyl groups. The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but for example, 1 to 10 carbon atoms are preferred, 1 to 6 carbon atoms are more preferred, and 1 to 3 carbon atoms are even more preferred. The aliphatic hydrocarbon group may further have substituents. R ４３ ~R ４５ It is preferable that this represents a hydrogen atom or an aliphatic hydrocarbon group.

[0130] In general formulas (4A) and (4), q represents an integer from 1 to 4, preferably an integer from 1 to 2, and more preferably 1.

[0131] In general formula (4A), L is an oxygen atom, or N(R) ４６ ) (Caution ４７ ) (Caution ４６ , R ４７ Each of these independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and preferably represents an oxygen atom. ４６ , R ４７ Each of these independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group. ４６ , R ４７ As for the aliphatic hydrocarbon group, the above-mentioned R ４３ ~R ４５ Examples include aliphatic hydrocarbon groups, and preferred examples are similar. The aliphatic hydrocarbon group may further have substituents. R ４６ , R ４７ It is preferable that this represents a hydrogen atom or an aliphatic hydrocarbon group.

[0132] R ７ and R ８ At least one of these may be a polarity changing group such as an acid-degradable group. Also, R １３However, it may also be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl groups or tetrahydrofuranyl groups are preferred.

[0133] In one preferred embodiment, -A of the above general formula (2) １ -R ７ , -A ２ -R ８ Preferably, at least one of these represents a group represented by the following formula (V).

[0134]

[0135] (In formula (V), Z ４ and Z ５ Each of these independently represents a monovalent organic group, and * represents a bonding site with other structures. ４ and Z ５ They may be joined together to form a ring.

[0136] Z ４ and Z ５ The monovalent organic group is, as a monovalent organic group, the above R ７ , R ８ Examples of monovalent organic groups can be given, and the preferred range is similar. Z ４ and Z ５The monovalent organic group is preferably an alkyl group or an alkenyl group. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 12. The alkenyl group may be linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 2 to 20, and more preferably 2 to 12. Z ４ and Z ５ These elements may be bonded together to form a ring. The resulting ring is not particularly limited and may be monocyclic or polycyclic. It may also be an aromatic ring or a non-aromatic ring (for example, a non-aromatic heterocyclic ring).

[0137] In one preferred embodiment, -A of the above general formula (3) ３ -R １３ It is preferable that represents the group represented by the above formula (V).

[0138] The group represented by the above formula (V) is preferably the group represented by the following formula (W).

[0139]

[0140] In formula (W), Cy represents a nitrogen-containing heterocycle or aromatic ring, and * represents a bonding site with other structures.

[0141] The nitrogen-containing heteroring of Cy may be monocyclic or polycyclic. The number of carbon atoms in the nitrogen-containing heteroring is not particularly limited, but is, for example, 3 to 20, preferably 3 to 15, and more preferably 3 to 10. The nitrogen-containing heteroring may have heteroatoms other than nitrogen (nitrogen atoms). Examples of nitrogen-containing heterorings include pyrrolidine rings, piperidine rings, and morpholine rings. The aromatic ring of Cy may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is not particularly limited, but is, for example, 5 to 20, preferably 5 to 15, and more preferably 5 to 10. Examples of aromatic rings include pyridine rings and indole rings.

[0142] The resulting compound represented by general formula (2) or general formula (3) may be isolated and purified before being used in step 2. Known methods can be used for the isolation and purification steps. Alternatively, the compound represented by general formula (2) or general formula (3) may be used directly in step 2 without isolation or purification (so-called "one-pot" method). The one-pot method will be described later.

[0143] [(B) A step of reacting a compound represented by general formula (2) or a compound represented by general formula (3) with a compound having two or more amino groups (hereinafter also referred to as "step 2" or "step (B)")] The compound represented by general formula (2) and the compound represented by general formula (3) are as described above. The compound having two or more amino groups (hereinafter also referred to as "compound (N)") is not particularly limited, but diamines can be given as an example. Diamines are not particularly limited, but include, for example, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamines; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether (also known as "4,4'-oxydianiline"), 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy- 4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetog Anamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoro Propane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,Examples include at least one diamine selected from 5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotidine, and 4,4'-diaminoquaterphenyl.

[0144] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0145] Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, are also preferably used.

[0146] In a preferred embodiment, compound (N) may also be a compound having three or more amino groups. Compounds having three or more amino groups are not particularly limited, but examples include 3,3'-diaminobenzidine (DAB), 3,4,4'-triaminodiphenyl ether, 1,2,4-triaminobenzene, 4-(4-aminophenyl)benzene-1,2-diamine, 4-(3,4-diaminophenoxy)-1,2-benzenediamine, bis(3,4-diaminodiphenyl)methanone, 2-amino-4-[(3,4-diaminophenoxyl)sulfonyl]phenylamine, triphenylene-2,3,6,7,10,11-hexaamine, phenazine-2,3,7,8-tetraamine, bis(3,4-diaminodiphenyl)hexafluoropropane, 2,4,6-triaminopyrimidine, and the like. Compounds having three or more amino groups may also be the hydrochloride salts of the aforementioned compounds having three or more amino groups. The number of amino groups in compound (N) is not particularly limited, but for example, it is five or less.

[0147] The amount of compound (N) used is preferably 0.7 to 1.1 moles, more preferably 0.8 to 1.0 moles, and even more preferably 0.85 to 0.95 moles, per mole (total amount if there are multiple) of the compound represented by general formula (2) or general formula (3).

[0148] Step 2 is preferably carried out in the presence of a solvent. The solvent is typically an organic solvent. There may be one or more organic solvents. The organic solvent that can be used in this reaction is preferably a good solvent for acid anhydride derivatives, triazine chloride compounds, tertiary amines, and the resulting polyimide precursor. Examples of organic solvents include diethylene glycol dimethyl ether (also called diglyme), N-methylpyrrolidone (NMP), N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone.

[0149] Examples of organic solvents include hydroxyl group-containing organic solvents. Examples of hydroxyl group-containing organic solvents include hydroxy acid ester solvents, hydroxy ether solvents, or alkylene glycol solvents. Examples of hydroxy acid ester solvents include methyl lactate, ethyl lactate, butyl lactate, or methyl 2-hydroxyisobutyrate. Examples of hydroxy ether solvents include ethylene glycol monoethyl ether and propylene glycol monomethyl ether (PGME). Examples of alkylene glycol solvents include ethylene glycol, diethylene glycol, or propylene glycol. In a preferred embodiment, the hydroxyl group-containing organic solvent is preferably ethyl lactate or propylene glycol monomethyl ether. In a preferred embodiment, it is preferable to carry out step (B) in a hydroxyl group-containing organic solvent.

[0150] The temperature for reacting the compound represented by the general formula (2) or the compound represented by the general formula (3) with the compound (N) is not particularly limited, and examples thereof include -10 to 10°C. Also, the reaction time is not particularly limited, and examples thereof include 0.5 to 6 hours. After reacting at the above temperature, if necessary, further heating may be performed to stir the reaction vessel. The temperature for further heating is, for example, 10 to 60°C, and the stirring time is, for example, 1 to 6 hours.

[0151] In Step 2, it is preferable to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds. The basic compound can be appropriately determined according to the raw materials, and examples thereof include triethylamine, diisopropylethylamine, pyridine, methylpyridine, dimethylpyridine, trimethylpyridine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, and the like. The method for producing the polyimide precursor or polyamideimide precursor of the present invention may include a step of precipitating a solid after Step 2. Specifically, after the reaction solution is filtered as necessary, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohol, or a mixed solution thereof, and the polymer component is precipitated to be precipitated as a solid and dried to obtain a precursor. In order to improve the purification degree, operations such as redissolving, reprecipitating, and drying the precursor may be repeated.

[0152] It is also preferable to perform the above Step (A) and the above Step (B) in one pot (one-pot synthesis). One-pot synthesis represents a synthesis in which reactants are sequentially (or at once) placed in a reaction vessel and a plurality of steps are continuously reacted. In the present invention, it is preferable because the purification process of the compound represented by the general formula (2) or the compound represented by the general formula (3) obtained in Step 1 becomes unnecessary, and a polyimide precursor or a polyamideimide precursor can be efficiently obtained.

[0153] The method for producing the polyimide precursor or polyamideimide precursor of the present invention may further have the following Step 3.

[0154] [Step of treating with an ion exchange resin (also referred to as "Step 3")] Specifically, Step 3 represents the step of adding an ion exchange resin to the reaction system (solution) in Step 2. Further, in Step 2, the precursor obtained by performing the precipitation step may be dissolved in a solvent, and an ion exchange resin may be added to the resulting solution. The solvent is not particularly limited, and the solvent in Step 1, tetrahydrofuran (THF), etc. can be used. By treating with an ion exchange resin, the amount of impurities in the precursor can be reduced. Examples of impurities whose amount can be reduced include chloride ions.

[0155] The ion exchange resin is not particularly limited, and an amphoteric ion exchange resin or an anion exchange resin can be used. Examples of amphoteric ion exchange resins include MB-1, MB-2, MB-4, EG-4A-HG, EG-5A-HG, ESP-1, ESP-2 (all manufactured by Organo Corporation). Examples of anion exchange resins include Amberlyst ＴＭ B20-HG·DRY, Amberlyst A21, Amberlyst HPR4780, Amberlyst IRA67, Amberlyst IRA96SB, Amberlyst IRA98, AMBERJET ＴＭ UP6040, Amberjet series (all manufactured by Organo Corporation), Diaion ＴＭ series (manufactured by Mitsubishi Chemical Corporation), Relite ＴＭ JA450 (manufactured by Mitsubishi Chemical Corporation), Amberlite IRA96SB (manufactured by Organo Corporation) can be mentioned.

[0156] The products manufactured by Organo Corporation described below can also be used. https: / / ier.organo.co.jp / product / material.html#product1

[0157] Also, the products manufactured by Mitsubishi Chemical Corporation described below can be used. https: / / www.m-chemical.co.jp / products / departments / mcc / ion / product / 1200472_7274.html

[0158] The amount of ion exchange resin used is not particularly limited and can be selected as appropriate. Preferably, the amount of ion exchange resin used is equal to or greater than the yield of the resulting resin.

[0159] The method for producing a polyimide precursor or polyamide-imide precursor of the present invention may include a step of precipitating a solid after step 3. Specifically, after filtering off the ion exchange resin coexisting in the reaction solution, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated to precipitate as a solid, which is then dried to obtain a polyimide precursor or polyamide-imide precursor. To improve the degree of purity, the polyimide precursor or polyamide-imide precursor may be repeatedly redissolved, reprecipitation, dried, etc.

[0160] The weight-average molecular weight (Mw) of the polyimide precursor or polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, even more preferably 5,000 to 50,000, and still more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000. The degree of dispersion of the molecular weight of the polyimide precursor or polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and still more preferably 2.0 or higher.

[0161] It is preferable that the sulfur element content in the polyimide precursor or polyamideimide precursor is less than 0.5% by mass relative to the total mass of the polyimide precursor or polyamideimide precursor.

[0162] The sulfur element content in the above precursor is measured as follows.

[0163] [Quantitative determination of sulfur element in resin (precursor) by combustion ion chromatography] Approximately 50 mg of the sample is placed on a sample board, and after weighing, measurement is performed by combustion ion chromatography under the following conditions. Sample combustion temperature: 900°C (inlet) / 1000°C (outlet) Absorption solution conditions: Approximately 0.01% H ２ O ２aq. +2ppm KH ２ PO ４ aq. (Internal standard) Absorption volume: 5 mL Column: Dionex IonPac AS22 Eluent: 4.5 mmol / L Na ２ CO ３ + 1.4 mmol / L NaHCO ３ Flow rate: 1.2 mL / min Column temperature: 35°C Absorption solution injection volume: 100 μL Concentration correction: Two constant-volume check measurements are performed, the amount of sulfur element in each sample is quantified, and the average value is used.

[0164] The sulfur content in the polyimide precursor or polyamideimide precursor is more preferably 100 ppm or less, even more preferably 10 ppm or less, and particularly preferably less than 5 ppm, from the viewpoint of preventing corrosion of metal wiring.

[0165] [Imidization rate of polyimide precursor or polyamideimide precursor] The imidization rate of polyimide precursor or polyamideimide precursor is １ It is calculated from the results of 1H-NMR (nuclear magnetic resonance) measurements. １ H-NMR spectrometer: Bruker, 400 MHz. Measurement solvent: Deuterium DMSO (dimethyl sulfoxide). The imidization rate is calculated from the integral ratio of the proton peaks of the benzene ring in the unit corresponding to the compound having two or more amino groups. (I): Unimidized benzene ring proton: Integral ratio of the proton peak around 6.9 ppm. (II): Imidized benzene ring proton: Integral ratio of the proton peak around 7.1 ppm. The imidization rate is expressed as follows: (Imidization rate) = II / (I + II)

[0166] The imidization rate of the polyimide precursor or polyamideimide precursor is preferably less than 15%, more preferably less than 10%, and even more preferably less than 5%. The above imidization rate can be obtained by the method for producing the polyimide precursor or polyamideimide precursor of the present invention.

[0167] The above-mentioned polyimide precursor or polyamideimide precursor preferably contains a structure represented by the following general formula (11).

[0168]

[0169] In general formula (11), R １５ and R １６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. * indicates the bond position. R １５ and R １６ The alkyl group in the alkoxy group may be linear or branched, and an alkyl group having 1 to 10 carbon atoms is preferred. Specifically, examples of alkyl groups in the alkoxy group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups. The alkyl group in the alkoxy group is preferably a methyl, ethyl, or n-propyl group, more preferably a methyl or ethyl group, and even more preferably a methyl group. The alkoxy group may further have substituents. The substituents are not particularly limited, but examples include aryl groups and (meth)acryloyloxy groups.

[0170] The aryl group in the aryloxy group may be monocyclic or polycyclic, and an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of the aryl group in the aryloxy group include a phenyl group, a naphthyl group, and the like. The aryloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups.

[0171] The aralkyl group in the aralkyloxy group can be an aralkyl group having 7 to 11 carbon atoms. Specifically, the aralkyl group in the aralkyloxy group can be a benzyl group, etc. The aralkyloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups, etc.

[0172] The structure represented by the above general formula (11) may be present in the polyimide precursor or polyamideimide precursor. For example, the structure represented by the above general formula (11) may be present at the end of the main chain of the polyimide precursor or polyamideimide precursor, or at the end of the side chain of the polyimide precursor or polyamideimide precursor. The structure represented by the above general formula (11) can be introduced by the method for producing the polyimide precursor or polyamideimide precursor of the present invention.

[0173] The presence of the structure represented by the above general formula (11) in the polyimide precursor or polyamideimide precursor is as follows: １ It can be measured by 1H-NMR. The structure represented by general formula (11) in the polyimide precursor or polyamideimide precursor is １ Identification is performed based on the results of 1H-NMR (nuclear magnetic resonance) measurements. １ H-NMR spectrometer: Bruker, 400 MHz. Measurement solvent: Deuterium DMSO (dimethyl sulfoxide). The peak of the methoxy group of triazine is detected at around 4.0 ppm. Regarding the polyimide precursor or polyamideimide precursor obtained by the method for producing the polyimide precursor or polyamideimide precursor of the present invention, １ The existence of the structure represented by general formula (11) can be confirmed by H-NMR.

[0174] It is preferable that the above-mentioned polyimide precursor or polyamideimide precursor contains a compound represented by the following general formula (12) in an amount of 10 ppm to 10,000 ppm.

[0175]

[0176] In general formula (12), R １７ and R １８ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. １７ and R １８The alkyl group in the alkoxy group may be linear or branched, and an alkyl group having 1 to 10 carbon atoms is preferred. Specifically, examples of alkyl groups in the alkoxy group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups. The alkyl group in the alkoxy group is preferably a methyl, ethyl, or n-propyl group, more preferably a methyl or ethyl group, and even more preferably a methyl group. The alkoxy group may further have substituents. The substituents are not particularly limited, but examples include aryl groups and (meth)acryloyloxy groups.

[0177] The aryl group in the aryloxy group may be monocyclic or polycyclic, and an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of the aryl group in the aryloxy group include a phenyl group, a naphthyl group, and the like. The aryloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups.

[0178] The aralkyl group in the aralkyloxy group can be an aralkyl group having 7 to 11 carbon atoms. Specifically, the aralkyl group in the aralkyloxy group can be a benzyl group, etc. The aralkyloxy group may further have substituents. The substituents are not particularly limited, but examples include alkyl groups, etc.

[0179] The compound represented by the above general formula (12) can be introduced by the method for producing a polyimide precursor or polyamideimide precursor of the present invention. Furthermore, the content of the compound represented by the following general formula (12) in the polyimide precursor or polyamideimide precursor can be adjusted by adjusting the content of various compounds in step 1 of the method for producing a polyimide precursor or polyamideimide precursor of the present invention.

[0180] The presence of the compound represented by the general formula (12) in the polyimide precursor or polyamideimide precursor, and its content, can be measured by GC (gas chromatography) as follows: (GC measurement sample preparation) Dissolve 0.1 g of polyimide precursor or polyamideimide precursor powder in 4.9 g of NMP in a sample bottle, and perform GC measurement on the liquid obtained by filtering through a Teflon filter. (GC conditions) Perform the measurement under the following conditions to confirm and quantify the compound represented by the general formula (12).

[0181]

[0182] It is preferable that the polyimide precursor or polyamide-imide precursor contains 10 ppm to 10,000 ppm of the compound represented by general formula (12). The method for producing the polyimide precursor or polyamide-imide precursor of the present invention can make the content of the compound represented by general formula (12) within the above range. It is more preferable that the polyimide precursor or polyamide-imide precursor contains 10 ppm to 1,000 ppm of the compound represented by general formula (12), and even more preferable that it contains 10 ppm to 100 ppm.

[0183] In one preferred embodiment, the amide solvent content in the polyimide precursor or polyamideimide precursor is preferably 100 ppm or less. When the amide solvent content in the polyimide precursor or polyamideimide precursor is 100 ppm or less, the polyimide precursor or polyamideimide precursor obtained by the production method of the present invention can be suitably used in the resin composition contained in the composition layer of the transfer film described later. The amide solvent content is more preferably 1000 ppm or less, and even more preferably 100 ppm or less. Furthermore, the lower limit of the amide solvent content is not particularly limited and may be 0 ppm (below the detection limit).

[0184] The content of the amide-based solvent in the polyimide precursor or polyamide-imide precursor can be measured by GC (gas chromatography) as follows. (GC measurement sample preparation) Dissolve polyimide precursor or polyamide-imide precursor powder (0.1 g) in THF (4.9 g) in a sample bottle, and perform GC measurement on the liquid filtered through a Teflon filter. (GC conditions) Perform measurement under the same conditions as those described in Table 1 above to quantify the amide-based solvent.

[0185] The above polyimide precursor or polyamide-imide precursor preferably has a repeating unit represented by the following general formula (21) or a repeating unit represented by the following general formula (22).

[0186]

[0187] In general formula (21) and general formula (22), A １１ , A １２ , and A １３ each independently represents an oxygen atom or -NR Ｚ１ -. Y ２ each independently represents a divalent organic group. X ３ represents a tetravalent organic group. X ４ represents a trivalent organic group. R ２１ , R ２２ , and R ２３ each independently represents a hydrogen atom or a monovalent organic group. R ｚ１ represents a hydrogen atom or a monovalent organic group.

[0188] A １１ , A １２ , and A １３ in general formula (21) and general formula (22) each independently represents an oxygen atom or -NR ｚ１ -, and an oxygen atom is preferred. R ｚ１ represents a hydrogen atom or a monovalent organic group, and a hydrogen atom is preferred.

[0189] X ３ is synonymous with R １１５ in formula (O), and the preferred range is also the same. X ４ is X ２This is synonymous with the same thing, and the preferred range is also similar.

[0190] Y in general formula (21) and general formula (22) ２ represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, with groups containing aromatic groups having 6 to 20 carbon atoms being more preferred. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of heteroatom-containing groups include phenolic hydroxyl groups and primary amino groups. ２ Examples include groups represented by -Ar- and -Ar-L-Ar-, with the group represented by -Ar-L-Ar- being preferred. However, Ar is independently an aromatic group, and L is a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２ The group consists of - or -NHCO-, or a combination of two or more of the above. The preferred ranges are as described above.

[0191] Y ２ It is preferable that it be derived from a compound having two or more amino groups. In one preferred embodiment, diamines are used as compounds having two or more amino groups. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, Y ２The diamine is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

[0192]

[0193] In the formula, A represents a single bond or a divalent linking group, and may be a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO ２ Preferably, the group is -, -NHCO-, or a combination thereof, and may be a single bond or a C1-C3 alkylene group substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ２ - More preferably, the group is selected from -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ -, or -C(CH ３ ) ２ It is even more preferable that it is -. In the formula, * represents a bonding site with another structure.

[0194] Specifically, an example of a diamine is the diamine used in step 2 described above.

[0195] Y ２ From the viewpoint of the flexibility of the resulting organic film, it is preferable that it be represented as -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２- or -NHCO-, or a group consisting of two or more of the above. Ar is preferably a phenylene group, and L is a carbon-1 or carbon-2 aliphatic hydrocarbon group, -O-, -CO-, -S-, or -SO- which may be substituted with a fluorine atom. ２ - is preferred. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0196] Also, Y ２ From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61). Formula (51)

[0197]

[0198] In formula (51), R ５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ５０ ~R ５７ At least one of the elements is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (21) or the bonding site with the nitrogen atom in formula (22). ５０ ~R ５７ Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0199]

[0200] In formula (61), R ５８ and R ５９Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (21) or a bonding site with the nitrogen atom in formula (22). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0201] In a preferred embodiment, as a compound having two or more amino groups (compound (N)), a compound having three or more amino groups can also be mentioned. Compounds having three or more amino groups are not particularly limited, but examples include 3,3'-diaminobenzidine (DAB), 3,4,4'-triaminodiphenyl ether, 1,2,4-triaminobenzene, 4-(4-aminophenyl)benzene-1,2-diamine, 4-(3,4-diaminophenoxy)-1,2-benzenediamine, bis(3,4-diaminodiphenyl)methanone, 2-amino-4-[(3,4-diaminophenoxyl)sulfonyl]phenylamine, triphenylene-2,3,6,7,10,11-hexaamine, phenazine-2,3,7,8-tetraamine, bis(3,4-diaminodiphenyl)hexafluoropropane, 2,4,6-triaminopyrimidine, and the like. The compound having three or more amino groups may be the hydrochloride salt of the compound having three or more amino groups as described above. In one preferred embodiment, Y ２ This is Y, which will be discussed later. １１ That's fine.

[0202] R ２１ , R ２２ These are R in general formula (2), respectively. ７ , R ８ This is synonymous with the same thing, and the preferred range is also similar.

[0203] As a preferred embodiment, the above-mentioned "General formula (2) -A １ -R ７ , -A ２ -R ８Preferably, at least one of them represents the group represented by the above formula (V). " is "the -A of the general formula (21) described later １１ -R ２１ , -A １２ -R ２２ At least one of these preferably represents a group represented by the above formula (V). R ２３ R in general formula (3) １３ This is synonymous with the same thing, and the preferred range is also similar.

[0204] As a preferred embodiment, the above-mentioned "General formula (3) -A ３ -R １３ It is preferable that this represents the group represented by the above formula (V). " is the -A of the general formula (22) described later. １３ -R ２３ It is preferable to replace with " which represents the group represented by the above formula (V).

[0205] The group represented by formula (V) above is preferably the group represented by formula (W) above.

[0206] The polyimide precursor may contain one repeating unit represented by general formula (21), or it may contain two or more. It may also contain structural isomers of the repeating unit represented by general formula (21). In addition to the repeating unit of general formula (21), the polyimide precursor may also contain other types of repeating units.

[0207] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by general formula (21) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The above upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by general formula (21).

[0208] The polyamide-imide precursor may contain one repeating unit represented by general formula (22), or it may contain two or more. It may also contain structural isomers of the repeating unit represented by general formula (22). In addition to the repeating unit of general formula (22), the polyamide-imide precursor may also contain other types of repeating units.

[0209] One embodiment of the polyamide-imide precursor in the present invention is one in which the content of repeating units represented by general formula (22) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The above upper limit of the total content is not particularly limited, and all repeating units in the polyamide-imide precursor except for the terminals may be repeating units represented by general formula (22).

[0210] The above-mentioned polyimide precursor or polyamideimide precursor preferably has a structure represented by the following general formula (N).

[0211]

[0212] In general formula (N), Y １１ *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position.

[0213] Y １２R represents a divalent linking group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably, a group containing an aromatic group having 6 to 20 carbon atoms. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. A phenolic hydroxyl group represents a hydroxyl group bonded to an aromatic group. A primary amino group is -NH ２ It represents.

[0214] R Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. Ｎ１ and R Ｎ２ If at least one of them represents a phenolic hydroxyl group, R Ｎ１ and R Ｎ２ Y which is combined with at least one of the １２ represents an aromatic group.

[0215] The synthesis of polyimide precursors or polyamideimide precursors having the structure represented by the above general formula (N) is generally carried out in the presence of a solvent such as NMP. This is because when a compound having two or more amino groups corresponding to general formula (N) is used as a raw material, unintended side reactions may occur, and such side reactions can be suppressed by using NMP. The method for producing polyimide precursors or polyamideimide precursors of the present invention makes it possible to produce polyimide precursors or polyamideimide precursors having the structure represented by the above general formula (N) in the presence of a solvent other than NMP (for example, an organic solvent containing a hydroxyl group). Considering this point, it is considered that the method for producing polyimide precursors or polyamideimide precursors of the present invention can broaden the variations of polyimide precursors or polyamideimide precursors that can be produced, regardless of the solvent.

[0216] The above-mentioned polyimide precursor or polyamideimide precursor may also preferably have a structure represented by the following general formula (N2).

[0217]

[0218] In general formula (N2), Y １３ This represents a divalent linking group containing an aliphatic group.

[0219] Examples of aliphatic groups include linear or branched aliphatic groups, and cyclic aliphatic groups. １３ The linking group containing the aliphatic group represented by is preferably a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof.

[0220] In one preferred embodiment, the polyimide precursor or polyamideimide precursor preferably has a repeating unit represented by the following general formula (23) or a repeating unit represented by the following general formula (24).

[0221]

[0222] In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

[0223] X １１ R in equation (O) １１５This is synonymous with the following, and the preferred range is also similar. １２ X in general formula (3) ２ This is synonymous with the following, and the preferred range is also similar. ２３ , R ２４ These are R in general formula (2), respectively. ７ , R ８ This is synonymous with the following, and the preferred range is also similar. ２５ R in general formula (3) １３ This is synonymous with the same thing, and the preferred range is also the same. Y １１ This is Y in general formula (N). １１ This is synonymous with [another synonym], and the same applies to the preferred range. The same also applies to [another synonym].

[0224] The polyimide precursor may contain one repeating unit represented by general formula (23), or it may contain two or more. It may also contain structural isomers of the repeating unit represented by general formula (23). In addition to the repeating unit of general formula (23), the polyimide precursor may also contain other types of repeating units.

[0225] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by general formula (23) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The above upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by general formula (23).

[0226] In a preferred embodiment, the polyamide-imide precursor may contain one repeating unit represented by general formula (24), or it may contain two or more. It may also contain structural isomers of the repeating unit represented by general formula (24). In addition to the repeating unit of general formula (24), the polyimide precursor may also contain other types of repeating units.

[0227] One embodiment of the polyamide-imide precursor in the present invention is one in which the content of repeating units represented by general formula (24) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The above upper limit of the total content is not particularly limited, and all repeating units in the polyamide-imide precursor except for the terminals may be repeating units represented by general formula (24).

[0228] [Method for Producing Resin Compositions and Resin Compositions] The present invention relates to a method for producing the following resin composition: A method for producing a resin composition comprising mixing (1) a polyimide precursor produced by the above-described method for producing a polyimide precursor or polyamideimide precursor, (2) a solvent, and (3) a polymerizable compound. (1) The polyimide precursor or polyamideimide precursor (hereinafter also referred to as "precursor (1)") produced by the above-described method for producing a polyimide precursor or polyamideimide precursor is as described above. (2) The solvent and (3) the polymerizable compound will be described later. The method for mixing the polyimide precursor (1), (2) the solvent, and (3) the polymerizable compound is not particularly limited. In addition to the precursor (1), (2) the solvent, and (3) the polymerizable compound, components described later may be mixed as needed.

[0229] The present invention relates to the following resin composition: (11) a polyimide precursor or polyamideimide precursor having repeating units represented by the following general formula (23) or the following general formula (24) (hereinafter also referred to as "precursor (11)"); (2) a solvent; (3) a resin composition containing a polymerizable compound (hereinafter also referred to as resin composition (11)).

[0230]

[0231] In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

[0232] Each group in general formula (23) and general formula (24) is the same as each group in general formula (23) and general formula (24) in the above-described method for producing a polyimide precursor or polyamideimide precursor, and the preferred embodiment is also the same. ２３ and R ２４ At least one of the groups has an ethylenically unsaturated bond, or the R of the general formula (24) above. ２５ It is preferable that it has a group having an ethylenically unsaturated bond. It is preferable that the group having an ethylenically unsaturated bond is a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group. The precursor (11) may have repeating units that the polyimide precursor or polyamideimide precursor obtained by the above-described method for producing a polyimide precursor or polyamideimide precursor may have. (2) Solvents and (3) polymerizable compounds will be described later.

[0233] The present invention also relates to the following resin composition: (12) A polyimide precursor or polyamideimide precursor comprising a structure represented by the following general formula (11), wherein the imidization rate of the polyimide precursor or polyamideimide precursor is less than 15% (hereinafter also referred to as "precursor (12)"); (2) A solvent; (3) A resin composition comprising a polymerizable compound (hereinafter also referred to as resin composition (12)).

[0234]

[0235] In general formula (11), R １５ and R １６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. * indicates the bond position.

[0236] Each group in general formula (11) is the same as each group in general formula (11) in the above-described method for producing a polyimide precursor or polyamideimide precursor, and the preferred embodiment is also the same. The precursor (12) may have repeating units that may be present in the polyimide precursor or polyamideimide precursor obtained by the above-described method for producing a polyimide precursor or polyamideimide precursor.

[0237] The method for identifying the structure represented by general formula (11) is as described above. The imidation rate of the precursor (12) is less than 15%, preferably less than 10%, and more preferably less than 5%. The above imidation rate can be achieved by the method for producing the polyimide precursor or polyamideimide precursor of the present invention. (2) Solvents and (3) polymerizable compounds will be described later.

[0238] The present invention also relates to the following resin composition: (13) A polyimide precursor or polyamideimide precursor containing 10 ppm to 10,000 ppm of a compound represented by the following general formula (12), wherein the imidization rate of the polyimide precursor or polyamideimide precursor is less than 15% (hereinafter also referred to as "precursor (13)"); (2) a solvent; (3) a polymerizable compound resin composition (hereinafter also referred to as resin composition (13)). (2) the solvent and (3) the polymerizable compound will be described later.

[0239]

[0240] In general formula (12), R １７ and R １８ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group.

[0241] Each group in general formula (12) is the same as each group in general formula (12) in the above-described method for producing a polyimide precursor or polyamideimide precursor, and the preferred embodiment is also the same. The precursor (13) may have repeating units that may be present in the polyimide precursor or polyamideimide precursor obtained by the above-described method for producing a polyimide precursor or polyamideimide precursor.

[0242] The method for identifying and quantifying the compound represented by general formula (12) is as described above. The imidation rate of the precursor (13) is less than 15%, preferably less than 10%, and more preferably less than 5%. The above imidation rate can be achieved by the method for producing the polyimide precursor or polyamideimide precursor of the present invention. (2) Solvents and (3) polymerizable compounds will be described later.

[0243] The polyimide precursor produced by the above-described method for producing the polyimide precursor, and precursors (11) to (13), are collectively referred to as "specific resin."

[0244] Furthermore, the resin composition in the above-mentioned method for producing the resin composition, the resin composition containing the above-mentioned precursor (11), (2) solvent, and (3) polymerizable compound, the resin composition containing the above-mentioned precursor (12), (2) solvent, and (3) polymerizable compound, and the resin composition containing the above-mentioned precursor (13), (2) solvent, and (3) polymerizable compound are collectively referred to as "the resin composition of the present invention."

[0245] The resin composition of the present invention may contain (4) a polymerization initiator. (4) The polymerization initiator will be described later.

[0246] A polyimide precursor is a resin that undergoes a chemical structure change upon external stimuli to become polyimide. Resins that undergo a chemical structure change upon heat to become polyimide are preferred, and resins that undergo a ring-closing reaction upon heat to form a ring structure to become polyimide are more preferred. It is preferable that the polyimide produced from the polyimide precursor in the resin composition of the present invention is insoluble in a developer mainly composed of an organic solvent. A polyamideimide precursor is a resin that undergoes a chemical structure change upon external stimuli to become polyamideimide. Resins that undergo a chemical structure change upon heat to become polyamideimide are preferred, and resins that undergo a ring-closing reaction upon heat to form a ring structure to become polyamideimide are more preferred. It is preferable that the polyamideimide produced from the polyamideimide precursor in the resin composition of the present invention is insoluble in a developer mainly composed of an organic solvent.

[0247] When a specific resin has a radical polymerization group, the resin composition of the present invention preferably contains a radical polymerization initiator. Furthermore, it may contain a sensitizer as needed. For example, a negative-type photosensitive film can be formed from such a resin composition of the present invention. The specific resin may also have a polarity conversion group such as an acid-degradable group. When the specific resin has an acid-degradable group, the resin composition preferably contains a photoacid generator. For example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film can be formed from such a resin composition of the present invention. The resin composition of the present invention may be a negative-type photosensitive resin composition (a resin composition capable of forming a negative-type photosensitive film) or a positive-type photosensitive resin composition (a resin composition capable of forming a positive-type photosensitive film), but it is preferably a negative-type photosensitive resin composition. The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers.

[0248] The weight-average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, even more preferably 5,000 to 50,000, and still more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000. The degree of dispersion of the molecular weight of the specific resin is preferably 1.5 or higher, more preferably 1.8 or higher, and still more preferably 2.0 or higher. When the resin composition of the present invention contains multiple types of specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the specific resins are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of specific resins are treated as a single resin are each within the above ranges.

[0249] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0250] The resin composition of the present invention may preferably contain at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of resins, including a specific resin and other resins, or it may contain two or more specific resins, but it is preferable that it contains two or more specific resins.

[0251] <(2) Solvent> The resin composition of the present invention may contain a solvent. Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0252] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0253] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0254] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0255] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0256] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0257] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0258] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0259] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0260] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0261] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone, the combination of dimethyl sulfoxide and γ-valerolactone, the combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass relative to the total mass of the solvent. In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as the solvent is also a preferred embodiment of the present invention. In such embodiments, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content should be determined by considering the solubility of specific resins and other components contained in the resin composition.In another preferred embodiment, when dimethyl sulfoxide and γ-butyrolactone are used in combination, it is preferable to contain 60 to 90% by mass of γ-butyrolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-butyrolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-butyrolactone and 15 to 25% by mass of dimethyl sulfoxide, based on the total mass of the solvent.

[0262] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0263] <(3) Polymerizable Compounds> The resin composition of the present invention may contain polymerizable compounds. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents. The polymerizable compound is a compound different from the specified resin described above.

[0264] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0265] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, it is preferable that it has 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6. From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0266] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0267] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0268] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0269] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0270] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0271] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0272] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0273] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0274] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0275] As a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is also preferred. In the present invention, urea bonds are defined as *-NR Ｎ -C(=O)-NR Ｎ-* is a combination represented by R Ｎ Each of the symbols independently represents a hydrogen atom or a monovalent organic group, and each of the symbols * represents a bonding site with a carbon atom. In this invention, a urethane bond is defined as *-O-C(=O)-NR Ｎ -* is a combination represented by R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. The resin composition may have improved chemical resistance, resolution, etc., due to the inclusion of the crosslinking agent U. The mechanism by which the above effects are obtained is unknown, but for example, it is thought that when curing by heating, a portion of the crosslinking agent U decomposes thermally, generating amines, etc., and these amines, etc., promote the cyclization of the precursor of the cyclized resin, such as the polyimide precursor. The crosslinking agent U may have only one urea bond or one urethane bond, or it may have one or more urea bonds and one or more urethane bonds, or it may have two or more urea bonds without any urethane bonds, or it may have two or more urethane bonds without any urea bonds. The total number of urea bonds and urethane bonds in the crosslinking agent U is one or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0276] Furthermore, examples of crosslinking agent U include the compounds described in paragraphs 0159-0169 of International Publication 2024 / 181276, the compounds described in paragraphs 0146-0156 of International Publication 2024 / 95884, the compounds described in paragraphs 0145-0155 of International Publication 2023 / 157911, and so on. This information is incorporated herein by reference.

[0277] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is about 200. From the viewpoint of suppressing warping of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent in the resin composition of the present invention.Preferably used as monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds with a boiling point of 100°C or higher under normal pressure are also preferred as monofunctional radical crosslinking agents. Other examples of bifunctional or more functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0278] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0279] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0280] [Other Crosslinking Agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by photosensitization with the photoacid generator or photobase generator described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. The acid or base is preferably an acid or base generated from the photoacid generator or photobase generator in the exposure process. As other crosslinking agents, compounds having at least one group selected from the group consisting of acyloxymethyl group, methylol group, ethylol group and alkoxymethyl group are preferred, and compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl group, methylol group, ethylol group and alkoxymethyl group is directly bonded to a nitrogen atom are more preferred. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atoms of the amino group are replaced with acyloxymethyl, methylol, ethylol, or alkoxymethyl groups. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compounds produced by the above method is acceptable. These compounds may also be oligomers formed by the self-condensation of methylol groups. Among the above amino group-containing compounds, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluryl, urea, or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluryl-based crosslinking agents and melamine-based crosslinking agents, as described later.

[0281] Other crosslinking agents include the compounds described in paragraphs 0324-0342 of International Publication No. 2024 / 143210, the compounds described in paragraphs 0219-0237 of International Publication No. 2024 / 070963, and the compounds described in paragraphs 0106-0124 of International Publication No. 2023 / 190062. This information is incorporated herein by reference.

[0282] The resin composition of the present invention may also preferably contain, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0283] - Epoxy Compounds (Compounds Containing Epoxy Groups) - Preferably, the epoxy compound is a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at temperatures below 200°C, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is less likely to occur. For this reason, including epoxy compounds is effective in suppressing low-temperature curing and warping of resin compositions.

[0284] The epoxy compound preferably contains polyethylene oxide groups. This further reduces the modulus of elasticity and suppresses warping. A polyethylene oxide group refers to a group with two or more repeating units of ethylene oxide, and preferably has 2 to 15 repeating units.

[0285] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epiclon (registered trademark, hereinafter the same) 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon HP-4770, Epiclon EXA-830LVP, Epiclon EXA-8183, Epiclon EXA-8169, Epiclon N-660, Epiclon N-665-EXP-S, Epiclon N-740 (product names, manufactured by DIC Corporation), Ricaresin (registered trademark, same applies hereinafter) BEO-20E, Ricaresin BEO-60E, Ricaresin HBE-100, Ricaresin DME-100, Ricaresin L-200 (product names, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (product names, manufactured by ADEKA Corporation), Ceroxa Ido (registered trademark, hereinafter the same) 2021P, Ceroxide 2081, Ceroxide 2000, EHPE3150, Epolid (registered trademark, hereinafter the same) GT401, Epolid PB4700, Epolid PB3600 (all product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-30 Examples include 00-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, and BREN-10S (all are trade names, manufactured by Nippon Kayaku Co., Ltd.).The following compounds are also preferably used.

[0286]

[0287] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0288] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7, in order to achieve both heat resistance and improved elongation.

[0289] - Oxetane compounds (compounds having an oxetanyl group) - Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. Specific examples include the Aronoxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221), which can be used individually or in combination of two or more.

[0290] -Benzoxazine compounds (compounds having a benzoxazolyl group)- Benzooxazine compounds are preferred because, due to the crosslinking reaction derived from a ring-opening addition reaction, degassing does not occur during curing, and furthermore, thermal shrinkage is reduced, suppressing the occurrence of warping.

[0291] Preferred examples of benzoxazine compounds include P-d type benzoxazine, F-a type benzoxazine (both trade names, manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used individually or in combination of two or more.

[0292] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The other crosslinking agents may be present as one type or as two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0293] [(4) Polymerization Initiator] The resin composition of the present invention may contain a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0294] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0295] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0296] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent 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.) is also suitably used.

[0297] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0298] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0299] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0300] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be suitably used. This is incorporated herein by reference.

[0301] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0302] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and others, the contents of which are incorporated herein by reference.

[0303] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, it is particularly preferable to use oxime compounds as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=N-O-C(=O)- linking group in their molecule.

[0304]

[0305] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. Additionally, oxime compounds with the following structures can also be used.

[0306]

[0307] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom can be used. Also, oxime compounds having a nitro group as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton can be used. These contents are incorporated herein by reference.

[0308] As a photopolymerization initiator, an aromatic ring group Ar, in which an electron-withdrawing group is introduced to the aromatic ring, is used. ＯＸ１ An oxime compound having the above aromatic ring group Ar (hereinafter also referred to as oxime compound OX) can also be used. ＯＸ１Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups. Acyl and nitro groups are preferred, acyl groups are more preferred because they easily form films with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, acyl groups, or amino groups. More preferred substituents are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic oxy groups, alkylsulfanyl groups, arylsulfanyl groups, or amino groups. Even more preferred substituents are alkoxy groups, alkylsulfanyl groups, or amino groups.

[0309] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2).

[0310]

[0311] In the formula, R Ｘ１ R represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group. Ｘ２ R represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group. Ｘ３ ~R Ｘ１４Each of these independently represents a hydrogen atom or a substituent. However, R Ｘ１０ ~R Ｘ１４ At least one of them is an electron-withdrawing group.

[0312] In the above formula, R Ｘ１２ R is an electron-withdrawing group, Ｘ１０ , R Ｘ１１ , R Ｘ１３ , R Ｘ１４ It is preferable that it is a hydrogen atom.

[0313] Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated herein by reference.

[0314] Particularly preferred oxime compounds include oxime compounds having specific substituents as shown in Japanese Patent Publication No. 2007-269779 and oxime compounds having a thioaryl group as shown in Japanese Patent Publication No. 2009-191061, the details of which are incorporated herein by reference.

[0315] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-arylsubstituted coumarin compounds.

[0316] Furthermore, the photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. More preferably, at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is preferred, and a metallocene compound or an oxime compound is even more preferred.

[0317] As photoradical polymerization initiators, compounds described in paragraphs 0175-0179 of International Publication No. 2021 / 020359 and compounds described in paragraphs 0048-0055 of International Publication No. 2015 / 125469 may also be used, and this is incorporated herein by reference.

[0318] As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents etc. improves, making precipitation less likely over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016 / 0 Examples include Cmpd1 to 7 described in Patent No. 34963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0319] If the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The resin composition may contain only one type of photopolymerization initiator or two or more types. If two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. In addition, since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0320] [Photosensitive Agent] The resin composition of the present invention may contain a photosensitive agent. The photosensitive agent in the present invention is preferably at least one photosensitive agent selected from a photoradical polymerization initiator, a photoacid generator, and a photobase generator. Examples of photoradical polymerization initiators include those described in [(4) Polymerization Initiators] above. When the resin composition contains a photoradical polymerization initiator, its content can be within a suitable range of the content of the photopolymerization initiator described above. Examples of photobase generators include compounds that correspond to photobase generators among the compounds described in <Base Generators> below. When the resin composition contains a photobase generator, its content can be within a suitable range of the content of the base generator described below.

[0321] [Sensitizer] The resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenone, Michlaz ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate Examples include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used. For details on sensitizing dyes, refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0322] If the resin composition contains a sensitizer, the sensitizer content 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, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0323] [Chain Transfer Agents] The resin compositions of the present invention may contain chain transfer agents. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include -S-S- and -SO2 molecules. ２ Compounds containing -S-, -N-O-, SH, PH, SiH, and GeH, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, are used. These can generate radicals by donating hydrogen to low-activity radicals, or by being oxidized and then deprotonated. Thiol compounds are particularly preferred.

[0324] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0325] If the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0326] <Base Generator> The resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted by heating, for example, resulting in good mechanical properties and chemical resistance of the cured product, and thus good performance as an interlayer insulating film for redistribution layers contained in semiconductor packages, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0327] Furthermore, examples of base-generating agents include compounds described in paragraphs 0319-0358 of International Publication 2024 / 203918, compounds described in paragraphs 0382-0414 of International Publication 2024 / 143209, and compounds described in paragraphs 0270-0300 of International Publication 2023 / 190063. This information is incorporated herein by reference.

[0328] When the resin composition contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generating agents can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0329] <Metal Adhesion Enhancers> The resin composition of the present invention preferably contains a metal adhesion enhancer from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion enhancers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0330] [Silane Coupling Agents] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferred as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

[0331]

[0332] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more.

[0333] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0334] Other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0335] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total value is within the above range.

[0336] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0337] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0338] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0339] Other migration inhibitors include, for example, the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the like, which are incorporated herein by reference.

[0340] Specific examples of migration inhibitors include the following compounds.

[0341]

[0342] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition.

[0343] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0344] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0345] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, and the like. This information is incorporated herein by reference.

[0346] If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0347] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0348] <Other Additives> The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-flocculation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these publications are incorporated herein. When these additives are included, it is preferable that their total content be 3% by mass or less of the solid content of the resin composition of the present invention.

[0349] [Surfactants] Various surfactants can be used as surfactants, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0350] By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (especially the fluidity) of the prepared coating liquid composition are further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further enhanced. Specifically, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid decreases, improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, it is possible to more favorably form a uniform film with less thickness variation.

[0351] Examples of fluorinated surfactants include the compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which are incorporated herein by reference. Fluorinated polymer compounds can also be preferably used as fluorinated surfactants, which include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Examples include the following compounds.

[0352]

[0353] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As a fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

[0354] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0355] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0356] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0357] [Higher Fatty Acid Derivatives] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may contain higher fatty acid derivatives such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the resin composition of the present invention during the drying process after coating.

[0358] Furthermore, higher fatty acid derivatives may also be compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0359] When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition. There may be only one type of higher fatty acid derivative, or there may be two or more types. If there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above range.

[0360] [Thermal Polymerization Initiators] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals in response to thermal energy, initiating or accelerating the polymerization reaction of polymerizable compounds. By adding thermal radical polymerization initiators, the polymerization reaction of resins and polymerizable compounds can be advanced, thereby improving solvent resistance. In addition, photopolymerization initiators may also have the function of initiating polymerization in response to heat, and may be added as thermal polymerization initiators.

[0361] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the details of which are incorporated herein by reference.

[0362] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[0363] [Inorganic Particles] Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0364] The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter of the inorganic particles is the primary particle diameter and also the volume-average particle diameter. The volume-average particle diameter can be measured, for example, by dynamic light scattering using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission, X-ray transmission, or laser diffraction / scattering.

[0365] [UV absorbers] Examples of UV absorbers include salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazines. Specific examples of UV absorbers include the compounds described in paragraphs 0341-0342 of International Publication No. 2021 / 112189, which are incorporated herein by reference.

[0366] The ultraviolet absorber may be used alone or in combination of two or more types. When the resin composition contains an ultraviolet absorber, the amount of ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid content mass of the resin composition.

[0367] [Organotitanium Compounds] By including organotitanium compounds in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0368] Suitable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), titanium diisopropoxidebis(ethylacetoacetate), etc. II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0369] In particular, from the viewpoint of better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0370] When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0371] [Antioxidants] By including antioxidants as additives, the elongation properties of the cured film and its adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348-0357 of International Publication No. 2021 / 112189, which are incorporated herein by reference.

[0372] The antioxidant content is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By adding 0.1 parts by mass or more, it is easier to obtain the effect of improving elongation characteristics and adhesion to metal materials even in high temperature and high humidity environments, and by adding 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitive agent. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.

[0373] [Anti-flocculants] Examples of anti-flocculants include sodium polyacrylate.

[0374] The anti-flocculation agent may be used alone or in combination of two or more types. When the resin composition contains an anti-flocculation agent, the content of the anti-flocculation agent is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid content mass of the resin composition.

[0375] [Phenol compounds] Examples of phenol compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0376] The phenolic compounds may be used individually or in combination of two or more. When the resin composition contains phenolic compounds, the content of the phenolic compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the resin composition.

[0377] [Other Polymer Compounds] Other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified forms into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0378] Other polymer compounds may be used individually or in combination of two or more. When the resin composition contains other polymer compounds, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the resin composition.

[0379] <Characteristics of the Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm ２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２ If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, a coating with excellent properties can be obtained on the coated surface.

[0380] <Restrictions on the substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. The lower limit of the water content of the resin composition is preferably 0.001% by mass or more, can be 0.05% by mass or more, and can also be 0.5% by mass or more, from the viewpoint of reducing the effort required to manage storage conditions, adhesion, developability, etc. Specific examples of water content of the resin composition include, for example, 0.05% by mass, 0.2% by mass, and 1.4% by mass. Methods for maintaining the water content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.

[0381] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. From the viewpoint of reducing the effort required to reduce the metal content, mechanical properties, and adhesion, the lower limit of the metal content in the resin composition is preferably 0.001 ppm by mass or more, and may also be 0.01 ppm by mass or more, relative to the total mass of the resin composition. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes of organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range. If the resin composition contains multiple metals, it is preferable that the sum of these metals is within the above range. Specific examples of metal content include, for example, 0.002 ppm by mass, 0.05 ppm by mass, and 0.3 ppm by mass, relative to the total mass of the resin composition.

[0382] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0383] Considering its application as a semiconductor material, the halogen atom content of the resin composition of the present invention is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of preventing wiring corrosion. In particular, the amount of halogen atoms existing in the form of halogen 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. Furthermore, from the viewpoint of reducing the effort required to reduce halogen ions, the lower limit of halogen ions in the resin composition can be 0.01 ppm by mass or more, or 0.1 ppm by mass or more, relative to the total mass of the resin composition. Specific examples of halogen ion amounts include, for example, 0.02 ppm by mass, 0.5 ppm by mass, and 2.5 ppm by mass, relative to the total mass of the composition. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. It is preferable that the total amount of fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, as well as their ions, are within the above ranges. Methods for adjusting the halogen atom content include ion exchange treatment.

[0384] Conventional containers can be used as containers for the resin composition of the present invention. To suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0385] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing methods include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

[0386] For the purpose of removing foreign matter such as dirt and fine particles from the resin composition of the present invention, filtration using a filter is preferable. The filter pore size is preferably, for example, 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. If the filter material is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. As an example of a connection configuration, an HDPE filter with a pore size of 1 μm is connected in series as the first stage, and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Furthermore, various materials may be filtered multiple times. When filtering multiple times, circulating filtration may be used. Furthermore, filtration may be performed under pressure. When filtration is performed under pressure, the pressure applied is preferably, for example, 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, even more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa. In addition to filtration using a filter, impurity removal treatment using an adsorbent may also be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, known adsorbents can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the resin composition filled into bottles may be subjected to a degassing step by placing it under reduced pressure.

[0387] The present invention relates to the following resin compositions: (11) a polyimide precursor or polyamideimide precursor (precursor (11)) having repeating units represented by the following general formula (23) or the following general formula (24); (3) a resin composition comprising a polymerizable compound.

[0388]

[0389] In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

[0390] The resin composition containing the above-mentioned precursors (11) and (3) polymerizable compounds is also referred to as "the second resin composition of the present invention."

[0391] The precursors (11) and (3) polymerizable compounds are as described above. In addition to the precursors (11) and (3) polymerizable compounds, the resin composition may also contain the components described above as necessary.

[0392] The preferred range for the content of each component in the second resin composition of the present invention is the same as the preferred range for the content of each component in the resin composition of the present invention described above, except for the solvent.

[0393] The second resin composition of the present invention may contain a solvent, but the solvent content in the resin composition is preferably 0.0001% to 10% by mass, more preferably 0.0005% to 8% by mass, even more preferably 0.001% to 5% by mass, and particularly preferably 0.01% to 4% by mass. Furthermore, the amide solvent content in the second resin composition of the present invention is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 5 ppm or less. Furthermore, the lower limit of the amide solvent content is not particularly limited and may be 0 ppm (below the detection limit).

[0394] The content of the amide solvent in the second resin composition of the present invention can be measured in the same manner as the measurement of the amide solvent content in the polyimide precursor or polyamideimide precursor described above.

[0395] The method for producing the second resin composition of the present invention is not particularly limited, but for example, it can be obtained by drying the above-described resin composition (11) to remove the solvent. Specifically, it can be obtained by applying the above-described resin composition (11) to a substrate to form a film, and then drying the formed film (layer). As a means of applying the resin composition to the substrate, coating is preferred. Specifically, as a means of application, the method described in the <film formation step> of the method for producing a cured product described later can be cited. The drying temperature and time can be determined by referring to the contents described in the <drying step> of the method for producing a cured product described later.

[0396] <Transfer Film> The present invention also relates to the following transfer film: A transfer film comprising: a support film; (11) a polyimide precursor or polyamideimide precursor having repeating units represented by the following general formula (23) or the following general formula (24) (precursor (11)); and (3) a resin composition containing a polymerizable compound (second resin composition of the present invention).

[0397]

[0398] In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group.２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

[0399] The transfer film may further include a cover film. The transfer film may also include layers other than the support film, composition layer, and cover film. Examples of layers other than the support film, composition layer, and cover film include a water-soluble resin layer containing a water-soluble resin such as PVA and / or PVP, a thermoplastic resin layer containing a thermoplastic resin, and an adhesion layer for providing adhesion.

[0400] (Support Film) The transfer film includes a support film. The support film is a component that supports the composition layer and is ultimately removed by a peeling process.

[0401] The support film may have either a single-layer or multi-layer structure. A film is preferred for the support film, and a resin film is more preferred. A film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heat, is also preferred as the support film. Examples of the above films include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, polycycloolefin film, and polycarbonate film, with polyethylene terephthalate film being preferred. Furthermore, it is preferable that the support film does not have deformation such as wrinkles or scratches.

[0402] (Composition layer) The transfer film of the present invention has a composition layer containing the second resin composition of the present invention, and preferably consists of the second resin composition of the present invention. The second resin composition of the present invention is as described above. The amide solvent content in the second resin composition of the present invention is preferably 100 ppm or less.

[0403] From the viewpoint of embedding properties and film handling properties, the solvent content in the composition layer is preferably 0.0001% to 10% by mass, more preferably 0.0005% to 8% by mass, even more preferably 0.001% to 5% by mass, and particularly preferably 0.01% to 4% by mass, relative to the entire composition layer. The composition layer may consist of multiple layers with different constituent components. The amide solvent content in the composition layer is preferably 100 ppm or less.

[0404] The average thickness of the composition layer is preferably 0.5 μm to 40 μm, more preferably 0.5 μm to 25 μm, and even more preferably 3 μm to 20 μm. An average thickness of 40 μm or less of the composition layer is preferable in terms of excellent pattern resolution, and an average thickness of 0.5 μm or more of the composition layer is preferable in terms of excellent embeddability and device reliability.

[0405] The method for manufacturing the transfer film of the present invention is not particularly limited, but for example, it can be obtained by applying the above-described resin composition (11) onto a support film to form a film, and then drying the formed film (layer) to remove the solvent. As a means of applying the resin composition onto the support film, coating is preferred. Specifically, as a means of application, the method described in the <film formation step> of the method for manufacturing a cured product described later can be used. The drying temperature and time can be determined by referring to the contents described in the <drying step> of the method for manufacturing a cured product described later.

[0406] <Cured Resin Composition> A cured resin composition can be obtained by curing the resin composition of the present invention or the second resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the second resin composition of the present invention. The curing of the resin composition is preferably done by heating, with a heating temperature of 120°C to 400°C being more preferable, 140°C to 380°C being even more preferable, and 170°C to 350°C being particularly preferable. The form of the cured resin composition is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By pattern processing of the resin composition, the shape of the cured product can also be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing a heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate of the resin composition of the present invention upon curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula: Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0407] <Characteristics of the Cured Resin Composition> 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, the cured product may have excellent mechanical properties. The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher. The same applies to the cured product of the second resin composition of the present invention.

[0408] (Method for Manufacturing Cured Products) The method for manufacturing cured products of the present invention preferably includes a film-forming step of applying a resin composition onto a substrate to form a film. The method for manufacturing cured products more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a developing step of developing the film exposed in the exposure step using a developer to form a pattern. The method for manufacturing cured products particularly preferably includes the film-forming step, the exposure step, the developing step, and at least one of a heating step of heating the pattern obtained in the developing step and a post-development exposure step of exposing the pattern obtained in the developing step. Furthermore, the method for manufacturing cured products may also preferably include the film-forming step and a step of heating the film. Details of each step will be described below.

[0409] <Membrane Formation Process> The resin composition of the present invention can be used in a membrane formation process in which it is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a membrane formation process in which the resin composition is applied to a substrate to form a film.

[0410] [Substrate] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs). Semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. These substrates may have layers such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) on their surface. The shape of the substrate is not particularly limited and may be circular or rectangular. If the substrate is circular, for example, a diameter of 100 to 450 mm is preferred, and 200 to 450 mm is more preferred. If it is rectangular, for example, the length of the shorter side is preferred to be 100 to 1000 mm, and 200 to 700 mm is more preferred. As the substrate, for example, a plate-shaped, preferably panel-shaped, substrate (substrate) is used.

[0411] When a resin composition is applied to the surface of a resin layer (for example, a layer made of cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0412] Coating is a preferred method for applying the resin composition onto a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Furthermore, a method can be applied in which a coating film, which has been previously applied and formed on a temporary support using the above application method, is transferred onto the substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used. In addition, a step of removing excess film at the edges of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may be employed in which the substrate is coated with various solvents to improve the wettability of the substrate before applying the resin composition to the substrate, and then the resin composition is applied.

[0413] <Drying Process> After the film formation process (layer formation process), the film may be subjected to a drying process to remove the solvent from the formed film (layer). That is, the method for producing a cured product of the present invention may include a drying process for drying the film formed in the film formation process. The drying process is preferably performed after the film formation process and before the exposure process. The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0414] <Exposure Process> The above film may be subjected to an exposure process in which the film is selectively exposed. The method for manufacturing the cured product may include an exposure process in which the film formed by the film formation process is selectively exposed. Selective exposure means exposing a part of the film. By selective exposure, exposed areas (exposed parts) and unexposed areas (unexposed parts) are formed in the film. The amount of exposure is not particularly limited as long as the resin composition of the present invention can be cured, but for example, it may be 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0415] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0416] In relation to the light source, the exposure wavelength can be found in: (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths: g, h, i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２Examples of exposures include (5) excimer laser (wavelength 157 nm), (6) extreme ultraviolet light; EUV (wavelength 13.6 nm), (7) YAG laser with second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0417] <Post-exposure heating step> The above film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The heating rate may also be changed as appropriate during heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0418] <Development Process> The film after exposure may be subjected to a development process in which a pattern is formed by developing it with a developer. That is, the method for manufacturing a cured product of the present invention may include a development process in which a pattern is formed by developing the film exposed in the exposure process with a developer. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed part of the film is removed by the development process is called negative development, and development in which the exposed part of the film is removed by the development process is called positive development.

[0419] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0420] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferably, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. The content of basic compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0421] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph 0387 of International Publication No. 2021 / 112189. This is incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0422] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0423] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the above content may be 100% by mass.

[0424] If the developer contains an organic solvent, it may further contain at least one of a basic compound and a base generator. At least one of the basic compound and base generator in the developer may penetrate the pattern, improving performance such as the pattern's elongation at break.

[0425] Furthermore, examples of basic compounds and base generators include those described in paragraphs 0458-0462 of International Publication No. 2024 / 203918, those described in paragraphs 0308-0312 of International Publication No. 2024 / 071380, and those described in paragraphs 0278-0282 of International Publication No. 2023 / 190061. This information is incorporated herein by reference.

[0426] [Method of supplying developer] There are no particular restrictions on the method of supplying the developer as long as a desired pattern can be formed. These include immersing a substrate on which a film has been formed in the developer, paddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, a method of supplying with a spray nozzle is more preferred. In addition, a step may be adopted in which the developer is continuously supplied with a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is supplied again with a straight nozzle, and the substrate is spun to remove the developer from the substrate. This step may be repeated multiple times. Examples of methods of supplying the developer in the development process include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept in a nearly stationary state on the substrate, a step in which the developer is vibrated on the substrate with ultrasound, etc., and a step that combines these.

[0427] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0428] In the developing process, after processing with the developer, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer in contact with the pattern dries completely may be employed.

[0429] [Rinsing Solution] If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0430] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0431] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. Preferred organic solvents are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA (propylene glycol monomethyl ether acetate), and PGME; more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME; and even more preferably cyclohexanone and PGMEA.

[0432] When the rinsing solution contains an organic solvent, the amount of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0433] The rinsing solution may contain at least one of a basic compound and a base generating agent. While not particularly limited, if the developer contains an organic solvent, a configuration in which the rinsing solution contains an organic solvent and at least one of a basic compound and a base generating agent is also a preferred embodiment of the present invention. Examples of basic compounds and base generating agents included in the rinsing solution include those exemplified above as basic compounds and base generating agents that may be included when the developer contains an organic solvent, and the preferred embodiment is similar. The basic compound and base generating agent included in the rinsing solution should be selected considering factors such as their solubility in the solvent in the rinsing solution.

[0434] When the rinse solution contains at least one of a basic compound and a base generating agent, the content of the basic compound or base generating agent is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the rinse solution. The lower limit of the above content is not particularly limited, but for example, 0.1% by mass or more is preferred. If the basic compound or base generating agent is solid in the environment in which the rinse solution is used, the content of the basic compound or base generating agent is also preferably 70 to 100% by mass, relative to the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generating agent, the rinse solution may contain only one of the basic compound and base generating agent, or it may contain two or more. When there are two or more of the basic compound and base generating agent, it is preferable that their total is within the above range.

[0435] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0436] [Method of supplying rinsing solution] There are no particular restrictions on the method of supplying the rinsing solution as long as a desired pattern can be formed. These include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution, supplying the rinsing solution to the substrate with a shower, and continuously supplying the rinsing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the rinsing solution, the removal of non-image areas, and manufacturing efficiency, there are methods of supplying the rinsing solution with a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuous supply with a spray nozzle is preferred, and from the viewpoint of the penetration of the rinsing solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. That is, the rinsing process is preferably a process of supplying the rinsing solution to the film after exposure using a straight nozzle or continuously supplying it, and it is more preferable to supply the rinsing solution using a spray nozzle. Possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0437] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0438] The developing process may include a step of bringing the processing solution into contact with the pattern after processing with the developer or after washing the pattern with the rinsing solution. Alternatively, methods such as supplying the processing solution before the developer or rinsing solution in contact with the pattern has completely dried may be employed.

[0439] Examples of the above-mentioned treatment solution include a treatment solution containing at least one of water and an organic solvent, and at least one of a basic compound and a base generating agent. Preferred embodiments of the organic solvent and at least one of the basic compound and base generating agent are the same as preferred embodiments of the organic solvent and at least one of the basic compound and base generating agent used in the rinse solution described above. The method of supplying the treatment solution to the pattern can be the same as the method of supplying the rinse solution described above, and the preferred embodiments are also the same.

[0440] The content of basic compounds or base generators in the treatment solution is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment solution. The lower limit of the above content is not particularly limited, but for example, it is preferably 0.1% by mass or more. Furthermore, if the basic compound or base generator is solid in the environment in which the treatment solution is used, the content of basic compounds or base generators is also preferably 70 to 100% by mass, relative to the total solid content of the treatment solution. When the treatment solution contains at least one of basic compounds and base generators, the treatment solution may contain only one type of basic compound or base generator, or it may contain two or more types. When there are two or more types of basic compounds and base generators, it is preferable that their total is within the above range.

[0441] <Heating Step> The pattern obtained by the developing step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the developing step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the developing step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a developing step, or a film obtained by a film formation step is heated. In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0442] The heating step is preferably a step in which the heating promotes the cyclization reaction of the polyimide precursor within the pattern by the action of bases generated from the base generating agent.

[0443] In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out heating at a heating rate of 1 to 8°C / second from the initial heating temperature to the maximum heating temperature, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0444] The starting temperature for heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature is initiated. For example, when the resin composition of the present invention is applied to a substrate and then dried, this is the temperature of the film (layer) after drying, and it is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0445] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0446] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0447] Heating may be carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to treat while irradiating with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such pretreatment steps can improve the properties of the film. The pretreatment step is preferably carried out for a short time of about 10 seconds to 2 hours, and more preferably for 15 seconds to 30 minutes. The pretreatment may consist of two or more steps; for example, the first pretreatment step may be carried out in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 200°C. Furthermore, cooling may be performed after heating, and in this case, the cooling rate is preferably 1 to 5°C / min.

[0448] The heating process is preferably carried out in a low-oxygen atmosphere, such as by flowing an inert gas like nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating means in the heating process is not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0449] <Post-development exposure step> The pattern obtained in the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a post-development exposure step in which the pattern after the development step is exposed, either in place of the heating step or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, reactions such as the cyclization of polyimide precursors etc. by photosensitivity of a photobase generator, or the elimination of acid-degradable groups by photosensitivity of a photoacid generator can be promoted. In the post-development exposure step, it is sufficient for at least a part of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The amount of exposure in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. ２ Preferably, 100 to 15,000 mJ / cm² ２ This is more preferable. The post-development exposure step can be performed, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

[0450] <Metal Layer Formation Process> The pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process) may be subjected to a metal layer formation process in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer formation process in which a metal layer is formed on the pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process).

[0451] The metal layer is not particularly limited, and existing metal species can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0452] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of the plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0453] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0454] The method for producing the cured product of the present invention may include a step of transferring the composition layer contained in the transfer film onto a substrate using the transfer film of the present invention, instead of the above-described <film formation step> and <drying step>. The substrate and transfer film are as described above.

[0455] The transfer can be carried out using a known laminator. Roll type, diaphragm type, press type, vacuum pressure type, etc., can be used. Examples of commercially available laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch type vacuum pressure laminators. Regarding the transfer method, the manufacturing methods described in paragraphs 0108 to 0111 of Japanese Patent Application Publication No. 2022-39763, paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696, and paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used.

[0456] <Applications> The manufacturing method of the cured product of the present invention, or the fields in which the cured product can be applied, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or etching to form patterns on insulating films for the above-mentioned mounting applications. For more information on these applications, please refer to, for example, Science & Technology Co., Ltd., "High-Functionality and Application Technologies of Polyimides," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimide Fundamentals and Applications," NTS, August 2010.

[0457] The method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used for manufacturing printing plates such as offset plates or screen printing plates, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0458] (Laminate and Method for Manufacturing a Laminate) The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention. The laminate is a laminate containing two or more layers made of the cured product, and may be a laminate with three or more layers. Of the two or more layers made of the cured product included in the above laminate, at least one is made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product due to the above shrinkage, it is also preferable that all the layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0459] In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

[0460] The laminate of the present invention preferably comprises two or more layers made of cured material, with a metal layer included between any of the layers made of cured material. The metal layer is preferably formed by the metal layer formation step described above. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer formation step in which a metal layer is formed on the layers made of cured material, between multiple cured material manufacturing steps. The preferred embodiment of the metal layer formation step is as described above. As the laminate, for example, a laminate is preferred that includes at least three layers in which a first layer made of cured material, a metal layer, and a second layer made of cured material are laminated in this order. It is preferable that both the first layer made of cured material and the second layer made of cured material are layers made of cured material of the present invention. That is, the laminate of the present invention preferably comprises two or more layers made of cured material of the present invention, with a metal layer included between any of the layers made of cured material. The resin composition of the present invention used to form the first layer made of cured material and the resin composition of the present invention used to form the second layer made of cured material may have the same composition or may have different compositions. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a redistribution layer.

[0461] <Lamination Process> The method for manufacturing a laminate of the present invention preferably includes a lamination process. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of a pattern (resin layer) or metal layer: (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process, and post-development exposure process. However, the method may also involve repeating at least one of the following: (a) film formation process and (d) heating process and post-development exposure process. Furthermore, at least one of the following: (d) heating process and post-development exposure process may be followed by (e) metal layer formation process. Needless to say, the lamination process may further include the above-mentioned drying process and the like as appropriate.

[0462] If further lamination is performed after the lamination process, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0463] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, a configuration with 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration with 2 to 9 resin layers is even more preferred. Each of the above layers may have the same composition, shape, film thickness, etc., or they may be different.

[0464] In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the steps in the order of (a) film formation, (b) exposure, (c) development, (d) heating and post-development exposure, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and post-development exposure, and (e) metal layer formation. By alternately performing the lamination step of stacking the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0465] (Surface Activation Treatment Step) The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer is surface activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment step may be performed on the resin composition layer before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the post-exposure resin composition layer. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on its surface can be improved. It is also preferable to perform the surface activation treatment on a portion or all of the post-exposure resin composition layer (resin layer). By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion to the metal layer and resin layer provided on the surface-activated surface can be improved. In particular, when developing negative film, if the resin composition layer is cured, it is less susceptible to damage from surface treatment and adhesion is easily improved. Surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This is incorporated herein by reference.

[0466] (Semiconductor Devices and Methods for Manufacturing the Same) The present invention also discloses semiconductor devices including a cured product or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product or a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0467] [Polyimide Precursor or Polyamideimide Precursor] The present invention relates to the following polyimide precursor or polyamideimide precursor: A polyimide precursor or polyamideimide precursor having repeating units represented by the following general formula (23) or the following general formula (24) (hereinafter also referred to as "precursor (11)").

[0468]

[0469] In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

[0470] The precursor (11) is synonymous with the precursor (11) in the resin composition (11) described above.

[0471] Furthermore, the present invention relates to the following polyimide precursor or polyamideimide precursor: A polyimide precursor or polyamideimide precursor comprising a structure represented by the following general formula (11), wherein the imidization rate of the polyimide precursor or polyamideimide precursor is less than 15% (hereinafter also referred to as "precursor (12)").

[0472]

[0473] In general formula (11), R １５ and R１６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. * indicates the bond position.

[0474] The precursor (12) is synonymous with the precursor (12) in the resin composition (12) described above.

[0475] Furthermore, the present invention relates to the following polyimide precursor or polyamideimide precursor: A polyimide precursor or polyamideimide precursor containing 10 ppm to 10,000 ppm of a compound represented by the following general formula (12), wherein the imidization rate of the polyimide precursor or polyamideimide precursor is less than 15% (hereinafter also referred to as "precursor (13)").

[0476]

[0477] In general formula (12), R １７ and R １８ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group.

[0478] The precursor (13) is synonymous with the precursor (13) in the resin composition (13) described above.

[0479] R in the above general formula (23) ２３ , R ２４ However, it is preferable that each independently represents a group represented by the following general formula (4A).

[0480]

[0481] In general formula (4A), A represents an organic group with a (q+1) valency, and L represents an oxygen atom, or N(R) ４６ ) (Caution ４７ ) (Caution ４６ , R ４７ Each of these independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and R ４３ ~R ４５ Each of these independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and q represents an integer from 1 to 4. * indicates the bond position.

[0482] Each group in general formula (4A) is the same as each group in general formula (4A) in the method for producing the polyimide precursor or polyamideimide precursor of the present invention described above, and the preferred range is also the same.

[0483] R in the above general formula (23) ２３ , R ２４ However, it is preferable that each independently represents a group represented by the following general formula (4).

[0484]

[0485] In general formula (4), A represents an organic group with (q+1) valence, and R ４３ ~R ４５ Each of these independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and q represents an integer from 1 to 4. * indicates the bond position.

[0486] Each group in general formula (4) is the same as each group in general formula (4) in the method for producing the polyimide precursor or polyamideimide precursor of the present invention described above, and the preferred range is also the same.

[0487] R in general formula (4) ４５ It is preferable that it be a hydrogen atom.

[0488] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0489] <Examples of synthesis of polyimide precursors or polyamideimidimide precursors (specific resins)> Synthesis Example 1 (Synthesis of A-1) A-1 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and ODA as the compound having two or more amino groups. Details of the synthesis method of A-1 are shown below. Mix 8.47 g (27.2 mmol) of 4,4'-oxydiphthalic acid dianhydride (ODPA), 7.25 g (55.6 mmol) of 2-hydroxyethyl methacrylate (HEMA), 0.015 g of hydroquinone, 1.38 g (13.6 mmol) of NMM (N-methylmorpholine), and 22.67 g of NMP (N-methylpyrrolidone), stir at 60°C for 3 hours, and cool to 25°C. Next, after cooling the above reaction solution in an ice bath, 14.34 g (81.7 mmol) of CDMT (2-chloro-4,6,-dimethoxy-1,3,5-triazine) is added, and a solution of 6.88 g (68.1 mmol) of NMM diluted with 17.54 g of NMP is added dropwise so that the temperature of the reaction solution does not exceed 0°C, and the mixture is stirred at or below 0°C for 30 minutes. Next, 5.13 g (25.6 mmol) of 4,4'-oxydianiline (ODA) dissolved in 32.38 g of NMP is added dropwise over 1 hour, and after raising the temperature to room temperature (25°C), the mixture is stirred for 4 hours. Then, 1.02 g (22.2 mmol) of ethanol is added, and the mixture is stirred for 1 hour, the polyimide precursor is precipitated in 2 L of water, and the water-polyimide precursor mixture is stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor is obtained by filtration, vacuum-dried, and then dissolved in 120 g of THF. Next, amphoteric ion exchange resin MB-1 (manufactured by Organo Corporation) is added and the mixture is stirred at 25°C for 4 hours to perform ion exchange treatment. The ion exchange resin is removed by filtration, the THF solution is precipitated in 4 L of water, and the polyimide precursor is filtered. The obtained polyimide precursor is then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (A-1). The structure of A-1 is represented by the following formula (A1). Polyimide precursor A-1 has the structure represented by the following formula (A1).

[0490]

[0491] Synthesis Example 2 (Synthesis of A-2) A-2 is synthesized using ODPA as the acid anhydride, 2-isobutoxyethanol as the side chain component, and ODA as the compound having two or more amino groups. The details of the synthesis method of A-2 are shown below. A-2 is synthesized in the same manner as in Synthesis Example 1, except that 7.25 g (55.6 mmol) of 2-hydroxyethyl methacrylate is replaced with 6.57 g (55.6 mmol) of 2-isobutoxyethanol. The structure of A-2 is represented by the following formula (A-2). The polyimide precursor A-2 has the structure represented by the following formula (A2).

[0492]

[0493] Synthesis Example 3 (Synthesis of A-3) A-3 is synthesized using ODPA as the acid anhydride, HEMA and 2-isobutoxyethanol as side chain components, and ODA as a compound having two or more amino groups. The details of the synthesis method of A-3 are shown below. A-3 is synthesized in the same manner as in Synthesis Example 1, except that 7.25 g (55.6 mmol) of 2-hydroxyethyl methacrylate is replaced with 3.63 g (27.8 mmol) of 2-hydroxyethyl methacrylate and 3.28 g (27.8 mmol) of 2-isobutoxyethanol. The structure of A-3 is represented by the following formula (A-3). The polyimide precursor A-3 has the structure represented by the following formula (A3).

[0494]

[0495] Synthesis Example 4 (Synthesis of A-4) A-4 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and m-tolidine as the compound having two or more amino groups. The details of the synthesis method of A-4 are shown below. Mix 20.83 g (67 mmol) of 4,4'-oxydiphthalic acid dianhydride, 17.79 g (136 mmol) of 2-hydroxyethyl methacrylate, 0.037 g of hydroquinone, 3.39 g (33.5 mmol) of NMM (N-methylmorpholine), and 51.28 g of THF (tetrahydrofuran), stir at 60°C for 3 hours, and cool to 25°C. Next, the reaction solution was cooled in an ice bath, then 35.27 g (200 mmol) of CDMT was added, and a solution of 16.84 g (166.5 mmol) of NMM diluted with 40.79 g of THF was added dropwise so that the temperature of the reaction solution would not exceed 0°C, and the mixture was stirred at or below 0°C for 30 minutes. Subsequently, 13.38 g (62.9 mmol) of m-tolidine dissolved in 81.46 g of PGME was added dropwise over 1 hour, and the mixture was heated to room temperature and stirred for 4 hours. Then, 12.3 g (267 mmol) of ethanol was added, and the mixture was stirred for 1 hour. The solution diluted with 80 g of acetonitrile was added to 4 L of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor is obtained by filtration, vacuum-dried, and then dissolved in 280 g of THF. Next, amphoteric ion exchange resin MB-1 is added and the mixture is stirred at 25°C for 4 hours to perform ion exchange treatment. The ion exchange resin is removed by filtration, the THF solution is precipitated in 4 L of water, and the polyimide precursor is filtered. The obtained polyimide precursor is then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (A-4). The structure of A-4 is represented by the following formula (A-4). Polyimide precursor A-4 has the structure represented by the following formula (A4).

[0496]

[0497] Synthesis Example 5 (Synthesis of A-5) A-5 is synthesized using BPDA as the acid anhydride, HBA as the side chain component, and BAPOBP as a compound having two or more amino groups. The details of the synthesis method of A-5 are shown below. A-5 is synthesized in the same manner as in Synthesis Example 4, except that 20.83 g (67 mmol) of 4,4'-oxydiphthalic acid dianhydride is replaced with 19.71 g (67 mmol) of 4,4'-biphthalic acid dianhydride (BPDA), 17.79 g (136 mmol) of 2-hydroxyethyl methacrylate is replaced with 19.61 g (136 mmol) of 4-hydroxybutyl acrylate (HBA), 13.38 g (62.9 mmol) of m-tolidine is replaced with 23.17 g (62.9 mmol) of BAPOBP, and PGME is replaced with ethyl lactate. The structure of A-5 is represented by the following formula (A-5). Polyimide precursor A-5 has the structure represented by the following formula (A5).

[0498]

[0499] Synthesis Example 6 (Synthesis of A-6) A-6 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and BAP as a compound having two or more amino groups. The details of the synthesis method of A-6 are shown below. A-6 is synthesized in the same manner as in Synthesis Example 1, except that 5.13 g (25.6 mmol) of 4,4'-oxydianiline is replaced with 6.61 g (25.6 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP). The structure of A-6 is represented by the following formula (A-6). The polyimide precursor A-6 has the structure represented by the following formula (A6).

[0500]

[0501] Synthesis Example 7 (Synthesis of A-7) A-7 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and HAB as the compound having two or more amino groups. The details of the synthesis method of A-7 are shown below. A-7 is synthesized in the same manner as in Synthesis Example 4, except that 13.38 g (62.9 mmol) of m-tolidine is replaced with 13.60 g (62.9 mmol) of HAB. The structure of A-7 is represented by the following formula (A-7). The polyimide precursor A-7 has the structure represented by the following formula (A7).

[0502]

[0503] Synthesis Example 8 (Synthesis of A-8) A-8 is synthesized using ODPA as the acid anhydride, 2-isobutoxyethanol as the side chain component, and HAB as the compound having two or more amino groups. The details of the synthesis method of A-8 are shown below. A-8 is synthesized in the same manner as in Synthesis Example 7, except that 2-hydroxyethyl methacrylate is replaced with 6.57 g (55.6 mmol) of 2-isobutoxyethanol. The structure of A-8 is represented by the following formula (A-8). The polyimide precursor A-8 has the structure represented by the following formula (A-8).

[0504]

[0505] Synthesis Example 9 (Synthesis of A-9) A-9 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and ODA as the compound having two or more amino groups. The details of the synthesis method of A-9 are shown below. A-9 is synthesized in the same manner as in Synthesis Example 1, except that CDMT is replaced with the same molar amount of DCMT (2,4-dichloro-6-methoxy-1,3,5-triazine). The structure of A-9 is represented by the following formula (A-9). The polyimide precursor A-9 has the structure represented by the following formula (A9).

[0506]

[0507] Synthesis Example 10 (Synthesis of A-10) A-10 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and ODA as the compound having two or more amino groups. The details of the synthesis method of A-10 are shown below. A-10 is synthesized in the same manner as in Synthesis Example 1, except that NMM is replaced with the same molar amount of TEA. The structure of A-10 is represented by the following formula (A-10). The polyimide precursor A-10 has the structure represented by the following formula (A10).

[0508]

[0509] Synthesis Example 11 (Synthesis of A-11) A-11 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and ODA as the compound having two or more amino groups. The details of the synthesis method of A-11 are shown below. A-11 is synthesized in the same manner as in Synthesis Example 1, except that NMM is replaced with the same molar amount of DABCO. The structure of A-11 is represented by the following formula (A-11). The polyimide precursor A-11 has the structure represented by the following formula (A-11).

[0510]

[0511] Synthesis Example 12 (Synthesis of A-12) A-12 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and DAB as a compound having two or more amino groups. The details of the synthesis method of A-12 are shown below. A-12 is synthesized in the same manner as in Synthesis Example 4, except that 13.38 g (62.9 mmol) of m-tolidine is replaced with 13.47 g (62.9 mmol) of DAB. The structure of A-12 is represented by the following formula (A-12). The polyimide precursor A-12 has the structure represented by the following formula (A12).

[0512]

[0513] Synthesis Example 13 (Synthesis of A-13) A-13 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and ODA as the compound having two or more amino groups. The details of the synthesis method of A-13 are shown below. A-13 is obtained in the same manner as in Synthesis Example 1, except that NMM is changed to 150 mmol. The structure of A-13 is represented by the following formula (A-13). The polyimide precursor A-13 has the structure represented by the following formula (A13).

[0514]

[0515] Comparative Synthesis Example 1 (Synthesis of A-14) (Comparative Example) A-14 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and ODA as the compound having two or more amino groups. The details of the synthesis method for A-14 are shown below. 8.47 g (27.2 mmol) of 4,4'-oxydiphthalic acid dianhydride (ODPA), 7.25 g (55.6 mmol) of 2-hydroxyethyl methacrylate (HEMA), 0.015 g of hydroquinone, 1.38 g (13.6 mmol) of NMM (N-methylmorpholine), and 22.67 g of NMP (N-methylpyrrolidone) are mixed and stirred at 60°C for 3 hours, then cooled to 25°C. Next, the reaction solution is cooled in an ice bath, and 22.6 g (81.7 mmol) of DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride is added. 17.54 g of NMP is added dropwise, ensuring the reaction solution temperature does not exceed 0°C, and the mixture is stirred at or below 0°C for 30 minutes. Subsequently, 5.13 g (25.6 mmol) of 4,4'-oxydianiline (ODA) is dissolved in 32.38 g of NMP and added dropwise over 1 hour. The mixture is then heated to room temperature (25°C) and stirred for 4 hours. Next, 1.02 g (22.2 mmol) of ethanol is added, and the mixture is stirred for 1 hour. The polyimide precursor is precipitated in 2 L of water, and the water-polyimide precursor mixture is stirred at 500 rpm for 15 minutes. The polyimide precursor is obtained by filtration, vacuum-dried, and then dissolved in 120 g of THF. Next, amphoteric ion exchange resin MB-1 (manufactured by Organo Corporation) is added and the mixture is stirred at 25°C for 4 hours to perform ion exchange treatment. The ion exchange resin is removed by filtration, the THF solution is precipitated in 4 L of water, and the polyimide precursor is filtered. The obtained polyimide precursor is then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (A-14). The structure of A-14 is represented by the following formula (A-14). Polyimide precursor A-14 has the structure represented by the following formula (A14).

[0516]

[0517] Comparative Synthesis Example 2 (Synthesis of A-15) (Comparative Example) 46.96 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) is placed in a separable flask, 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone are added and stirred at room temperature, and 24.66 g of pyridine is added while stirring to obtain the reaction mixture. After the exothermic reaction is complete, it is allowed to cool to room temperature and left at room temperature for 16 hours. Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone is added to the reaction mixture over 40 minutes while stirring, followed by 27.42 g of 4,4'-oxydianiline (ODA) suspended in 119.73 g of γ-butyrolactone, which is added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and stirred for 1 hour, then 136.83 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution. The obtained reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of crude polymer. The produced crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered off and vacuum dried to obtain powdered polymer (polyimide precursor) A-15. The molecular weight of polymer A-15 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 20,000. The structure of A-15 is represented by the following formula (A-15).

[0518]

[0519] Comparative Synthesis Example 3 (Synthesis of A-16) (Comparative Example) We attempt to synthesize the compound by substituting the starting materials in Comparative Synthesis Example 2, but the OH group of the compound unit having two or more amino groups and the NH group to be left in the side chain ２ The reaction causes gelation, making synthesis impossible. The raw materials are listed in Table 3.

[0520] Comparative Synthesis Example 4 (Synthesis of A-17) (Comparative Example) We attempt to synthesize the compound by substituting the raw materials in Comparative Synthesis Example 2, but the OH group of the compound unit having two or more amino groups and the NH group to be left in the side chain ２ The reaction causes gelation, making synthesis impossible. The raw materials are listed in Table 3.

[0521] Comparative Synthesis Example 5 (Synthesis of A-18) (Comparative Example) In Comparative Synthesis Example 2, the solvent is replaced with PGME and 4,4'-oxydianiline (ODA) is replaced with the same molar amount of m-tolidine to attempt synthesis. However, the activated carboxylic acid derivative reacts with the alcohol-based solvent, and polymerization does not proceed. The raw materials are listed in Table 3.

[0522] Comparative Synthesis Example 6 (Synthesis of A-19) (Comparative Example) 21.18 g (68.1 mmol) of 4,4'-oxydiphthalic acid dianhydride (ODPA), 18.12 g (139 mmol) of 2-hydroxyethyl methacrylate (HEMA), 0.038 g of hydroquinone, 23.93 g (30.3 mmol) of pyridine, and 76.7 g of diglim are mixed and stirred at 60°C for 3 hours, then cooled to 25°C. Subsequently, the reaction solution is cooled to -10°C, and then 16.774 g (141 mmol) of thionyl chloride dissolved in 59.35 g of diglim is added dropwise over 60 minutes, the temperature is raised to 30°C, and the mixture is stirred for 1.5 hours. Next, the mixture is cooled to 0°C, and 12.27 g (61.2 mmol) of 4,4'-oxydianiline (ODA) dissolved in 92.46 g of NMP is added dropwise over 1 hour, followed by stirring for 1 hour. Then, 12.55 g (272 mmol) of ethanol is added, and the mixture is stirred for 1 hour to precipitate the polyimide precursor in 4 L of water. The water-polyimide precursor mixture is then stirred at 500 rpm for 15 minutes. The polyimide precursor is filtered and obtained, then vacuum-dried, and dissolved in 300 g of THF. Next, 50 g of MB-1 (manufactured by Organo Corporation) is added as an ion exchange resin, and the mixture is stirred at 25°C for 4 hours to perform ion exchange treatment. The ion exchange resin is removed by filtration, the THF solution is precipitated in 4 L of water, and the polyimide precursor is filtered. The obtained polyimide precursor is then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (A-19). The weight-average molecular weight (Mw) of the obtained polyimide precursor (A-19) is 24,000. The structure of A-19 is represented by the following formula (A-19).

[0523]

[0524] Comparative Synthesis Example 7 (Synthesis of A-20) (Comparative Example) We attempt to synthesize the compound by substituting the raw materials in Comparative Synthesis Example 6, but the OH group of the compound unit having two or more amino groups and the NH group to be left in the side chain ２ The reaction causes gelation, making synthesis impossible. The raw materials are listed in Table 3.

[0525] Comparative Synthesis Example 8 (Synthesis of A-21) (Comparative Example) We attempt to synthesize the compound by substituting the raw materials in Comparative Synthesis Example 6, but the OH group of the compound unit having two or more amino groups and the NH group to be left in the side chain ２ The reaction causes gelation, making synthesis impossible. The raw materials are listed in Table 3.

[0526] Comparative Synthesis Example 9 (Synthesis of A-22) (Comparative Example) In Comparative Synthesis Example 6, the solvent was replaced with PGME and 4,4'-oxydianiline (ODA) was replaced with the same molar amount of m-tolidine to attempt synthesis. However, the activated carboxylic acid derivative reacted with the alcohol-based solvent, and polymerization did not proceed. The raw materials are listed in Table 3.

[0527] Synthesis Example 14 (Synthesis of A-23) A-23 is synthesized using TMA as the acid anhydride, HEMA as the side chain component, and ODA as a compound having two or more amino groups. 5.23 g (27.2 mmol) of trimellitic anhydride (TMA), 3.63 g (27.8 mmol) of 2-hydroxyethyl methacrylate, 0.015 g of hydroquinone, 1.38 g (13.6 mmol) of NMM (N-methylmorpholine), and 22.67 g of NMP (N-methylpyrrolidone) are mixed and stirred at 60°C for 3 hours, then cooled to 25°C. Next, after cooling the above reaction solution in an ice bath, 14.34 g (81.7 mmol) of CDMT is added, and a solution of 6.88 g (68.1 mmol) of NMM diluted with 17.54 g of NMP is added dropwise so that the temperature of the reaction solution does not exceed 0°C, and the mixture is stirred at or below 0°C for 30 minutes. Next, 5.13 g (25.6 mmol) of 4,4'-oxydianiline dissolved in 32.38 g of NMP is added dropwise over 1 hour, and after raising the temperature to room temperature, the mixture is stirred for 4 hours. Then, 1.02 g (22.2 mmol) of ethanol is added, and the mixture is stirred for 1 hour, the polyamide-imide precursor is precipitated in 2 L of water, and the water-polyamide-imide precursor mixture is stirred at a speed of 500 rpm for 15 minutes. The polyamide-imide precursor is obtained by filtration, vacuum-dried, and then dissolved in 120 g of THF. Next, amphoteric ion exchange resin MB-1 is added and the mixture is stirred at 25°C for 4 hours to perform ion exchange treatment. The ion exchange resin is removed by filtration, the THF solution is precipitated in 4 L of water, and the polyamide-imide precursor is filtered. The obtained polyamide-imide precursor is then dried under reduced pressure at 45°C for 2 days to obtain polyamide-imide precursor (A-23). ​​The structure of A-23 is represented by the following formula (A-23). ​​Polyamide-imide precursor A-23 has the structure represented by the following formula (A23).

[0528]

[0529] Synthesis Example 15 (Synthesis of A-24) A-24 is synthesized using ODPA and BPDA as acid anhydrides, HEMA and 2-isobutoxyethanol as side chain components, and m-tolidine as a compound having two or more amino groups. 6.33 g (20.4 mmol) of 4,4'-oxydiphthalic acid dianhydride, 2.00 g (6.8 mmol) of 4,4'-biphthalic acid dianhydride, 5.07 g (38.9 mmol) of 2-hydroxyethyl methacrylate, 16.7 g (1.97 mmol) of 2-isobutoxyethanol, 0.015 g of hydroquinone, 1.38 g (13.6 mmol) of NMM (N-methylmorpholine), and 22.67 g of NMP (N-methylpyrrolidone) are mixed and stirred at 60°C for 3 hours, then cooled to 25°C. Next, after cooling the reaction solution in an ice bath, 16.64 g (81.7 mmol) of CDET is added, and a solution of 6.88 g (68.1 mmol) of NMM diluted with 17.54 g of NMP is added dropwise so that the temperature of the reaction solution does not exceed 0°C, and the mixture is stirred at or below 0°C for 30 minutes. Next, 5.43 g (25.6 mmol) of m-tolidine dissolved in 32.38 g of NMP is added dropwise over 1 hour, the temperature is raised to room temperature, and the mixture is stirred for 4 hours. Then, 1.02 g (22.2 mmol) of ethanol is added, the mixture is stirred for 1 hour, the polyimide precursor is precipitated in 2 L of water, and the water-polyimide precursor mixture is stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor is obtained by filtration, vacuum dried, dissolved in 120 g of THF, and then amphoteric ion exchange resin MB-1 is added and the mixture is stirred at 25°C for 4 hours to perform ion exchange treatment. The ion exchange resin is removed by filtration, the THF solution is precipitated in 4 L of water, and the polyimide precursor is filtered. The obtained polyimide precursor is then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (A-24). The structure of A-24 is represented by the following formula (A-24). Polyamideimide precursor A-24 has the structure represented by the following formula (A24).

[0530]

[0531] Synthesis Example 16 (Synthesis of A-25) A-25 is synthesized using ODPA and BPDA as acid anhydrides, HEMA and 2-isobutoxyethanol as side chain components, and m-tolidine as a compound having two or more amino groups. The details of the synthesis method of A-25 are shown below. A-15 is obtained in the same manner as in Synthesis Example 15, except that CDET is changed to the same molar amount of CDBT. The structure of A-25 is represented by the following formula (A-25). The polyimide precursor A-25 has the structure represented by the following formula (A25).

[0532]

[0533] Synthesis Example 17 (Synthesis of A-26) A-26 is synthesized using ODPA and BPDA as acid anhydrides, HEAA, HEMA, and 2-isobutoxyethanol as side chain components, and m-tol as a compound having two or more amino groups. The details of the synthesis method for A-26 are shown below. Mix 16.32 g (52.6 mmol) of 4,4'-oxydiphthalic acid dianhydride (ODPA), 5.16 g (17.5 mmol) of 4,4'-biphthalic acid dianhydride (BPDA), 7.46 g (57.3 mmol) of 2-hydroxyethyl methacrylate (HEMA), 4.95 g (43.0 mmol) of 2-hydroxyethyl acrylamide (HEAA), 5.08 g (43.0 mmol) of 2-isobutoxyethanol, 0.04 g of hydroquinone, 3.55 g (35.1 mmol) of NMM (N-methylmorpholine), and 53.72 g of THF (tetrahydrofuran), stir at 60°C for 3 hours, and then cool to 25°C. Next, the reaction solution is cooled in an ice bath, then 36.95 g (210.5 mmol) of CDMT (2-chloro-4,6,-dimethoxy-1,3,5-triazine) is added, followed by 42.74 g of THF, and then 17.74 g (175.4 mmol) of NMM is added dropwise so that the temperature of the reaction solution does not exceed 0°C, and the mixture is stirred at or below 0°C for 30 minutes. Subsequently, 14.30 g (67.3 mmol) of m-tolidine (m-tol) is dissolved in 63.22 g of PGME, and this solution is added dropwise over 1 hour. After raising the temperature to room temperature (25°C), the mixture is stirred for 4 hours. Then, 12.28 g (266 mmol) of ethanol is added, and the mixture is stirred for 1 hour. The polyimide precursor is precipitated in 2 L of water, and the water-polyimide precursor mixture is stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor is obtained by filtration, vacuum-dried, and then dissolved in 300 g of THF. Next, amphoteric ion exchange resin MB-1 (manufactured by Organo Corporation) is added and the mixture is stirred at 25°C for 4 hours to perform ion exchange treatment. The ion exchange resin is removed by filtration, the THF solution is precipitated in 5 L of water, and the polyimide precursor is filtered. The obtained polyimide precursor is then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (A-26). The structure of A-26 is represented by the following formula (A-26).Polyimide precursor A-26 has a structure represented by the following formula (A26).

[0534]

[0535] Synthesis Example 18 (Synthesis of A-27) A-27 is synthesized using ODPA and BPDA as acid anhydrides, HPMA, HEMA and 2-isobutoxyethanol as side chain components, and m-tol as a compound having two or more amino groups. Details of the synthesis method of A-27 are shown below. It is synthesized in the same manner as in Synthesis Example 17, except that 4.95 g (43.0 mmol) of 2-hydroxyethylacrylamide (HEAA) is replaced with 6.16 g (43.0 mmol) of N-(2-hydroxypropyl)methacrylamide (HPMA). The structure of A-27 is represented by the following formula (A-27). The polyimide precursor A-27 has the structure represented by the following formula (A27).

[0536]

[0537] Synthesis Example 19 (Synthesis of A-28) A-28 is synthesized using ODPA as the acid anhydride, HEA as the side chain component, and ODA as the compound having two or more amino groups. The details of the synthesis method of A-28 are shown below. It is synthesized in the same manner as in Synthesis Example 1, except that 7.25 g (55.6 mmol) of 2-hydroxyethyl methacrylate (HEMA) is replaced with 6.46 g (55.6 mmol) of 2-hydroxyethyl acrylate (HEA). The structure of A-28 is represented by the following formula (A-28). The polyimide precursor A-28 has the structure represented by the following formula (A28).

[0538]

[0539] Synthesis Example 20 (Synthesis of A-29) A-29 is synthesized using ODPA as the acid anhydride, HEMA as the side chain component, and DABA as a compound having two or more amino groups. The details of the synthesis method for A-29 are shown below. The synthesis is carried out in the same manner as in Synthesis Example 1, except that 5.13 g (25.6 mmol) of 4,4'-oxydianiline (ODA) dissolved in 2.38 g of NMP is replaced with 5.18 g (25.6 mmol) of 4,4'-diaminobenzanilide (DABA) dissolved in 75.25 g of methanol. The structure of A-29 is represented by the following formula (A-29). The polyimide precursor A-29 has the structure represented by the following formula (A29).

[0540]

[0541] Synthesis Example 21 (Synthesis of A-30) A-30 is synthesized using BPDA as the acid anhydride, HEMA as the side chain component, and CHDA as a compound having two or more amino groups. The details of the synthesis method for A-30 are shown below. It is synthesized in the same manner as in Synthesis Example 1, except that 8.47 g (27.2 mmol) of 4,4'-oxydiphthalic acid dianhydride (ODPA) is replaced with 8.00 g (27.2 mmol) of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), and 5.13 g (25.6 mmol) of 4,4'-oxydianiline (ODA) is replaced with 2.92 g (25.6 mmol) of 1,4-cyclohexanediamine (CHDA). The structure of A-30 is represented by the following formula (A-30). Polyimide precursor A-30 has a structure represented by the following formula (A30).

[0542]

[0543] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured using gel permeation chromatography (GPC) and expressed as polystyrene equivalents. Mw and Mn were determined using an HLC-8220GPC (manufactured by Tosoh Corporation), with the following columns connected in series: Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation). NMP (N-methyl-2-pyrrolidone) was used as the eluent. For GPC measurement, a UV (ultraviolet) wavelength 254 nm detector was used.

[0544] Each example and comparative example uses precursors A-1 to A-13, A-14 to A-15, A-19, and A-23 to A-30 synthesized in Synthesis Examples 1 to 21 and Comparative Synthesis Examples 1, 2, and 6. Table 3 lists the "acid anhydride," "side chain component," "compound having two or more amino groups," "solvent," "triazine chloride compound," and "tertiary amine" used in the synthesis of precursors A-1 to A-13, A-14 to A-15, A-19, and A-23 to A-30. Table 3 also lists the "Mw" of the synthesized precursors A-1 to A-13, A-14 to A-15, A-19, and A-23 to A-30. Furthermore, although they cannot be synthesized as described above, Table 3 lists the "acid anhydrides," "side chain components," "compounds having two or more amino groups," "solvents," "triazine chloride compounds," and "tertiary amines" used in the synthesis of precursors A-16 to A-18 and A-20 to A-22. Note that the solvents (polymerization solvents) listed in Table 3 are solvents used when reacting compounds having two or more amino groups, and are used for preparing solutions of compounds having two or more amino groups.

[0545] [Imidization rate of polyimide precursor or polyamideimide precursor] The imidization rate of polyimide precursor or polyamideimide precursor is １ It is calculated from the results of 1H-NMR (nuclear magnetic resonance) measurements. １H-NMR spectrometer: Bruker, 400 MHz. Measurement solvent: Deuterium DMSO (dimethyl sulfoxide). The imidization rate is calculated from the integral ratio of the proton peaks of the benzene ring in the unit corresponding to the compound having two or more amino groups. (I): Unimidized benzene ring proton: Integral ratio of the proton peak around 6.9 ppm. (II): Imidized benzene ring proton: Integral ratio of the proton peak around 7.1 ppm. The imidization rate is expressed as follows: (Imidization rate) = II / (I + II)

[0546] The imidization rate is evaluated as follows: A: Less than 5% B: 5% or more but less than 10% C: 10% or more but less than 15% D: 15% or more

[0547] The results obtained are shown in Table 3.

[0548] The sulfur element content in the above precursor is measured as follows.

[0549] [Quantitative determination of sulfur element in resin (precursor) by combustion ion chromatography] Place 50 mg of the sample (the above precursor) on a sample board, weigh it, and then perform combustion ion chromatography under the following conditions. Sample combustion temperature: 900°C (inlet) / 1000°C (outlet) Absorption solution conditions: Approximately 0.01% H ２ O ２ aq. +2ppm KH ２ PO ４ aq. (Internal standard) Absorption volume: 5 mL Column: Dionex IonPac AS22 Eluent: 4.5 mmol / L Na ２ CO ３ + 1.4 mmol / L NaHCO ３ Flow rate: 1.2 mL / min Column temperature: 35°C Absorption solution injection volume: 100 μL Concentration correction: Two constant-volume check measurements are performed, the amount of sulfur element in each sample is quantified, and the average value is used.

[0550] The amount of sulfur in the above precursor is shown in Table 3.

[0551] The presence of the structure represented by the above general formula (11) in the polyimide precursor or polyamideimide precursor is as follows:１ It can be measured by 1H-NMR. The structure represented by general formula (11) in the polyimide precursor or polyamideimide precursor is １ Identification is performed based on the results of 1H-NMR (nuclear magnetic resonance) measurements. １ H-NMR spectrometer: Bruker, 400 MHz. Measurement solvent: Deuterium DMSO (dimethyl sulfoxide). The peak of the methoxy group of triazine is detected at around 4.0 ppm. Regarding the polyimide precursor or polyamideimide precursor obtained by the method for producing the polyimide precursor or polyamideimide precursor of the present invention, １ The existence of the structure represented by general formula (11) can be confirmed by H-NMR.

[0552] For the obtained precursors A-1 to A-14 and A-23 to A-30, the existence of the structure represented by general formula (11) can be confirmed. This structure is represented by (A1) to (A14) and (A23) to (A30) in precursors A-1 to A-14 and A-23 to A-30. For the obtained polyimide precursors A-15 and A-19, the existence of the structure represented by general formula (11) cannot be confirmed. As mentioned above, polyimide precursors A-16 to A-18 and A-20 to A-22 cannot be synthesized and therefore cannot be measured.

[0553] The presence of the compound represented by the above general formula (12) in the polyimide precursor or polyamideimide precursor, and its content, can be measured by GC (gas chromatography) as follows. (GC measurement sample preparation) Dissolve the polyimide precursor or polyamideimide precursor powder (0.1 g) in NMP (4.9 g) in a sample bottle, filter the liquid through a Teflon filter, and perform GC measurement on the resulting liquid. (GC conditions) Perform the measurement under the following conditions to confirm and quantify the compound represented by the general formula (12).

[0554]

[0555] The presence of the compound represented by general formula (12) can be confirmed for the obtained precursors A-1 to A-14 and A-23 to A-30. Table 3 shows the structure of the compound represented by general formula (12) and the content of the compound represented by general formula (12) for each precursor. The presence of the compound represented by general formula (12) cannot be confirmed for the obtained polyimide precursors A-15 and A-19. As mentioned above, polyimide precursors A-16 to A-18 and A-20 to A-22 cannot be synthesized and therefore cannot be measured.

[0556] Table 3 shows the relationship between the content A of the triazine chloride compound and the content B of the tertiary amine used in the synthesis of the resulting precursors A-1 to A-13 and A-23 to A-30, under the heading "Relationship between A and B". Note that the content is expressed on a molar basis.

[0557]

[0558] The components in Table 3 are as follows:

[0559] (Acid anhydrides) ODPA: 4,4'-oxydiphthalic acid dianhydride BPDA: 4,4'-biphthalic acid dianhydride TMA: trimellitic acid anhydride

[0560] (Side chain components) HEMA: 2-hydroxyethyl methacrylate HBA: 4-hydroxybutyl acrylate HEAA: 2-hydroxyethyl acrylamide HPMA: N-(2-hydroxypropyl) methacrylamide

[0561] (Compounds having two or more amino groups) ODA: 4,4'-oxydianiline m-tol: m-tolidine BAPOBP: 4,4'-bis(3-aminophenoxy)biphenyl BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane HAB: 3,3'-dihydroxybenzidine DAB: 3,3'-diaminobenzidine DABA: 4,4'-diaminobenzanilide CHDA: 1,4-cyclohexanediamine

[0562] (Solvents) NMP: N-methylpyrrolidone PGME: Propylene glycol monomethyl ether EL: Ethyl lactate GBL: γ-butyrolactone

[0563] (Triazine Chloride Compounds) The following are examples of triazine chloride compounds that can be used.

[0564]

[0565] (Tertiary amines) NMM: N-methylmorpholine TEA: Triethylamine DABCO: 1,4-diazabicyclo[2.2.2]octane

[0566] (Other activators) DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride DCC: N,N'-dicyclohexylcarbodiimide

[0567] (Compounds represented by general formula (12)) DMT-OH: Dimethoxy-1,3,5-triazine-2-ol MT-DOH: Methoxy-1,3,5-triazine-2,4-diol DET-OH: Diethoxy-1,3,5-triazine-2-ol DBT-OH: Dibenzyloxy-1,3,5-triazine-2-ol

[0568] <Examples 1-30 and Comparative Examples 1-3> Each resin composition is obtained by mixing the components (precursors and other components) listed in Tables 4-6 below. The other components are used in the amounts (mass%) listed in Tables 4-6 below. Tables 4-6 below show the resin content (mass%) and the content (mass%) of other components relative to the total solids content of each resin composition. The solids concentration in each resin composition is 35% by mass. The "ratio" of the solvent is the mass ratio (mass%) of each solvent to the total amount of solvent. The obtained resin composition is pressure filtered using a polytetrafluoroethylene filter with a pore width of 20.0 μm. In the table, a "-" in the "precursor" column indicates that the corresponding compound was not used in the synthesis of the resin. Also, a "-" in the column for each component other than the precursor indicates that the corresponding component is not contained in the resin composition.

[0569]

[0570]

[0571]

[0572] Details of each component listed in the table above are as follows:

[0573] <Polymerizable Compounds> The polymerizable compounds used are listed below.

[0574]

[0575]

[0576] <Polymerization Initiators> The following are the polymerization initiators to be used: C-1: IRGACURE OXE 01 (manufactured by BASF) C-2: IRGACURE OXE 02 (manufactured by BASF)

[0577] <Base Generating Agents> The following are the base generating agents to be used.

[0578]

[0579] <Migration Inhibitors> The following are the migration inhibitors that can be used.

[0580]

[0581] <Metal Adhesion Modifiers> The following are metal adhesion modifiers to be used.

[0582]

[0583] <Polymerization Inhibitors> The following are the polymerization inhibitors to be used.

[0584]

[0585] <Solvent> As a solvent, for example, the following can be used, and in the examples, one of the following will be selected and used: DMSO: Dimethyl sulfoxide GBL: γ-Butyrolactone NMP: N-Methylpyrrolidone

[0586] <Evaluation> The evaluation will be conducted as follows, and the results will be recorded in Tables 4-6 above.

[0587] [Method for Fabricating Reliability Evaluation Substrates] The resin compositions and comparative compositions prepared in each example and comparative example are applied to the surface of a Waltz TEG (test elementary group) substrate SIPOS-TEG SI06 by spin coating and dried at 100°C for 300 seconds. The film thickness is set to a thickness of 10 μm for the resulting cured product. After that, a photomask for TEG substrate evaluation is placed on top and 400 mJ / cm² is applied. ２ Broadband light is irradiated. After exposure, development is performed using cyclopentanone, rinsed with PGMEA, and then treated with N in a Koyo Thermo Systems CLH-2 clean oven. ２ The reliability evaluation substrate is fabricated by heating it to 230°C for 180 minutes at a heating rate of 5°C / min under atmospheric conditions.

[0588] [PCT Test] In each example and comparative example, a PCT test will be performed using the above-mentioned reliability evaluation substrate with a Hirayama Seisakusho HAST apparatus PC-422R8D, under the conditions of 121°C, 100% RH (relative humidity), and 250 hours. After the test, the substrate will be observed with an optical microscope to visually check for the occurrence of foreign matter or wiring corrosion.

[0589] [Method for Evaluating the Coated Surface (In-Plane Uniformity)] The resin composition prepared in each example and comparative example, as well as the comparative composition, are applied to the surface of an 8-inch silicon substrate by spin coating and dried at 100°C for 300 seconds. The film thickness is set to a thickness of 10 μm for the resulting cured product (coated film). The film thickness of the coated surface is measured using a contact-type film thickness gauge (Decktack), and the in-plane uniformity is calculated as follows: In-plane uniformity = (Average film thickness) - (Measured film thickness that deviates most from the average)

[0590] In-plane uniformity is evaluated as follows:

[0591] A: Smaller than 0.25 μm B: 0.25 μm or larger but less than 0.5 μm C: 0.5 μm or larger but less than 0.75 μm D: 0.75 μm or larger

[0592] [Residual film rate in exposed areas] The resin compositions and comparative compositions prepared in each example and comparative example are applied to a silicon wafer by spin coating and dried at 100°C for 300 seconds. Then, 400 mJ / cm² is applied. ２ The sample is irradiated with broadband light. After exposure, it is developed using cyclopentanone and rinsed with PGMEA. The percentage of remaining film in the exposed area is determined from the change in film thickness before and after development. Percentage of remaining film in the exposed area (%) = [Film thickness after development in the exposed area / Film thickness before development in the unexposed area] × 100

[0593] The residual film percentage in the exposed area is evaluated as follows. A rating of D or higher indicates that it can be used without practical problems.

[0594] A: 90% or more B: 85% or more but less than 90% C: 80% or more but less than 85% D: 70% or more but less than 80% E: Less than 70%

[0595] <Examples 31-32 and Comparative Example 4> The components (precursors and other components) listed in Table 7 below were mixed to obtain each resin composition. The other components were used in the amounts (mass%) listed in Table 7 below. Table 7 below shows the resin content (mass%) and the other component content (mass%) relative to the total solids content of each resin composition. The solids concentration in each resin composition was 35% by mass. The obtained resin compositions were subjected to pressure filtration using a polytetrafluoroethylene filter with a pore width of 20.0 μm.

[0596]

[0597] The details of each component listed in the table above are as described above.

[0598] <Evaluation> The evaluation will be conducted as follows, and the results will be recorded in Table 7 above.

[0599] [Method for Fabricating Reliability Evaluation Substrates] The resin compositions and comparative compositions prepared in each example and comparative example are applied to a support film. A transfer film is formed by drying at 120°C so that the composition layer thickness is 10 μm. A laminator is then applied to the surface of a Waltz TEG (test elementary group) substrate SIPOS-TEG SI06 to transfer the composition layer onto the substrate. A photomask for TEG substrate evaluation is then placed on top, and a pressure of 400 mJ / cm² is applied. ２ Broadband light is irradiated. After exposure, development is performed using cyclopentanone, rinsed with PGMEA, and then treated with N in a Koyo Thermo Systems CLH-2 clean oven. ２ The reliability evaluation substrate is fabricated by heating it to 230°C for 180 minutes at a heating rate of 5°C / min under atmospheric conditions.

[0600] [PCT Test] In each example and comparative example, a PCT test will be performed using the above-mentioned reliability evaluation substrate with a Hirayama Seisakusho HAST apparatus PC-422R8D, under the conditions of 121°C, 100% RH (relative humidity), and 250 hours. After the test, the substrate will be observed with an optical microscope to visually check for the occurrence of foreign matter or wiring corrosion.

[0601] [Method for Evaluating the Coated Surface (In-Plane Uniformity)] The resin composition prepared in each example and comparative example, as well as the comparative composition, are applied to the surface of an 8-inch silicon substrate by spin coating and dried at 100°C for 300 seconds. The film thickness is set to a thickness of 10 μm for the resulting cured product (coated film). The film thickness of the coated surface is measured using a contact-type film thickness gauge (Decktack), and the in-plane uniformity is calculated as follows: In-plane uniformity = (Average film thickness) - (Measured film thickness that deviates most from the average)

[0602] In-plane uniformity is evaluated as follows:

[0603] A: Smaller than 0.25 μm B: 0.25 μm or larger but less than 0.5 μm C: 0.5 μm or larger but less than 0.75 μm D: 0.75 μm or larger

[0604] [Evaluation of Residual Solvent] The content of amide solvents in the composition layer is measured by GC (gas chromatography) as follows. (GC Measurement Sample Preparation) The resin composition is applied to the support film. It is dried at 120°C to form a transfer film having the composition layer on the support film. 0.10 g of the composition layer from the formed transfer film is scraped off into a sample bottle, dissolved in THF (4.9 g), and the liquid filtered through a Teflon filter is subjected to GC measurement. (GC Conditions) The amide solvent is quantified by measurement under the following conditions.

[0605]

[0606] Furthermore, an amide solvent / THF solution containing 10 ppm of the amide solvent was prepared, and the results of GC measurement under the above conditions were used as a single calibration curve. The amide solvents used were N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylformamide (DEF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), 1,3-dimethylimidazolidinone (DMI), 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. The quantitative value is the sum of the contents of the above amide solvents.

[0607] In the composition layers using the resin compositions of Examples 31 and 32, no amide solvent was detected. Therefore, the amide solvent content in precursor A-4 and precursor A-5 were both 100 ppm or less.

[0608] From the above results, it can be seen that the embodiments of the present invention provide a method for producing a polyimide precursor in which the generation of impurities and imidization are suppressed. Furthermore, it can be seen that when the polyimide precursor obtained by the method for producing a polyimide precursor of the present invention is applied to a resin composition, it is possible to form a film that has excellent in-plane uniformity of the coated film after application and also has excellent PCT properties.

[0609] According to the present invention, it is possible to provide a method for producing a polyimide precursor or polyamide-imide precursor in which the generation of impurities and imidation are suppressed, and a method for producing a curable resin composition including the method for producing a polyimide precursor or polyamide-imide precursor. Furthermore, according to the present invention, it is possible to provide a polyimide precursor or polyamide-imide precursor in which impurities are reduced and imidation is suppressed, and a resin composition, transfer film, cured product, and laminate using the same.

[0610] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2024-223105 filed on 18 December 2024 and Japanese Patent Application No. 2025-244102 filed on 10 December 2025, the contents of which are incorporated herein by reference.

Claims

1. A process of reacting an acid anhydride derivative with a triazine chloride compound represented by the following general formula (1) in the presence of a tertiary amine to produce a compound represented by the following general formula (2) or a compound represented by the following general formula (3); (B) A process of reacting the compound represented by the general formula (2) or the compound represented by the general formula (3) with a compound having two or more amino groups, in this order, a method for producing a polyimide precursor or a polyamide-imide precursor. In the general formula (1), R １ ~R ２ each independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxy group. In the general formula (2), A １ and A ２ each independently represents an oxygen atom or -NR Ｚ -. R ｚ represents a hydrogen atom or a monovalent organic group. X １ represents a tetravalent organic group. R ３ ~R ６ each independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxy group. R ７ , R ８ each independently represents a hydrogen atom or a monovalent organic group. In the general formula (3), A ３ represents an oxygen atom or -NR Ｚ -. R ｚ represents a hydrogen atom or a monovalent organic group. X ２ represents a trivalent group. R ９ ~R １２ each independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxy group. R １３ represents a hydrogen atom or a monovalent organic group.

2. R in the general formula (2) ７ and R ８ A method for producing a polyimide precursor or polyamideimide precursor according to claim 1, wherein at least one of the members has a polymerizable functional group.

3. A method for producing a polyimide precursor or polyamideimide precursor according to claim 1, wherein steps (A) and (B) are performed in a single pot.

4. The method for producing a polyimide precursor or polyamideimide precursor according to claim 1, wherein in step (A), the relationship between the content A of the triazine chloride compound and the content B of the tertiary amine on a molar basis is A ≥ B.

5. A method for producing a polyimide precursor or polyamideimide precursor according to claim 1, wherein step (B) is performed in an organic solvent containing a hydroxyl group.

6. The method for producing a polyimide precursor or polyamide-imide precursor according to claim 5, wherein the hydroxyl group-containing organic solvent is a hydroxy acid ester, a hydroxy ether, or an alkylene glycol solvent.

7. The method for producing a polyimide precursor or polyamide-imide precursor according to claim 6, wherein the hydroxyl group-containing organic solvent is ethyl lactate or propylene glycol monomethyl ether.

8. The method for producing a polyimide precursor or polyamideimide precursor according to claim 1, wherein the polyimide precursor or polyamideimide precursor has a structure represented by the following general formula (N). In general formula (N), Y １１ *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position.

9. The method for producing a polyimide precursor or polyamideimide precursor according to claim 1, wherein the polyimide precursor or polyamideimide precursor has a structure represented by the following general formula (N2). In general formula (N2), Y １３ This represents a divalent linking group containing an aliphatic group.

10. The method for producing a polyimide precursor or polyamideimide precursor according to claim 1, wherein the polyimide precursor or polyamideimide precursor includes a structure represented by the following general formula (11). In general formula (11), R １５ and R １６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. * indicates the bond position.

11. The method for producing a polyimide precursor or polyamideimide precursor according to claim 1, wherein the polyimide precursor or polyamideimide precursor contains 10 ppm to 10,000 ppm of a compound represented by the following general formula (12). In general formula (12), R １７ and R １８ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group.

12. The method for producing a polyimide precursor or polyamideimide precursor according to claim 1, wherein the amide solvent content in the polyimide precursor or polyamideimide precursor is 100 ppm or less.

13. A method for producing a resin composition comprising: (1) a polyimide precursor or polyamideimide precursor produced by the method described in claim 1; (2) a solvent; and (3) a polymerizable compound.

14. (11) A polyimide precursor or polyamideimide precursor having a repeating unit represented by the following general formula (23) or the following general formula (24); (2) A solvent; (3) A resin composition comprising a polymerizable compound. In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

15. R in the general formula (23) ２３ and R ２４ At least one of the groups has an ethylenically unsaturated bond, or the R of the general formula (24) ２５ The resin composition according to claim 14, wherein the resin composition has a group having an ethylenically unsaturated bond.

16. The resin composition according to claim 15, wherein the group having an ethylenically unsaturated bond is a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group.

17. (12) A polyimide precursor or polyamideimide precursor having a structure represented by the following general formula (11), wherein the imidization rate of the polyimide precursor or polyamideimide precursor is less than 15%. (2) A solvent. (3) A resin composition comprising a polymerizable compound. In general formula (11), R １５ and R １６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. * indicates the bond position.

18. (13) A polyimide precursor or polyamideimide precursor containing 10 ppm to 10,000 ppm of a compound represented by the following general formula (12), wherein the imidization rate of the polyimide precursor or polyamideimide precursor is less than 15%. (2) A solvent. (3) A resin composition containing a polymerizable compound. In general formula (12), R １７ and R １８ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group.

19. The resin composition according to any one of claims 14 to 18, further comprising (4) a polymerization initiator.

20. A transfer film comprising: a support film; and a composition layer comprising: (11) a polyimide precursor or polyamideimide precursor having repeating units represented by the following general formula (23) or the following general formula (24); and (3) a polymerizable compound resin composition. In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

21. The transfer film according to claim 20, wherein the amide solvent content in the resin composition is 100 ppm or less.

22. A cured product obtained by curing the resin composition according to any one of claims 14 to 18.

23. A laminate comprising two or more layers made of the cured product described in claim 22, wherein a metal layer is included between any of the layers made of the cured product.

24. A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of claims 14 to 18 onto a substrate to form a film.

25. A method for producing a cured product according to claim 24, comprising an exposure step of selectively exposing the film, and a developing step of developing the film using a developer to form a pattern.

26. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 24.

27. A semiconductor device comprising the cured product described in claim 22.

28. A polyimide precursor or polyamideimide precursor having a repeating unit represented by the following general formula (23) or the following general formula (24). In general formula (23) and general formula (24), X １１ R represents a tetravalent organic group. ２３ and R ２４ Each of these independently represents a hydrogen atom or a monovalent organic group. １１ Each of these is independently, *-Y １２ (R Ｎ１ ) (Caution Ｎ２ ) - * represents the base. Y １２ R represents a divalent linking group. Ｎ１ and R Ｎ２ Each of these independently represents a hydrogen atom, a phenolic hydroxyl group, or a primary amino group. Ｎ１ and R Ｎ２ At least one of these represents a phenolic hydroxyl group or a primary amino group. * indicates the bond position. X １２ R represents a trivalent organic group. ２５ This represents a hydrogen atom or a monovalent organic group.

29. A polyimide precursor or polyamideimide precursor comprising a structure represented by the following general formula (11), wherein the imidation rate of the polyimide precursor or polyamideimide precursor is less than 15%. In general formula (11), R １５ and R １６ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. * indicates the bond position.

30. A polyimide precursor or polyamideimide precursor containing 10 ppm or more and 10,000 ppm or less of a compound represented by the following general formula (12), wherein the imidization rate of the polyimide precursor or polyamideimide precursor is less than 15%. In general formula (12), R １７ and R １８ Each of these independently represents a chlorine atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group.

31. The R in the general formula (23) ２３ , R ２４ each independently represents a group represented by the following general formula (4A). The polyimide precursor or polyamide-imide precursor according to claim 28. In the general formula (4A), A represents a (q + 1)-valent organic group, L represents an oxygen atom, or N(R ４６ )(R ４７ )(R ４６ , R ４７ each independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group), R ４３ to R ４５ each independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and q represents an integer of 1 to 4. * represents the bonding position.

32. The R in the general formula (23) ２３ , R ２４ each independently represents a group represented by the following general formula (4). The polyimide precursor or polyamide-imide precursor according to claim 28. In the general formula (4), A represents a (q + 1)-valent organic group, and R ４３ to R ４５ each independently represents a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group, and q represents an integer of 1 to 4. * represents the bonding position.

33. R in the general formula (4) ４５ The polyimide precursor or polyamideimide precursor according to claim 32, wherein is a hydrogen atom.

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