Thermosetting resin composition, cured film, substrate, and electronic component

Abstract

The present invention provides: a thermosetting resin composition which contains a portion sealed by a thermally crosslinkable functional group, and which is a polyimide precursor having a lower viscosity and a higher concentration than in the prior art; and after the polyimide is heated and hardened, the residual stress can be reduced under the condition that the heat resistance (dimensional stability) and the mechanical strength are maintained. A thermosetting resin composition containing polyamic acids (A) obtained by reacting a compound represented by formula (1), a compound represented by formula (2), and / or a compound represented by formula (3) and / or a compound represented by formula (4), the polyamic acids (A) being capable of forming an ester bond with each other by heating (R1 to R4 each represent a predetermined group). H2N-R2-NH2 (2) H2N-R4 (4) # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polyimide precursor for use in, for example, semiconductor devices and a composition containing the same. Background Art

[0002] In recent years, the performance improvement based on the miniaturization of semiconductor devices has gradually reached its limit, and as a solution thereto, attempts have been made to improve the performance based on three-dimensional packaging. Therefore, it is necessary to densely mount complex components such as semiconductors, wirings, insulating layers, connections between substrates based on vias, and the use of insertors. Along with this, due to the bonding of components having different coefficients of linear thermal expansion or the thinning of each layer, the influence of residual stress has become more important.

[0003] However, in general, inorganic substrates or metals such as wirings have a low coefficient of linear thermal expansion (Coefficient of Thermal Expansion, CTE), and when the coefficient of linear thermal expansion of the organic material coated thereon is high, thermal stress is generated due to the CTE difference, and warping occurs on the substrate, resulting in deformation of the device. In addition, it is known that defects such as interfacial peeling occur due to the release of residual stress.

[0004] A polyimide precursor is obtained as a polyamic acid obtained by solution polymerization of an aromatic diamine and an aromatic dianhydride, and then polyimide is formed by thermal ring closure. The polyimide obtained in this way is widely used in semiconductor devices for stress buffer layers and the like due to its excellent properties such as high heat resistance, electrical insulation, and chemical resistance, but there is also a strong demand to reduce residual stress in polyimide materials.

[0005] Various studies on reducing the residual stress of such polyimides are known. For example, Patent Document 1 and Patent Document 2 disclose that low residual stress is exhibited when coated on an inorganic substrate such as glass or a silicon wafer or various metals in a polyimide material having a specific structure. In addition, Non-Patent Document 1 and Non-Patent Document 2 point out that in a specific polyeneimide, due to its rigid structure and molecular chain reorientation during thermal imidization, it is highly oriented in the plane of the substrate, so that the CTE is suppressed to be equal to or less than that of an inorganic substrate.

[0006] However, in a general polyimide containing these polyimides, the polyamic acid as a precursor has a high viscosity due to the size of its molecular weight and hydrogen bonding properties. Therefore, if the concentration is not lowered, the polyamic acid solution loses its fluidity and solidifies, so in fact, the coating method is limited. Therefore, when the concentration of these polyamic acid solutions is lowered, it is difficult to coat a thick film at one time, and multiple coatings are required, resulting in a complicated process.

[0007] In order to obtain a low-viscosity, high-concentration solution, it is known that oligomerization can be achieved by sealing the ends with thermally crosslinkable functional groups (Non-Patent Document 3). By forming an oligomer with a low molecular weight, the viscosity can be reduced and a high-concentration solution can be prepared. The low molecular weight oligomer becomes a high molecular weight body through thermal crosslinking after coating, and mechanical strength can be obtained. As crosslinking groups, various crosslinking groups are known, but maleimide terminals or ethynyl terminals are often used (Patent Document 3, Patent Document 4, Patent Document 5).

[0008] However, in the high molecular weight conversion based on such thermal crosslinking, true stress is generated due to the formation of crosslinking bonds, and in addition, since the crosslinking bond sites hinder the in-plane orientation of the polyimide, there is a problem of further increasing the residual stress originally possessed by the polyimide.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1 Japanese Patent Laid-Open No. 60-250031

[0012] Patent Document 2 Japanese Patent Laid-Open No. 61-60725

[0013] Patent Document 3 Japanese Patent Laid-Open No. 09-104755

[0014] Patent Document 4 Japanese Patent Laid-Open No. 01-054029

[0015] Patent Document 5 Japanese Patent Laid-Open No. 2012-197403

[0016] Non-Patent Documents

[0017] Non-Patent Document 1 "Journal of Polymer Science: Part B: Polymer Physics", Vol. 36, 1261 - 1273 (1998)

[0018] Non-Patent Document 2 "Journal of Photopolymer Science and Technology", Vol. 7, No. 2, 275 - 280, 1994

[0019] Non-Patent Document 3 "Journal of the Fiber Society", Vol. 50, No. 3, P106 - 118, 1994 Summary of the Invention

[0020] Problems to be Solved by the Invention

[0021] The present invention has been made in view of the above actual situation, and the problem is to provide a thermosetting resin composition and its use, wherein the thermosetting resin composition is a polyimide precursor having a lower viscosity and a higher concentration than before, containing a site sealed with a thermally crosslinkable functional group, and capable of reducing residual stress while maintaining the heat resistance (dimensional stability) and mechanical strength required as a polyimide after heat curing.

[0022] Technical means for solving the problem

[0023] The present inventors have conducted intensive studies to solve the above problems, and as a result, they have found a polyimide precursor composition which can obtain a good polyimide satisfying heat resistance (dimensional stability), mechanical strength, and low residual stress by introducing phenolic hydroxyl groups and carboxyl groups into the molecular terminals or side chains of polyamic acid, thereby completing the present invention.

[0024] The present invention includes the following structures. [1]

[0026] A thermosetting resin composition comprising a polyamic acid (A) obtained by reacting

[0027] a compound having two or more acid anhydride groups represented by formula (1),

[0028] a diamine compound represented by formula (2), and

[0029] at least one of a dicarboxylic anhydride represented by formula (3) and a monoamine compound represented by formula (4)

[0030] By heating, ester bonds can be formed between polyamic acids (A).

[0031]

[0032] H2N-R 2 -NH2 (2)

[0033]

[0034] H2N-R 4 (4)

[0035] (R 1 to R 4 are each independently an organic group having 1 to 100 carbon atoms which may contain Si, and in at least one of R 1 to R 4 at least one hydrogen in at least one hydrocarbon group contained in the organic group is substituted with a carboxyl group, and in R 1 to R 4In at least one of them, at least one hydrogen in at least one hydrocarbon group contained in the organic group is substituted with a phenolic hydroxyl group.) [2]

[0037] The thermosetting resin composition according to [1], wherein the R 1 and R 2 are a wholly aromatic amide structure or a wholly aromatic ester structure, and R 3 and R 4 contain an aromatic ring.) [3]

[0039] A cured film obtained from the thermosetting resin composition according to [1] or [2]. [4]

[0041] A substrate having the cured film according to [3]. [5]

[0043] An electronic component using the cured film according to [3] or the substrate according to [4].

[0044] Effects of the Invention

[0045] The thermosetting resin composition of the preferred embodiment of the present invention can be obtained, for example, at a concentration of 15% by weight (hereinafter expressed as wt%) to 30 wt% and a viscosity at room temperature (25°C) of 0.5 Pa·s to 15 Pa·s. The cured film after heat curing has high heat resistance (dimensional stability), a glass transition temperature of 400°C or higher. In addition, while maintaining mechanical strength and toughness, the residual stress when coated on an inorganic substrate such as a silicon wafer or glass with a low coefficient of thermal expansion and cured can be 5 MPa or less. The polyimide film obtained from the thermosetting resin composition of the present invention can suppress deformation or warping caused by thermal stress in the process of components, and improve the reliability and yield of electronic components.) Detailed Embodiments

[0046] The present invention provides a thermosetting resin composition containing polyamic acid (A).

[0047] 1 Polyamic acid (A)

[0048] The polyamic acid (A) contained in the thermosetting resin composition of the present invention is obtained by reacting a compound having two or more acid anhydride groups represented by formula (1), a diamine compound represented by formula (2), and at least one of a dicarboxylic anhydride represented by formula (3) and a monoamine compound represented by formula (4).

[0049] R in formula (1) to formula (4) 1 to R 4Each independently is an organic group having 1 to 100 carbon atoms which may contain Si. In R 1 to R 4 in at least one of them, at least one hydrogen in at least one hydrocarbon group contained in the organic group is substituted with a carboxyl group. In R 1 to R 4 in at least one of them, at least one hydrogen in at least one hydrocarbon group contained in the organic group is substituted with a phenolic hydroxyl group. Here, the so-called phenolic hydroxyl group means a hydroxyl group directly linked to an aromatic ring. Examples of the aromatic ring include a phenyl group, a biphenyl group, a naphthyl group, etc., but are not limited to these.

[0050] The thermosetting resin composition in the present invention must form a crosslinking bond based on ester bonds between polyamic acids (A) by heating. Therefore, when only the dicarboxylic anhydride represented by formula (3) and the monoamine compound represented by formula (4) are used in the reaction, in R 1 to R 3 in at least one of them, at least one hydrogen in at least one hydrocarbon group contained in the organic group must be substituted with a carboxyl group, and in R 1 to R 3 in at least one of them, at least one hydrogen in at least one hydrocarbon group contained in the organic group must be substituted with a phenolic hydroxyl group.

[0051] In addition, when only the monoamine represented by formula (4) among the dicarboxylic anhydride represented by formula (3) and the monoamine compound represented by formula (4) is used in the reaction, in R 1 , R 2 and R 4 in at least one of them, at least one hydrogen in at least one hydrocarbon group contained in the organic group must be substituted with a carboxyl group, and in R 1 , R 2 and R 4 in at least one of them, at least one hydrogen in at least one hydrocarbon group contained in the organic group must be substituted with a phenolic hydroxyl group.

[0052] The polyamic acid (A) has a structural unit represented by the following formula (5). The structural unit represented by formula (5) is formed by the reaction of a compound having two or more acid anhydride groups represented by formula (1) and a diamine compound represented by formula (2). In formula (5), R 1 represents the same group as R 1 defined in the compound represented by formula (1) described in [1], and R 2 represents the same group as R 2 defined in the compound represented by formula (2) described in [1].

[0053]

[0054] In addition, the polyamic acid (A) has at least one of the following molecular terminal groups in Formula (6) and Formula (7). The molecular terminal group represented by the following Formula (6) is formed by the reaction of the diamine compound represented by Formula (2) with the amino group of the dicarboxylic anhydride represented by Formula (3), and the molecular terminal group represented by the following Formula (7) is formed by the reaction of the monoamine compound represented by Formula (4) with the acid anhydride group of the compound having two or more acid anhydride groups represented by Formula (1). In the reaction for obtaining the polyamic acid (A), if the dicarboxylic anhydride represented by Formula (3) is not used, the molecular terminal group represented by Formula (6) will not be formed in the polyamic acid (A), and if only the monoamine represented by Formula (4) is not used, the molecular terminal group represented by Formula (7) will not be formed. R in Formula (6) 3 represents the same group as R in the compound represented by Formula (3) described in [1], and R in Formula (7) 3 represents the same group as R in the compound represented by Formula (4) described in [1]. 4 represents the same group as R in the compound represented by Formula (4) described in [1]. 4 defines the same group.

[0055]

[0056] -NH-R 4 (7)

[0057] Here, the carboxyl groups contained in the R 1 to R 4 are the carboxyl groups contained in R in Formulas (1) to (4) before the synthesis of the polyamic acid (A) having the structural unit represented by Formula (5) and at least one of the molecular terminal groups represented by Formulas (6) and (7), and are different from the carboxyl groups generated after the synthesis of the polyamic acid (A) (in Formula (5), the two carboxyl groups not included in R 1 to R 4 ; in Formula (6), the one carboxyl group not included in R 1 and R 2 ; these carboxyl groups are used to form an imide through intramolecular cyclization by heating). These carboxyl groups form crosslinking bonds based on ester bonds with phenolic hydroxyl groups by heating. 3 is not included; these carboxyl groups form crosslinking bonds based on ester bonds with phenolic hydroxyl groups by heating).

[0058] As the polyamic acid (A), one kind of polyamic acid (A) synthesized by using each of the raw materials represented by Formulas (1) to (4) can be used, or two or more kinds of polyamic acids (A) synthesized from different combinations of raw materials can be used. In the case of using two or more kinds, different polyamic acids (A) can be synthesized and doped respectively, or the raw materials can be charged at once to obtain two or more kinds of polyamic acids (A), etc., and the manufacturing method is not limited.

[0059] The thermosetting resin composition containing the polyamic acid (A) forms an ester bond (crosslinking bond based on an ester bond) with each other based on the polyamic acid (A) by heating, due to the carboxyl group and phenolic hydroxyl group contained in any one of the R 1 to R 4 . In addition, the phenolic hydroxyl group and carboxyl group participating in the formation of the crosslinking bond based on the ester bond are contained in the R 1 to R 4 . In the case of the carboxyl group, the carboxyl groups generated after the synthesis of the polyamic acid (A) (in formula (5), two carboxyl groups not contained in R 1 and R 2 ; in formula (6), one carboxyl group not contained in R 3 3 ) are not contained in the carboxyl groups participating in the formation of the crosslinking bond based on the ester bond.

[0060] Here, the ratio of the phenolic hydroxyl group to the carboxyl group contained in the polyamic acid (A) is described. When using one type of polyamic acid (A), in the thermosetting resin composition containing the polyamic acid (A), the total molar amount n ph of the phenolic hydroxyl groups participating in the formation of the crosslinking bond based on the ester bond by heat treatment and the total molar amount n c of the carboxyl groups are preferably 0.8 ≦ n ph / n c ≦ 1.2, more preferably 0.9 ≦ n ph / n c ≦ 1.1, and most preferably 0.95 ≦ n ph / n c ≦ 1.05, for the reasons of good crosslinkability, heat resistance, and mechanical properties after curing.

[0061] In addition, when using two or more types of polyamic acid (A), the total molar amount n ph of the phenolic hydroxyl groups contained in all the polyamic acid (A) in the thermosetting resin composition and participating in the formation of the crosslinking bond based on the ester bond by heat treatment and the total molar amount n c of the carboxyl groups are preferably 0.8 ≦ n ph / n c ≦ 1.2, more preferably 0.9 ≦ n ph / n c ≦ 1.1, and most preferably 0.95 ≦ n ph / n c ≦ 1.05, for the reasons of good crosslinkability, heat resistance, and mechanical properties after curing.

[0062] For example, in polyamic acid (A'), which is a kind of polyamic acid (A), and polyamic acid (A"), when the molar amount of phenolic hydroxyl groups that participate in the formation of crosslinking bonds based on ester bonds by heat treatment in each polyamic acid (A) is different from the molar amount of carboxyl groups, as long as the total molar amount n ph of phenolic hydroxyl groups in the entire thermosetting resin composition c and the total molar amount n

[0063] of carboxyl groups are within the preferred range. In such a case, crosslinking bonds based on ester bonds can be formed between polyamic acid (A'), between polyamic acid (A"), or between polyamic acid (A') and polyamic acid (A"). 1 to R 4 in polyamic acid (B) having a carboxyl group but no phenolic hydroxyl group, and R 1 to R 4 in polyamic acid (C) having a phenolic hydroxyl group but no carboxyl group, in the thermosetting resin composition, an ester bond can be formed between polyamic acid (B) and polyamic acid (C) by heating.

[0064] Hereinafter, compounds having two or more acid anhydride groups, diamine compounds, dicarboxylic anhydrides, and monoamine compounds used for obtaining polyamic acid (A) will be described.

[0065] 1-1 Compound having two or more acid anhydride groups

[0066] In the present invention, the compound having two or more acid anhydride groups used in the synthesis of polyamic acid is not particularly limited as long as it is a compound represented by the formula (1). According to the presence or absence of carboxyl groups and phenolic hydroxyl groups in R 1 in the formula (1), it is classified into: a compound (a1) having neither a carboxyl group nor a phenolic hydroxyl group among compounds having two or more acid anhydride groups, a compound (a2) having a carboxyl group but no phenolic hydroxyl group among compounds having two or more acid anhydride groups, a compound (a3) having a phenolic hydroxyl group but no carboxyl group among compounds having two or more acid anhydride groups, and a compound (a4) having both a carboxyl group and a phenolic hydroxyl group among compounds having two or more acid anhydride groups, which will be described below.

[0067] 1-1-1 Compound (a1) having neither carboxyl group nor phenolic hydroxyl group among compounds having two or more acid anhydride groups compound (a1)

[0068] In the present invention, specific examples of the compound (a1) having neither a carboxyl group nor a phenolic hydroxyl group among the compounds having two or more acid anhydride groups used in the synthesis of the polyamic acid (A) include: copolymers of radical polymerizable monomers having an acid anhydride group such as styrene-maleic anhydride copolymer and methyl methacrylate-maleic anhydride copolymer with other radical polymerizable monomers, and tetracarboxylic dianhydrides. Examples of the tetracarboxylic dianhydride include: pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2',3,3'-diphenylsulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenylether tetracarboxylic dianhydride, 2,2',3,3'-diphenylether tetracarboxylic dianhydride, 2,3,3',4'-diphenylether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(trimellitic anhydride), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, ethane tetracarboxylic dianhydride and butane tetracarboxylic dianhydride, p-phenylene bis(trimellitic monoester anhydride), 4,4'-[(isopropylidene)bis(p-phenyleneoxy)]diphthalic dianhydride, ethylenediaminetetraacetic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, 3,3,4-tricarboxy-1,2,3,4-tetrahydronaphthalene succinic dianhydride, 4,4'-bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl, 1,4-phenylene bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate), compounds represented by the following formulas a1-1 to a1-73, etc., and the group represented by R in formula (1) does not contain a carboxyl group and a phenolic hydroxyl group, and is not particularly limited as long as the object of the present invention can be achieved. 1 The group represented does not contain a carboxyl group and a phenolic hydroxyl group, and is not particularly limited as long as the object of the present invention can be achieved.

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] Among these, from the viewpoints of reducing residual stress or improving heat resistance and toughness when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, suitable ones are pyromellitic dianhydride, 4,4'-bis(phthalic anhydride), 4,4'-bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl, 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate), naphthalene-2,6-diylbis(1,3-dihydroisobenzofuran-5-carboxylate), etc., which are Rs in the following formula (1). 1 are wholly aromatic esters or wholly aromatic amides. Among them, most suitable are 4,4'-bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl and 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate). In addition, the so-called wholly aromatic ester means a wholly aromatic ester containing only aromatic rings and ester bonds in which one or more directly connected hydrogens can be substituted by one or more functional groups selected from carboxyl groups and phenolic hydroxyl groups. Further, the so-called wholly aromatic amide means a wholly aromatic amide containing only aromatic rings and amide bonds in which one or more directly connected hydrogens can be substituted by one or more functional groups selected from carboxyl groups and phenolic hydroxyl groups (hereinafter, the same applies to this specification).

[0075] 1-1-2 Compound having carboxyl group but no phenolic hydroxyl group among compounds having two or more acid anhydride groups (a2)

[0076] In the present invention, in the compound having two or more acid anhydride groups, the compound (a2) having a carboxyl group but not having a phenolic hydroxyl group has two acid anhydride groups, and in the R in the formula (1). 1 The groups represented respectively contain a carboxyl group but do not contain a phenolic hydroxyl group, and are not particularly limited as long as the object of the present invention can be achieved. Specific examples of the compound (a2) include mellitic acid, 4,4'-(1,3,5,7-tetraoxo-5,7-dihydro-1H,3H-benzo[1,2-c:4,5-c']difuran-4,8-diyl)dibenzoic acid, etc. From the viewpoints of reducing residual stress or improving heat resistance and toughness when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, more suitable are Rs in the formula (1). 1 are wholly aromatic esters or wholly aromatic amides.

[0077] 1-1-3 Compound having phenolic hydroxyl group but no carboxyl group among compounds having two or more acid anhydride groups (a3)

[0078] In the present invention, in the compound having two or more acid anhydride groups, the compound (a3) having a phenolic hydroxyl group but not having a carboxyl group has two acid anhydride groups, and in the R in the formula (1). 1The group represented by [R] contains at least one phenolic hydroxyl group but does not contain a carboxyl group, and there is no particular limitation as long as the object of the present invention can be achieved. Specific examples of the compound (a3) include: 4-hydroxy-1H,5H-benzo[1,2-c:4,5-c']difuran-1,3,5,7-tetrone, 3,6-dihydroxybenzene-1,2,4,5-tetracarboxylic 1,2:4,5-dianhydride, 5,5'-carbonylbis(4-hydroxyisobenzofuran-1,3-dione), 5,5'-(hydroxymethylene)bis(isobenzofuran-1,3-dione), etc. From the viewpoint of reducing the residual stress when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, or improving the heat resistance and toughness, [R] in formula (1) is more preferably a wholly aromatic ester or a wholly aromatic amide. 1 is a wholly aromatic ester or a wholly aromatic amide.

[0079] 1-1-4 Compound having both carboxyl group and phenolic hydroxyl group among compounds having two or more acid anhydride groups (a4)

[0080] In the present invention, among the compounds having two or more acid anhydride groups, the compound (a4) having both a carboxyl group and a phenolic hydroxyl group has two or more acid anhydride groups, and [R] in formula (1) 1 represents a group containing both a carboxyl group and a phenolic hydroxyl group, and there is no particular limitation as long as the object of the present invention can be achieved. From the viewpoint of reducing the residual stress when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, or improving the heat resistance and toughness, [R] in formula (1) is more preferably a wholly aromatic ester or a wholly aromatic amide. 1 is a wholly aromatic ester or a wholly aromatic amide.

[0081] 1-1-5 Forms of compounds having two or more acid anhydride groups that can be used in the present invention

[0082] The compounds having two or more acid anhydride groups that can be used in the present invention are classified as described above: the compound (a1) having neither a carboxyl group nor a phenolic hydroxyl group among the compounds having two or more acid anhydride groups, the compound (a2) having a carboxyl group but not a phenolic hydroxyl group among the compounds having two or more acid anhydride groups, the compound (a3) having a phenolic hydroxyl group but not a carboxyl group among the compounds having two or more acid anhydride groups, and the compound (a4) having both a carboxyl group and a phenolic hydroxyl group among the compounds having two or more acid anhydride groups. One or two or more compounds belonging to one of these classifications can be used, or they can be arbitrarily mixed and used with one or two or more compounds belonging to other classifications.

[0083] In addition, the compounds having two or more acid anhydride groups that can be used in the present invention are not limited to the compounds described in this specification, and various other forms of compounds can also be used within the scope of achieving the object of the present invention. Therefore, as described above, the compounds having two or more acid anhydride groups that can be used in the present invention can be used alone or in combination of two or more within the scope of achieving the object of the present invention. Therefore, as a combination of two or more, the compounds described in this specification, the compounds described in this specification and those other than them, or the compounds other than the compounds described in this specification can be used within the scope of achieving the object of the present invention.

[0084] 1-2 Diamine compound

[0085] In the present invention, if the diamine compound used in the synthesis of the polyamic acid (A) is a compound represented by the formula (2), there is no particular limitation. Depending on the presence or absence of a carboxyl group and a phenolic hydroxyl group in R 2 in the formula, it is classified into: a diamine compound (a5) having neither a carboxyl group nor a phenolic hydroxyl group, a diamine compound (a6) having a carboxyl group but not a phenolic hydroxyl group, a diamine compound (a7) having a phenolic hydroxyl group but not a carboxyl group, and a diamine compound (a8) having both a carboxyl group and a phenolic hydroxyl group, which will be described below.

[0086] 1-2-1 Diamine compound (a5) having neither carboxyl group nor phenolic hydroxyl group

[0087] In the present invention, specific examples of the diamine compound (a5) that does not have either a carboxyl group or a phenolic hydroxyl group include: p-phenylenediamine, m-phenylenediamine, p-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-1,3-diphenylpropane, 2,2-bis(4-aminophenyl)propane, bis(4-amino-3-methylphenyl)methane, 1,2-bis-(4-amino-3-methylphenyl)ethane, bis(4-amino-2-methylphenyl)methane, 1,2-bis-(4-amino-2-methylphenyl)ethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl-2,2'-propane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,4-bis[(4-aminophenyl)methyl]benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]fluoropropane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]biphenyl, 1,3-bis[4-(4-aminobenzyl)phenyl]propane, 1,6-bis[4-(4-aminobenzyl)phenyl]hexane, 5-phenylmethyl-1,3-diaminobenzene, 5-[4-(4-alkylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 5-[4-(4-(4-alkylcyclohexyl)cyclohexyl)phenyl]methyl-1,3-diaminobenzene, 5-[((alkylcyclohexyl)ethylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-alkylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-alkylcyclohexane, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, 5,4'-diamino-2-phenylbenzimidazole, 4,4'-diaminoazobenzene, bis(4-aminophenyl) terephthalate, compounds represented by the following general formula (II) to general formula (VIII), and the group represented by R in the formula (2) does not contain a carboxyl group or a phenolic hydroxyl group, and if the object of the present invention can be achieved, there is no particular limitation. 2 The group represented by does not contain a carboxyl group or a phenolic hydroxyl group, and if the object of the present invention can be achieved, there is no particular limitation.

[0088] H2N-A 1 -NH2 (II)

[0089]

[0090] In formula (II), A 1-(CH2) m -, where m is an integer from 1 to 6.

[0091] In Formula (IV), Formula (VI) and Formula (VIII), A 1 is a single bond, -O-, -S-, -S-S-, -SO2-, -CO-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-, -(CH2) m -, -O-(CH2) m -O- or -S-(CH2) m -S-, where m is an integer from 1 to 6.

[0092] In Formula (VII) and Formula (VIII), A 2 is a single bond, -O-, -S-, -CO-, -C(CH3)2-, -C(CF3)2- or an alkylene group with 1 to 3 carbon atoms, and the hydrogen bonded to the cyclohexane ring or benzene ring may be substituted with -F or -CH3.

[0093] As the diamine represented by Formula (II), for example, the diamines represented by Formula (II-1) to Formula (II-3) can be cited.

[0094]

[0095] As the diamine represented by Formula (III), for example, the diamines represented by Formula (III-1) and Formula (III-2) can be cited.

[0096]

[0097] As the diamine represented by Formula (IV), for example, the diamines represented by Formula (IV-1) to Formula (IV-3) can be cited.

[0098]

[0099] As the diamine represented by Formula (V), for example, the diamines represented by Formula (V-1) to Formula (V-5) can be cited.

[0100]

[0101] As the diamine represented by Formula (VI), for example, the diamines represented by Formula (VI-1) to Formula (VI-31) can be cited.

[0102]

[0103]

[0104] As the diamine represented by formula (VII), for example, diamines represented by formula (VII-1) to formula (VII-6) can be mentioned.

[0105]

[0106] As the diamine represented by formula (VIII), for example, diamines represented by formula (VIII-1) to formula (VIII-11) can be mentioned.

[0107]

[0108]

[0109] Among the specific examples of the diamine compounds represented by formula (II) to formula (VIII), from the viewpoints of excellent mechanical properties and thermal properties of the cured product obtained from the thermosetting resin composition and the ease of obtaining commercially available products, it is preferable to use the compounds represented by formula VI-30, formula VI-31, and formula VIII-8.

[0110] As a specific example of the diamine compound (a5) having neither a carboxyl group nor a phenolic hydroxyl group, a diamine compound represented by formula (IX) can be further mentioned.

[0111]

[0112] In formula (IX), A 3 is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, or -(CH2) p -, where p is an integer of 1 to 6.

[0113] In formula (IX), R 7 is hydrogen, a group having a steroid skeleton, a group having at least one ring structure selected from the group consisting of a cyclohexane ring and a benzene ring. When the positional relationship of the two amino groups bonded to the benzene ring is para, R 7 can be an alkyl group having 1 to 30 carbon atoms, or when the positional relationship is meta, R 7 can be a phenyl group in which at least one hydrogen of an alkyl group having 1 to 10 carbon atoms or a phenyl group can be substituted by -F, -CH3, -OCH3, -OCH2F, -OCHF2, or -OCF3. In the alkyl group having 1 to 30 carbon atoms and the alkyl group having 1 to 10 carbon atoms, at least one -CH2- can be substituted by -CF2-, -CHF-, -O-, -CH=CH-, or -C≡C-, and at least one -CH3 can be substituted by -CH2F, -CHF2, or -CF3.

[0114] In formula (IX), two amino groups are bonded to the phenyl ring carbon, and the bonding position relationship of the two amino groups is preferably meta or para. More preferably, the two amino groups are bonded to the 3rd and 5th positions, or the 2nd and 5th positions when the bonding position of “R 7 -A 3 -” is set as the 1st position.

[0115] Examples of the diamine represented by formula (IX) include diamines represented by formula (IX-1) to formula (IX-11).

[0116]

[0117] In formula (IX-1), formula (IX-2), formula (IX-7) and formula (IX-8), R 18 is an organic group having 1 to 30 carbon atoms. Among these, an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms is preferred, and an alkyl group having 5 to 12 carbon atoms or an alkoxy group having 5 to 12 carbon atoms is more preferred. In addition, in formula (IX-3) to formula (IX-6) and formula (IX-9) to formula (IX-11), R 19 is an organic group having 1 to 30 carbon atoms. Among these, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkyl group having 3 to 10 carbon atoms or an alkoxy group having 3 to 10 carbon atoms is more preferred.

[0118] Examples of the diamine compound represented by formula (IX) further include diamine compounds represented by the following formula (IX-12) to formula (IX-17).

[0119]

[0120] In formula (IX-12) to formula (IX-15), R 20 is hydrogen or an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 4 to 16 carbon atoms, and more preferably an alkyl group having 6 to 16 carbon atoms. In formula (IX-16) and formula (IX-17), R 21 is hydrogen or an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms.

[0121] Examples of the diamine compound represented by formula (IX) further include diamine compounds represented by the following formula (IX-18) to formula (IX-38).

[0122]

[0123]

[0124] In the formulas (IX-18), (IX-19), (IX-22), (IX-24), (IX-25), (IX-28), (IX-30), (IX-31), (IX-36), and (IX-37), R 22 is an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms. Further, in the formulas (IX-20), (IX-21), (IX-23), (IX-26), (IX-27), (IX-29), (IX-32) to (IX-35), and (IX-38), R 23 is hydrogen, -F, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, -CN, -OCH2F, -OCHF2, or -OCF3, preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms. In the formulas (IX-33) and (IX-34), A 9 is an alkylene group having 1 to 12 carbon atoms.

[0125] As the diamine compound represented by the formula (IX), the diamine compounds represented by the following formulas (IX-39) to (IX-48) can be further exemplified.

[0126]

[0127] In the present invention, the diamine compounds used in the synthesis of the polyamic acid (A) can be further exemplified by the compounds represented by the following formulas (XI) to (XII).

[0128]

[0129] In the formulas (XI) and (XII), R 10 is hydrogen or -CH3, and R 11 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and A 6 are each independently a single bond, -C(=O)-, or -CH2-.

[0130] In the formula (XII), R 13 and R 14 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or a phenyl group.

[0131] In the formula (XI), preferably, one of the two "NH2-Ph-A 6 -O-" (-Ph- represents a phenylene group) is bonded to the 3-position of the steroid nucleus, and the other is bonded to the 6-position. Further, preferably, the two amino groups are each bonded to a carbon atom of the phenyl ring, relative to A 6bonded to the meta or para position via the bonding position.

[0132] As the diamine compound represented by the formula (XI), for example, the diamine compounds represented by the formula (XI-1) to the formula (XI-4) can be cited.

[0133]

[0134] In the formula (XII), two "NH2-(R 14 -)Ph-A 6 -O-" (-Ph- represents a phenylene group) are respectively bonded to the carbon of the phenyl ring, preferably bonded to the carbon at the meta or para position relative to the carbon to which the steroid nucleus is bonded. In addition, the two amino groups are respectively bonded to the carbon of the phenyl ring, preferably bonded to the meta or para position relative to A 6 bonded to the meta or para position.

[0135] As the diamine compound represented by the formula (XII), for example, the diamine compounds represented by the formula (XII-1) to the formula (XII-8) can be cited.

[0136]

[0137] In the present invention, the diamine compounds used in the synthesis of the polyamic acid (A) further include the compounds represented by the formula (XIII) and the formula (XIV).

[0138]

[0139] In the formula (XIII), R 15 is hydrogen or an alkyl group having 1 to 20 carbon atoms, and at least one -CH2- of the alkyl group having 2 to 20 carbon atoms can be substituted by -O-, -CH=CH- or -C≡C-, A 7 are each independently -O- or an alkylene group having 1 to 6 carbon atoms, A 8 is a single bond or an alkylene group having 1 to 3 carbon atoms, the ring T is 1,4-phenylene or 1,4-cyclohexylene, and h is 0 or 1.

[0140]

[0141] In the formula (XIV), R 16 is an alkyl group having 2 to 30 carbon atoms, and among these, an alkyl group having 6 to 20 carbon atoms is preferred. R 17 is hydrogen or an alkyl group having 1 to 30 carbon atoms, and among these, an alkyl group having 1 to 10 carbon atoms is preferred. A 7 are each independently -O- or an alkylene group having 1 to 6 carbon atoms.

[0142] In the formula (XIII), the two amino groups are respectively bonded to the carbon of the phenyl ring, preferably relative to A 7and are bonded to the meta-position or para-position.

[0143] Examples of the diamine compound represented by the formula (XIII) include 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-methylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]4-methylcyclohexane, and diamine compounds represented by the formula (XIII-1) to the formula (XIII-9).

[0144]

[0145]

[0146] In the formulas (XIII-1) to (XIII-3), R 24 is preferably hydrogen or an alkyl group having 1 to 20 carbon atoms. In the formulas (XIII-4) to (XIII-9), R 25 is preferably hydrogen or an alkyl group having 1 to 10 carbon atoms.

[0147] In the formula (XIV), the two amino groups are respectively bonded to the phenyl ring carbon, and are preferably bonded to the meta-position or para-position with respect to A 7 and are bonded to the meta-position or para-position.

[0148] Examples of the diamine compound represented by the formula (XIV) include diamine compounds represented by the formula (XIV-1) to the formula (XIV-3).

[0149]

[0150] In the formulas (XIV-1) to (XIV-3), R 26 is an alkyl group having 2 to 30 carbon atoms, and among these, an alkyl group having 6 to 20 carbon atoms is preferred. R 27 is hydrogen or an alkyl group having 1 to 30 carbon atoms, and among these, hydrogen or an alkyl group having 1 to 10 carbon atoms is preferred.

[0151] As described above, in the present invention, as specific examples of the diamine compound (a5) that does not have either a carboxyl group or a phenolic hydroxyl group, for example, diamine compounds represented by the formula (II) to the formula (XIV) can be used, but diamine compounds other than these can also be used. For example, naphthalene-based diamines having a naphthalene structure, fluorene-based diamines having a fluorene structure, or siloxane-based diamines having a siloxane bond can be used alone or in combination with other diamines.

[0152] The siloxane-based diamine is not particularly limited, and a substance represented by the following formula (XV) can be used.

[0153]

[0154] In the formula, R 5 and R 6 are independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and A 4 is independently a methylene group, a phenylene group, or a phenylene group in which at least one hydrogen is substituted with an alkyl group, x is independently an integer of 1 to 6, and y is an integer of 1 to 70.

[0155] As specific examples of the siloxane diamine (XV), the following can be cited: Silaplane (registered trademark) FM-3311, FM-3321, FM-3325 (manufactured by JNC Corporation), Shin-Etsu Silicone (registered trademark) PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.), DOWSIL (trademark) BY 16-853U, BY 16-871 (manufactured by Dow-Toray Co., Ltd.), DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A31, DMS-A32, DMS-A35 (manufactured by Gelest).

[0156] Among the specific examples of the diamine compound (a5) that does not have either a carboxyl group or a phenolic hydroxyl group, from the viewpoint of reducing the residual stress when the thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and hardened, or improving the heat resistance and toughness, p-phenylenediamine, 4,4'-diaminobenzanilide, 5,4'-diamino-2-phenylbenzimidazole, 4,4'-diaminoazobenzene, bis(4-aminophenyl) terephthalate, etc., in which R 2 in formula (2) is a wholly aromatic ester or a wholly aromatic amide are further preferred. Among them, p-phenylenediamine, 4,4'-diaminobenzanilide, and 5,4'-diamino-2-phenylbenzimidazole are particularly preferred.

[0157] 1-2-2 Diamine compound (a6) having carboxyl group but no phenolic hydroxyl group

[0158] In the present invention, in the formula (2) of the diamine compound (a6) having a carboxyl group but not having a phenolic hydroxyl group, R 2The bases represented respectively contain carboxyl groups but do not contain phenolic hydroxyl groups, and there is no particular limitation as long as the object of the present invention can be achieved. Specific examples of such compounds include: 3,5-diaminobenzoic acid, 3,5-diamino-4-methylbenzoic acid, 4,6-diaminoazobenzene-2,4'-dicarboxylic acid, 4,6-diaminoazobenzene-2,2'-dicarboxylic acid, 2,4-diaminobenzoic acid, 4,6-diaminoisophthalic acid, 3,3'-diaminoazobenzene-4,4'-dicarboxylic acid, 2,6-diaminobenzoic acid, 2,5-diaminobenzoic acid, 2,5-diamino-4-methylbenzoic acid, 2,5-diaminoterephthalic acid, 3,4-diaminobenzoic acid, 4,5-diamino-2-methoxybenzoic acid, 4-amino-3-(2-amino-1H-imidazol-1-yl)benzoic acid, 2,2'-diaminoazobenzene-5,5'-dicarboxylic acid, 2,3-diaminobenzoic acid, 2,3-diamino-4-methylbenzoic acid, 2,3-diaminoterephthalic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 2,4-diamino-6-(4-methoxyphenyl)furo[2,3-d]pyrimidine-5-carboxylic acid, 4-(2,4-diaminophenoxy)benzoic acid, 2,2'-[(4,4'-diamino[1,1'-biphenyl]-3,3'-diyl)dioxy]diacetic acid, 4,4'-[(4,4'-diamino[1,1'-biphenyl]-3,3'-diyl)dioxy]dibutyric acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 4,4-(3,3'-diamino-1,1'-biphenyl-4,4'-diylbisoxy)dibutyric acid, lysine, cystine, ornithine, diaminononanoic acid, 2,6-diaminoheptanedioic acid, etc. From the viewpoint of reducing the residual stress when the thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, or improving the heat resistance and toughness, R in formula (2) is more suitable. 2 is a wholly aromatic ester or a wholly aromatic amide. Among these, 3,5-diaminobenzoic acid is most suitable.

[0159] 1-2-3 Diamine compound (a7) having phenolic hydroxyl group but no carboxyl group

[0160] In the present invention, the diamine compound (a7) having a phenolic hydroxyl group but not having a carboxyl group, if R in the formula (2) 2There are no particular limitations as long as the groups represented contain phenolic hydroxyl groups but do not contain carboxyl groups. Specific examples of such compounds include: 2,3-diaminophenol, 2,3-diamino-p-cresol, 3,4-diamino-2-nitrophenol, 3,4-diamino-2-nitro-5-methylphenol, 3,4-diamino-2-nitro-6-methylphenol, 3,4-diaminophenol, 4,5-diaminobenzene-1,2-diol, 5,6-diamino-8-hydroxynaphthalene-1,4-dione, 3,4-diaminophenyl 2-deoxy-β-D-ribofuranoside, 2,6-diaminophenol, 2,6-diaminohydroquinone, 2,4-diaminoresorcinol, 2,6-diaminohydroquinone-1-methyl ether, 2,6-diamino-4-methoxyphenol, 2,6-diaminohydroquinone-1-ethyl ether, 2,4-diamino-5-methoxyresorcinol, 4,6-diamino-2-methyl-1,3,5-benzenetriol, 2,6-diamino-4-nitrophenol, 2,6-diamino-4-tert-butylphenol, 2,6-diamino-4-(diethylamino)phenol, 2,4-diamino-1,3-dioxinaphthalene, 3,5-diaminobiphenyl-4-ol, 2,4-diaminophenol, 2,4-diamino-o-cresol, 4,6-diamino-m-cresol, 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,4-diamino-5-methoxyphenol, 3,5-diaminocatechol-1-methyl ether, 4,6-diaminogallol, 2-(2,4-diaminophenoxy)ethanol, 2,4-diamino-1-naphthol, 3,5-diaminooxydiphenyl, 3,5-diaminophenol, 2-methyl-3,5-diaminophenol, 3,5-diamino-4-methylphenol, 3,5-diaminocatechol, 4,6-diaminobenzene-1,2,4,5-tetraol, 1,4-diamino-2-naphthol, 1,4-diamino-2,3-dioxinaphthalene, 2-[(4-aminobenzylidene)amino]-5-aminophenol, 3-oxydianiline, 4,4'-diamino-3'-oxido-3-methyldiphenyl, 3,3-dihydroxydianiline, 2-hydroxydianiline, 4,4'-diamino-2,2'-dioxidodiphenyl, 4,4'-diamino-6,6'-dioxido-3,3'-Dimethyldiphenyl, 3,4'-diaminobiphenyl-4,3'-diol, 3,3'-diamino-2,2'-dioxydiphenyl, 4,4'-bis[2-aminophenol], 5,5'-diamino-1,1'-biphenyl-2,2'-diol, 4,4'-diamino-1,1'-dioxynaphthyl-(2,2'), 5-hydroxybenzidine, 2',4-diaminobiphenyl-3-ol, 2,6-diaminonaphthol-(1), 1,6-diaminonaphthol-(2), 4,8-diaminonaphthol-(1), 4,8-diamino-1,7-dioxynaphthalene, 4,8-diamino-1,5-dioxynaphthalene, 4,5-diaminonaphthol-(1), 1,8-diamino-2,7-dioxynaphthalene, etc. From the viewpoint of reducing the residual stress or improving the heat resistance and toughness when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, R in formula (2) is more suitable. 2 is a wholly aromatic ester or a wholly aromatic amide.

[0161] 1-2-4 Diamine compound (a8) having both carboxyl group and phenolic hydroxyl group

[0162] In the present invention, the diamine compound (a8) having both a carboxyl group and a phenolic hydroxyl group, R in formula (2) 2 represents a group containing a carboxyl group and a phenolic hydroxyl group, and is not particularly limited as long as the object of the present invention can be achieved. Specific examples of such compounds include: 3,5-diamino-4-hydroxybenzoic acid, 3,5-diaminosalicylic acid, 2,6-diamino-3-hydroxybenzoic acid, 2-amino-5-(3-amino-4-hydroxybenzamide)benzoic acid, 5-amino-4-hydroxy-2-nitrobenzoic acid, etc. From the viewpoint of reducing the residual stress or improving the heat resistance and toughness when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, R in formula (2) 2 is a wholly aromatic ester or a wholly aromatic amide.

[0163] 1-2-5 Forms of diamine compounds that can be used in the present invention

[0164] The diamine compounds that can be used in the present invention are classified as described above: diamine compounds (a5) having neither a carboxyl group nor a phenolic hydroxyl group, diamine compounds (a6) having a carboxyl group but not a phenolic hydroxyl group, diamine compounds (a7) having a phenolic hydroxyl group but not a carboxyl group, and diamine compounds (a8) having both a carboxyl group and a phenolic hydroxyl group. One or more compounds belonging to one of these classifications can be used, or they can be arbitrarily mixed with one or more compounds belonging to other classifications.

[0165] In addition, the diamine compounds that can be used in the present invention are not limited to the compounds described in this specification, and various other forms of compounds can also be used within the scope of achieving the object of the present invention. Therefore, as described above, the diamine compounds that can be used in the present invention can be used alone or in combination of two or more within the scope of achieving the object of the present invention. Therefore, as a combination of two or more, the compounds described in this specification, the compounds described in this specification and compounds other than those, or compounds other than the compounds described in this specification can be used within the scope of achieving the object of the present invention.

[0166] 1-3 Dicarboxylic anhydride

[0167] In the present invention, if the dicarboxylic anhydride used in the synthesis of polyamic acid is the dicarboxylic anhydride represented by the formula (3), there is no particular limitation. According to the presence or absence of a carboxyl group and a phenolic hydroxyl group in R 3 in the formula (3), it is classified into: a dicarboxylic anhydride (a9) having neither a carboxyl group nor a phenolic hydroxyl group, a dicarboxylic anhydride (a10) having a carboxyl group but not a phenolic hydroxyl group, a dicarboxylic anhydride (a11) having a phenolic hydroxyl group but not a carboxyl group, and a dicarboxylic anhydride (a12) having both a carboxyl group and a phenolic hydroxyl group, which will be described below.

[0168] 1-3-1 Dicarboxylic anhydride (a9) having neither carboxyl group nor phenolic hydroxyl group

[0169] In the present invention, specific examples of the dicarboxylic anhydride (a9) that does not have either a carboxyl group or a phenolic hydroxyl group include: succinic anhydride, 1,2-cyclopropanedicarboxylic anhydride, 2-methylsuccinic anhydride, 3-oxabicyclo[3.2.0]heptane-2,4-dione, 2-ethylsuccinic anhydride, α,α-dimethylsuccinic anhydride, 2,3-dimethylsuccinic anhydride, cyclopentane-1,2-dicarboxylic anhydride, 1,2-dimethyl-1,2-cyclopropanedicarboxylic anhydride, 3,3-dimethyl-1,2-cyclopropanedicarboxylic anhydride, 2,2,3-trimethylsuccinic anhydride, 3-isopropylfuran-2,5(3H,4H)-dione, 3-propyl-oxolane-2,5-dione, 3-ethyl-3-methyloxolane-2,5-dione, 3-(methoxymethyl)oxolane-2,5-dione, hexahydrophthalic anhydride, 2-oxaspiro[4.4]nonane-1,3-dione, 3-isobutylfuran-2,5(3H,4H)-dione, tetramethyloxolane-2,5-dione, butylsuccinic anhydride, 3-acetylaminotetrahydrofuran-2,5-dione, 2,5-dioxooxolan-3-yl acetate, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylhexahydrophthalic anhydride, 2-oxaspiro[4.5]decane-1,3-dione, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-cyclopentyloxolane-2,5-dione, 3-(2-methylbutan-2-yl)oxolane-2,5-dione, 3-pentyloxolane-2,5-dione, 3-(3-methylbutyl)oxolane-2,5-dione, 3-tert-butyl-4-methyloxolane-2,5-dione, 3-pyrrolidinyl-3,4-dihydrofuran-2,5-dione, 2-methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, 5-methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, 7-methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, 1-methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, 8-methyl-2-oxaspiro[4.5]decane-1,3-dione, phenylsuccinic anhydride, 3,6-dimethylcyclohexane-1,2-dicarboxylic anhydride, 3-(hexan-3-yl)oxolane-2,5-dione, hexylsuccinic anhydride, 3-(4-methylpentan-2-yl)oxolane-2,5-dione, 3-(4-oxopentyl)oxolane-2,5-dione, (octahydro-1,2,4-methanocyclopentadiene-5,6-dicarboxylic) anhydride, 2-benzylsuccinic anhydride, 3-(heptan-4-yl)oxolane-2,5-dione, 3-oxaspiro[bicyclo[3.2.1]octane-6,3'-oxolane]-2',5'-dione, 1,4-dimethyl-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, 7-methoxy-octahydro-2-benzofuran-1,3,5-trione, phthalic anhydride, 4-methylphthalic anhydride, 3-methylphthalic anhydride, 5,6-dimethyl-1,3-isobenzofurandione, 4,7-dimethyl-1,3-isobenzofurandione, 4,6-dimethyl-1,3-isobenzofurandione, 3-methoxyphthalic anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 4,5,6,7-tetramethylisobenzofuran-1,3-dione, 5-methyl-6-(1-methylethyl)-1,3-isobenzofurandione, 3-tert-butylphthalic anhydride, 4-tert-butylphthalic anhydride, 3-acetoxyphthalic anhydride, 4-(methoxycarbonyl)phthalic anhydride, 5,6-dimethoxyisobenzofuran-1,3-dione, 5-acetoxy-1,3-dihydroisobenzofuran-1,3-dione, 4-methyl-1,2-naphthalenedicarboxylic anhydride, 8-methylnaphtho[2,3-c]furan-1,3-dione, biphenyl-2,3-dicarboxylic anhydride, 5-phenyl-1,3-dihydroisobenzofuran-1,3-dione, 5,6,7,8,9,10-hexahydrobenzocyclooctene-1,2-dicarboxylic anhydride, 4,7-dipropyl-1,3-dihydroisobenzofuran-1,3-dione, 5-(4-methyl-2-thienyl)isobenzofuran-1,3-dione, dibenzofuran-1,2-dicarboxylic anhydride, 6,6-dimethyl-7,8-dihydronaphtho[1,2-c]furan-1,3,9(6H)-trione, 5-phenoxy-2-benzofuran-1,3-dione, 4-ethoxycarbonyl-3,5-dimethylphthalic anhydride, 4-butoxycarbonyl-1,2-benzenedicarboxylic anhydride, 9,10-phenanthrenedicarboxylic anhydride, 4-phenethylphthalic anhydride, 10-methyl-10H-furo[3,4-a]carbazole-1,3-dione, 4-methyl-1H,3H,5H-furo[3,4-b]carbazole-1,3-dione, 4-methyl-dibenzofuran-1,2-dicarboxylic anhydride, 5-(benzyloxy)-1,3-dihydroisobenzofuran-1,3-dione, 4-benzoylphthalic anhydride, 6-(acetylamino)naphtho[2,3-c]furan-1,3-dione, 3,6-bis(acetylamino)phthalic anhydride, 10-ethyl-10H-furo[3,4-a]carbazole-1,3-dione, 4-[(1R)-1,2,2-trimethylcyclopentyl]-6-methylisobenzofuran-1,3-dione, 4-phenoxycarbonylphthalic anhydride, 5-(5-tert-butyl-2-thienyl)isobenzofuran-1,3-dione, 5-phenylnaphtho[1,2-c]furan-1,3-dione, 4-phenyl-1H,3H-naphtho[2,3-c]furan-1,3-dione, 9,9-dimethyl-9,10-dihydrophenanthrene-1,2-dicarboxylic anhydride, 5-(4-tert-butylphenyl)isobenzofuran-1,3-dione, 4,7-dimethyl-5,6-di-tert-butyl-1,3-Isobenzofurandione, 3-decylphthalic anhydride, 4-methyl-8-methoxydibenzofuran-1,2-dicarboxylic anhydride, 9-acetoxy-1,3,6,7,8,9-hexahydro-7,7-dimethylnaphtho[1,2-c]furan-1,3-dione, 9-acetoxy-6,7-dihydronaphtho[1,2-c]furan-1,3-dione, 8-(4-methylphenyl)thieno[2,3-f]isobenzofuran-5,7-dione, 4,7-di(2-thienyl)isobenzofuran-1,3-dione, octyl 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylate, 6-hexyl-1H-furo[3,4-f]isoindole-1,3,5,7-tetrone, etc.,

[0170] These compounds are only examples, and the group represented by R in the formula (3) 3 does not contain a carboxyl group and a phenolic hydroxyl group. If the object of the present invention can be achieved, there is no particular limitation. Among these, from the viewpoint of reducing the residual stress or improving the heat resistance when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and hardened, those suitable are the R in the formula (3) 3 compounds containing an aromatic ring.

[0171] 1-3-2 Dicarboxylic anhydride (a10) having carboxyl group but no phenolic hydroxyl group

[0172] In the present invention, the dicarboxylic anhydride (a10) having a carboxyl group but not having a phenolic hydroxyl group has one acid anhydride group, and the groups represented by R in the formula (3) 3 each contain a carboxyl group but do not contain a phenolic hydroxyl group. If the object of the present invention can be achieved, there is no particular limitation. Specific examples of such compounds include: trimellitic anhydride, 1,3-dihydro-1,3-dioxo-4,7-dichloroisobenzofuran-5-carboxylic acid, 1,2,4-naphthalenetricarboxylic-1,2-anhydride, 1,3-dioxo-6-[(tert-butylperoxy)carbonyl]-1,3-dihydroisobenzofuran-5-carboxylic acid, dioxo-1,3-dihydro-2-benzofuran-4,5,6,7-tetracarboxylic acid, 1,3-dioxoisobenzofuran-5,6-dicarboxylic acid-6-benzyl, 1,3-dioxoisobenzofuran-4-carboxylic acid, 2,3,6-naphthalenetricarboxylic-2,3-anhydride, 1,6,7-naphthalenetricarboxylic-6,7-anhydride, 5-(1,3-dioxoisobenzofuran-5-yloxy)isophthalic acid, etc. Among these, from the viewpoint of reducing the residual stress or improving the heat resistance when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and hardened, those suitable are the R in the formula (3) 3 compounds containing an aromatic ring.

[0173] 1-3-3 Dicarboxylic anhydride (a11) having phenolic hydroxyl group but no carboxyl group

[0174] In the present invention, the dicarboxylic anhydride (a11) having a phenolic hydroxyl group but not having a carboxyl group has one acid anhydride group, and the R in the formula (3) 3 represents a group that contains a phenolic hydroxyl group but does not contain a carboxyl group, and is not particularly limited as long as the object of the present invention can be achieved. Specific examples of such compounds include: 3-hydroxyphthalic anhydride, 4-(diethylamino)-9-hydroxynaphtho[2,3-c]furan-1,3-dione, 4-hydroxyphthalic anhydride, 4,6-dihydroxyisobenzofuran-1,3-dione, methyl 1,3-dihydro-1,3-dioxo-4-methyl-6-hydroxyisobenzofuran-5-carboxylate, 4,7-bis(trimethylsilyl)-5-hydroxyisobenzofuran-1,3-dione, 6-hydroxy-10-(1,3-benzodioxol-5-yl)furo[3',4':6,7]naphtho[1,2-d]-1,3-dioxole-7,9-dione, rufescidride, etc. Among these, from the viewpoint of reducing the residual stress or improving the heat resistance when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, the R in the formula (3) 3 is preferably a compound containing an aromatic ring.

[0175] 1-3-4 Dicarboxylic anhydride (a12) having both carboxyl group and phenolic hydroxyl group

[0176] In the present invention, the dicarboxylic anhydride (a12) having both a carboxyl group and a phenolic hydroxyl group has one acid anhydride group, and the R in the formula (3) 3 represents a group that contains a carboxyl group and a phenolic hydroxyl group, and is not particularly limited as long as the object of the present invention can be achieved. From the viewpoint of reducing the residual stress or improving the heat resistance when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, the R in the formula (3) 3 is preferably a compound containing an aromatic ring.

[0177] 1-3-5 Forms of dicarboxylic anhydrides that can be used in the present invention

[0178] The dicarboxylic anhydrides that can be used in the present invention are classified as above: dicarboxylic anhydrides (a9) having neither a carboxyl group nor a phenolic hydroxyl group, dicarboxylic anhydrides (a10) having a carboxyl group but not a phenolic hydroxyl group, dicarboxylic anhydrides (a11) having a phenolic hydroxyl group but not a carboxyl group, and dicarboxylic anhydrides (a12) having both a carboxyl group and a phenolic hydroxyl group. One or more compounds belonging to one of these classifications can be used, or they can be arbitrarily mixed with one or more compounds belonging to other classifications.

[0179] In addition, the dicarboxylic anhydride that can be used in the present invention is not limited to the compounds described in this specification, and various other forms of compounds can also be used within the scope of achieving the object of the present invention. Therefore, as described above, the dicarboxylic anhydride that can be used in the present invention can be used alone or in combination of two or more within the scope of achieving the object of the present invention. Therefore, as a combination of two or more, within the scope of achieving the object of the present invention, the compounds described in this specification can be used with each other, the compounds described in this specification and compounds other than those, or compounds other than the compounds described in this specification can be used with each other.

[0180] 1-4 Monoamine compound

[0181] In the present invention, if the monoamine compound used in the synthesis of polyamic acid is the monoamine compound represented by the formula (4), there is no particular limitation. According to the presence or absence of a carboxyl group and a phenolic hydroxyl group in R 4 in the formula (4), it is classified into: a monoamine compound (a13) that does not have either a carboxyl group or a phenolic hydroxyl group, a monoamine compound (a14) that has a carboxyl group but does not have a phenolic hydroxyl group, a monoamine compound (a15) that has a phenolic hydroxyl group but does not have a carboxyl group, and a monoamine compound (a16) that has both a carboxyl group and a phenolic hydroxyl group, which will be described below.

[0182] 1-4-1 Monoamine compound (a13) having neither carboxyl group nor phenolic hydroxyl group

[0183] In the present invention, specific examples of the monoamine compound (a13) that does not have either a carboxyl group or a phenolic hydroxyl group used in the synthesis of polyamic acid (A) include: methylamine, ethylamine, propylamine, isopropylamine, adamantylamine, aniline, benzylamine, amphetamine, phenethylamine, toluidine, 2,3-dimethylaniline, 3,4-dimethylaniline, 2,4,6-trimethylamine, 1-naphthylamine, 2-naphthylamine, aminotetralin, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine and other monoamine compounds.

[0184] These compounds are only examples. As long as the group represented by R 4 in the formula (4) does not contain a carboxyl group and a phenolic hydroxyl group and can achieve the object of the present invention, there is no particular limitation. Among these, from the viewpoint of reducing the residual stress or improving the heat resistance when coating and curing the thermosetting resin composition on a substrate with a low coefficient of thermal expansion, the suitable one is that R 4 in the formula (4) contains a compound having an aromatic ring.

[0185] 1-4-2 Monoamine compound (a14) having carboxyl group but no phenolic hydroxyl group

[0186] In the present invention, the monoamine compound (a14) that has a carboxyl group but does not have a phenolic hydroxyl group in R4 The bases represented respectively contain a carboxyl group but do not contain a phenolic hydroxyl group, and there is no particular limitation if the object of the present invention can be achieved. Specific examples of such compounds include: 4-aminobenzoic acid, 3-aminobenzoic acid, 5-aminoisophthalic acid, 4-amino-3-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 4-amino-2-methylbenzoic acid, 5-amino-2-methylbenzoic acid, 4-amino-2-methoxybenzoic acid, 4-amino-3-methoxybenzoic acid, 4-amino-2-fluorobenzoic acid, 4-amino-3-fluorobenzoic acid, 6-amino-2-naphthoic acid, N α-acetyl-L-lysine, D-alanine, DL-alanine, L-alanine, β-alanine, m-aminobenzoic acid (4-aminobenzoic acid), p-aminobenzoic acid (3-aminobenzoic acid), 3-exo-aminobicyclo[2.2.1]Hept-5-ene-2-exo-carboxylic acid, 3-amino-N-Boc-L-alanine, (S)-4-amino-2-(Boc-amino)butyric acid, (S)-3-aminobutyric acid, 4-aminobutyric acid, D(-)-2-aminobutyric acid, DL-2-aminobutyric acid, L(+)-2-aminobutyric acid, ω-aminooctanoic acid, 7-aminocephalosporanic acid, 1-amino-1-cyclohexanecarboxylic acid, trans-2-amino-1-cyclohexanecarboxylic acid, trans-2-amino-4-cyclohexene-1-carboxylic acid, (1R,3S)-3-aminocyclopentanecarboxylic acid, (1S,3R)-3-aminocyclopentanecarboxylic acid, 1-amino-1-cyclopentanecarboxylic acid, cis-2-amino-1-cyclopentanecarboxylic acid, 1-amino-1-cyclopropanecarboxylic acid, 2-amino-3,5-difluorobenzoic acid, 3-amino-2,6-difluorobenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, 3-amino-4,4-dimethylvaleric acid hydrate, 2-amino-4-fluorobenzoic acid, 2-amino-5-fluorobenzoic acid, 2-amino-6-fluorobenzoic acid, 6-aminohexanoic acid, p-aminohippuric acid, 2-aminoisobutyric acid, 3-aminoisonicotinic acid, 5-aminolevulinic acid hydrochloride, 2-amino-6-methoxybenzoic acid, (2S,3S)-2-amino-3-methoxybutyric acid, 2-amino-3-methylbenzoic acid, 2-amino-4-methylbenzoic acid (4-amino-2-methylbenzoic acid), 2-amino-5-methylbenzoic acid, 4-aminomethylbenzoic acid, (S)-(+)-2-amino-2-methylbutyric acid hydrate, trans-4-(aminomethyl)cyclohexanecarboxylic acid, 3-amino-5-methylhexanoic acid, (S)-3-amino-4-methylvaleric acid, 3-amino-2-naphthoic acid, 2-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 2-amino-3-nitrobenzoic acid, 2-amino-4-nitrobenzoic acid, 2-amino-5-nitrobenzoic acid, 6-aminopenicillanic acid, (S)-(-)-2-amino-4-pentenoic acid, DL-2-amino-4-pentenoic acid, p-aminophenylacetic acid, 3-(3-aminophenyl)propanoic acid, 2-(4-aminophenylthio)acetic acid, 3-aminophthalic acid, 3-aminopyrazine-2-carboxylic acid, 4-amino-3-pyridinecarboxylic acid, 5-amino-2-pyridinecarboxylic acid, 2-aminoterephthalic acid, 3-aminothieno[2,3-b]pyridine-2-carboxylic acid, 11-aminoundecanoic acid, 5-aminovaleric acid, anthranilic acid, D(-)-aspartic acid, DL-aspartic acid, L-aspartic acid, L-aspartic acid 1-benzyl ester, L-aspartic acid 4-benzyl ester, L-aspartic acid 4-tert-butyl ester, L-aspartyl-L-phenylalanine, L-aspartyl-L-phenylalanine methyl ester, L-asparagine, DL-asparagine, D-asparagine, L-glutamic acid γ-benzyl ester, 5-benzyloxy-DL-tryptophan, O-benzyl-L-tyrosine, N-Boc-D-lysine, Nα-Boc-D-lysine, N. ε-Benzyloxycarbonyl-L-lysine, S-carboxymethyl-L-cysteine, L-carnosine, 3,5-dimethylanthranilic acid, α,α-diphenylglycine, DL-ethionine, (R)-3-(4-fluorophenyl)-β-alanine, (S)-4-fluorophenylglycine, 4-fluoro-DL-tryptophan, Gabapentin, D-glutamic acid, L-glutamic acid, D-glutamic acid-5-benzyl ester, DL-glutamic acid, L(+)-glutamine, glycine, glycylglycine, glycylglycylglycine, D-histidine, DL-histidine, L-histidine, D-homophenylalanine, DL-homophenylalanine, L-homophenylalanine, DL-isoleucine, L(+)-isoleucine, (R)-α-ethylalanine, D-leucine, DL-leucine, L-leucine, L-tert-leucine, D-tert-leucine, DL-methionine, D-methionine, L-methionine, DL-methionine sulfoxide, 5-methoxy-DL-tryptophan, 5-methoxy-L-tryptophan, methyl 2-amino-3-carboxybenzoate, L-aspartic acid 4-methyl hydrochloride, DL-α-methylisoleucine, (R)-3-(4-methylphenyl)-β-alanine, DL-2-methylserine hydrate, 6-methyl-DL-tryptophan, 7-methyl-DL-tryptophan, O-methyl-L-tyrosine, sodium L-aspartate hydrate, 6-nitroanthranilic acid, 4-nitro-L-phenylalanine, DL-norleucine, L-norleucine, L-norvaline, DL-phenylalanine, D-phenylalanine, L(-)-phenylalanine, D(-)-α-phenylglycine, DL-α-phenylglycine, L(+)-α-phenylglycine, sodium L-glutamate hydrate, 3-(m-tolyl)-DL-β-alanine, Nε-trifluoroacetyl-L-lysine, DL-tryptophan, D-tryptophan, L-tryptophan, DL-valine, D-valine, L-valine, etc. Among these, from the viewpoint of reducing residual stress or improving heat resistance when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and cured, suitable ones are those in formula (4) such as 4-aminobenzoic acid, 3-aminobenzoic acid, 5-aminoisophthalic acid, 4-amino-3-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 4-amino-2-methylbenzoic acid, 5-amino-2-methylbenzoic acid, 4-amino-2-methoxybenzoic acid, 4-amino-3-methoxybenzoic acid, 4-amino-2-fluorobenzoic acid, 4-amino-3-fluorobenzoic acid, 6-amino-2-naphthoic acid, etc. 4 Compounds containing an aromatic ring. Among these, the most suitable ones are 4-aminobenzoic acid and 5-aminoisophthalic acid.

[0187] 1-4-3 Monoamine compound (a15) having phenolic hydroxyl group but no carboxyl group

[0188] In the present invention, the monoamine compound (a15) having a phenolic hydroxyl group but not having a carboxyl group is R in the formula (4). 4The bases represented respectively contain phenolic hydroxyl groups but do not contain carboxyl groups, and there is no particular limitation if the object of the present invention can be achieved. Specific examples of such compounds include: 4-aminophenol, 3-amino-4-methylphenol, 4-amino-m-cresol, 5-amino-o-cresol, 4-amino-3,5-dimethylphenol, 5-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 8-amino-2-naphthol, 4-amino-1-naphthol, trans-4-aminoadamantan-1-ol hydrochloride, 5-aminobenzene-1,3-diol hydrochloride, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, (±)-2-amino-1-butanol, (R)-(-)-2-amino-1-butanol, 4-amino-1-butanol, 4-amino-2-butanol, 2-amino-4-tert-butylphenol, 2-amino-p-cresol, 2-amino-m-cresol, trans-4-aminocyclohexanol, cis-4-aminocyclohexanol hydrochloride, trans-2-aminocyclohexanol hydrochloride, 4-amino-α-diethylamino-o-cresol dihydrochloride, 2-amino-4,6-dihydroxypyrimidine, (1S,2R)-(+)-2-amino-1,2-diphenylethanol, (1S,2R)-(-)-2-amino-1,2-diphenylethanol, 2-aminoethanol, 2-(2-aminoethoxy)ethanol, (R)-2-(1-aminoethyl)phenol, 2-amino-2-ethyl-1,3-propanediol, 5-aminofluorescein, 6-amino-1-hexanol, 2-amino-4-hydroxyacetophenone hydrochloride, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-4-hydroxy-6-methylpyrimidine, 1-(4-amino-2-hydroxyphenyl)ethan-1-one, 2-amino-3-hydroxypyridine, (1S,2R)-(-)-cis-1-amino-2-indanol, (R)-(-)-2-amino-3-methyl-1-butanol, DL-2-amino-3-methyl-1-butanol, cis-2-aminomethyl-1-cyclohexanol hydrochloride, 4-(aminomethyl)phenol, 5-amino-2-methylphenol, 2-amino-2-methyl-1,3-propanediol, 1-amino-2-methyl-2-propanol, 2-amino-2-methyl-1-propanol, 8-amino-2-naphthol, 8-amino-1-naphthol-3,6-disulfonic acid sodium salt n-hydrate, 2-amino-3-nitrophenol, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-4-nitrophenol, 4-amino-2-nitrophenol, (1S,2S)-2-amino-1-(4-nitrophenyl)propane-1,3-diol, p-aminophenethyl alcohol, m-aminophenol, o-aminophenol, p-aminophenol, (±)-2-amino-1-phenylethanol, 2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoro-2-propanol, (1S,2S)-(+)-2-amino-1-phenyl-1,3-propanediol, (R)-3-amino-3-phenylpropan-1-ol, (S)-3-amino-3-phenylpropan-1-ol, D(+)-2-amino-3-phenyl-1-propanol, L(+)-2-amino-3-phenyl-1-propanol, 2-amino-1,3-propanediol, (R)-(-)-1-amino-2-propanol, (R)-(-)-2-amino-1-propanol, (S)-(-)-1-amino-2-propanol, (S)-(-)-2-amino-1-propanol, 1-amino-2-propanol, 3-amino-1-propanol, DL-1-amino-2-propanol, 3-amino-2-pyrrolidone, (6-amino-3-pyridyl)methanol, (1R,2S,3R,4R)-2,3-dihydroxy-4-(hydroxymethyl)-1-aminocyclopentane hydrochloride, dopamine hydrochloride, D(+)-galactosamine hydrochloride, D(+)-glucosamine hydrochloride, L-histidinol dihydrochloride, 3-endo-hydroxymethylbicyclo[2.2.1]heptan-2-endo-amine hydrochloride, 3-exo-hydroxymethylbicyclo[2.2.1]heptan-2-exo-amine hydrochloride, cis-2-hydroxymethyl-1-cyclohexylamine hydrochloride, trans-2-hydroxymethyl-1-cyclohexylamine hydrochloride, L(+)-isoleucinol, D(-)-leucinol, L(+)-leucinol, D(+)-methioninol, L-methioninol, methyl 3-amino-5-hydroxybenzoate, methyl 4-aminosalicylate, 3-O-methyldopamine hydrochloride, octopamine hydrochloride, DL-phenylpropanolamine, (S)-(+)-2-phenylglycinol, D(-)-α-phenylglycinol, DL-2-phenylglycinol, L-serine ethyl ester hydrochloride, DL-serine methyl ester hydrochloride, L-serine methyl ester hydrochloride, 5-hydroxytryptamine hydrochloride, sphingosine 1-phosphate, D-erythro-sphingosine 1-phosphate, L-hydroxybutyric acid methyl hydrochloride, 2-amino-2-hydroxymethyl-1,3-propanediol, tris(hydroxymethyl)aminomethane hydrochloride, triphosphate, tyramine, L-tyrosine tert-butyl ester, L-tyrosine ethyl ester hydrochloride, L-tyrosine methyl ester, L-valinol, etc. Among these, from the viewpoint of reducing the residual stress or improving the heat resistance when a thermosetting resin composition is coated on a substrate with a low coefficient of thermal expansion and hardened, suitable ones are those such as 4-aminophenol, 3-amino-4-methylphenol, 4-amino-m-cresol, 5-amino-o-cresol, 4-amino-3,5-dimethylphenol, 5-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 8-amino-2-naphthol, 4-amino-1-naphthol, etc., where R in formula (4), 4 compounds containing an aromatic ring. Among these, the most suitable ones are 4-aminophenol and 5-amino-1-naphthol.

[0189] 1-4-4 Monoamine compound (a16) having both carboxyl group and phenolic hydroxyl group

[0190] In the present invention, the monoamine compound (a16) having both a carboxyl group and a phenolic hydroxyl group has a carboxyl group and a phenolic hydroxyl group in the group represented by R in the formula (4). If the object of the present invention can be achieved, there is no particular limitation. Specific examples of the compound (a16) include: 3-amino-4-hydroxybenzoic acid, 3-amino-5-hydroxybenzoic acid, N-((2S,3R)-3-amino-2-hydroxy-4-phenylbutyryl)-L-leucine, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, DL-2-benzylserine, DL-3-(3,4-dihydroxyphenyl)alanine, L-3-(3,4-dihydroxyphenyl)alanine, folic acid, 5-hydroxyanthranilic acid, D-tyrosine, L-tyrosine, DL-m-tyrosine, D(-)-4-hydroxyphenylglycine, DL-4-amino-3-hydroxybutyric acid, (S)-(+)-2-amino-3-hydroxy-3-methylbutyric acid, (S)-(+)-2-amino-2-methyl-3-hydroxypropionic acid, DL-homoserine, L-homoserine, D-homoserine, L-5-hydroxytryptophan, (±)-ibotenic acid, DL-2-methylserine, DL-serine, D-serine, L-serine, DL-hydroxybutyric acid, D-hydroxybutyric acid, L-(-)-hydroxybutyric acid, L-thyroxine, etc. From the viewpoint of reducing the residual stress or improving the heat resistance when a thermosetting resin composition is coated on a substrate having a low coefficient of thermal expansion and cured, the R in the formula (4) is preferably a compound containing an aromatic ring. 4 The group represented by 4 4 contains an aromatic ring.

[0191] 1-4-5 Forms of monoamine compounds that can be used in the present invention

[0192] The monoamine compounds that can be used in the present invention are classified as described above: monoamine compounds (a13) having neither a carboxyl group nor a phenolic hydroxyl group, monoamine compounds (a14) having a carboxyl group but not a phenolic hydroxyl group, monoamine compounds (a15) having a phenolic hydroxyl group but not a carboxyl group, and monoamine compounds (a16) having both a carboxyl group and a phenolic hydroxyl group. One or more compounds belonging to one of these classifications can be used, or one or more compounds belonging to each of the other classifications can be arbitrarily mixed and used.

[0193] In addition, the monoamine compounds that can be used in the present invention are not limited to the compounds described in this specification, and various other forms of compounds can also be used within the scope of achieving the object of the present invention. Therefore, as described above, the monoamine compounds that can be used in the present invention can be used alone or in combination of two or more within the scope of achieving the object of the present invention. Therefore, as a combination of two or more, the compounds described in this specification, the compounds described in this specification and compounds other than those, or compounds other than the compounds described in this specification can be used within the scope of achieving the object of the present invention.

[0194] 1-5 Crosslinking bonds other than ester bonds

[0195] The polyamic acids (A) contained in the thermosetting resin composition of the present invention, within the scope of achieving the object of the present invention, optionally contain, in the structure of R 1 to R 4 in Formulas (5) to (7) (when the molecular terminal groups in Formula (6) are not included in the polyamic acid (A), R 1 , R 2 and R 4 in Formulas (5) and (7); when the molecular terminal groups in Formula (7) are not included in the polyamic acid (A), R 1 to R 3 in Formulas (5) and (6)), functional groups or a combination of a plurality of functional groups for forming crosslinking bonds other than ester bonds, whereby crosslinking bonds other than ester bonds are also formed by heat treatment. Examples of the functional groups for forming crosslinking bonds other than the ester bonds include, but are not limited to, unsaturated hydrocarbon groups, alkoxysilyl groups, etc. In addition, examples of the combination of functional groups for forming crosslinking bonds other than ester bonds include, but are not limited to, an amino group and a carboxyl group for forming a crosslinking bond based on an amide bond. The functional groups and the combination of functional groups for forming crosslinking bonds other than the ester bonds, if they are in the structure of R 1 to R 4 in the polyamic acid represented by Formulas (5) to (7) (when the molecular terminal groups in Formula (6) are not included in the polyamic acid (A), R 1 , R 2 and R 4 in Formulas (5) and (7); when the molecular terminal groups in Formula (7) are not included in the polyamic acid (A), R 1 to R 3 in Formulas (5) and (6)), can be located at any position.

[0196] In the case of introducing a functional group for forming a crosslinking bond other than the ester bond, there are the following methods: When synthesizing the polyamic acid (A), the compounds described in 1-1 to 1-4 are replaced as needed with R in formulas (1) to (4). 1 to R 4 in the structure (when the compound of formula (3) is not used in the synthesis of the polyamic acid (A), R in formulas (1), (2), and (4). 1 , R 2 and R 4 , and when the compound of formula (4) is not used, R in formulas (1) to (3). 1 to R 3 ) with a compound having a functional group for forming a crosslinking bond other than the ester bond and used, etc., but not limited thereto.

[0197] For example, in order to introduce an unsaturated hydrocarbon group as a functional group for forming a crosslinking bond other than the ester bond, a part of the dicarboxylic anhydride (a9) having neither a carboxyl group nor a phenolic hydroxyl group, the dicarboxylic anhydride (a10) having a carboxyl group but not a phenolic hydroxyl group, the dicarboxylic anhydride (a11) having a phenolic hydroxyl group but not a carboxyl group, or the dicarboxylic anhydride (a12) having both a carboxyl group and a phenolic hydroxyl group described in 1-3 can be replaced with maleic anhydride, citraconic anhydride, itaconic anhydride, allyl nadic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, cyclohexene-1,2-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, allyl succinic anhydride, etc., dicarboxylic anhydrides having a crosslinkable unsaturated hydrocarbon structure and used (limited to the case where the compound of formula (3) is used in the synthesis of the polyamic acid (A)).

[0198] In addition, for example, in order to introduce an alkoxysilyl group as a functional group for forming a crosslinking bond other than the ester bond;

[0199] a part of the dicarboxylic anhydride (a9) having neither a carboxyl group nor a phenolic hydroxyl group, the dicarboxylic anhydride (a10) having a carboxyl group but not a phenolic hydroxyl group, the dicarboxylic anhydride (a11) having a phenolic hydroxyl group but not a carboxyl group, or the dicarboxylic anhydride (a12) having both a carboxyl group and a phenolic hydroxyl group described in 1-3 can be replaced with p-(trimethoxysilyl)phenylsuccinic anhydride, p-(triethoxysilyl)phenylsuccinic anhydride, m-(trimethoxysilyl)phenylsuccinic anhydride, m-(triethoxysilyl)phenylsuccinic anhydride, trimethoxysilylpropylsuccinic anhydride, triethoxysilylpropylsuccinic anhydride, the compound represented by the following formula (α), the compound represented by the following formula (β), etc., dicarboxylic anhydrides having a crosslinkable alkoxysilyl group (limited to the case where the compound of formula (3) is used in the synthesis of the polyamic acid (A));

[0200]

[0201] Part of the monoamine compound (a13) having neither a carboxyl group nor a phenolic hydroxyl group, the monoamine compound (a14) having a carboxyl group but no phenolic hydroxyl group, the monoamine compound (a15) having a phenolic hydroxyl group but no carboxyl group, and the monoamine compound (a16) having both a carboxyl group and a phenolic hydroxyl group described in 1-4 is replaced with a crosslinkable alkoxysilane monoamine compound such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane (limited to the case where the compound of formula (4) is used in the synthesis of polyamic acid (A)).

[0202] In the case of introducing a combination of functional groups for forming crosslinking bonds other than the ester bond, there is the following method: When synthesizing polyamic acid (A), the compounds described in 1-1 to 1-4 are replaced as needed with R in formulas (1) to (4). 1 to R 4 in the structure (when the polyamic acid (A) does not contain the molecular terminal group of formula (6), it is R in formulas (5) and (7). 1 、R 2 and R 4 ; when the polyamic acid (A) does not contain the molecular terminal group of formula (7), it is R in formulas (5) and (6). 1 to R 3) Methods such as using a compound having a combination of functional groups for forming crosslinking bonds other than ester bonds are used, but are not limited thereto. In addition, the following method can be adopted: in the case where a part of the functional groups overlaps with the functional groups required for forming a crosslinking bond based on an ester bond in the present invention, that is, a part of the carboxyl group and phenolic hydroxyl group (in this case, the carboxyl group), among the compounds described in 1-1 to 1-4 (when the compound of formula (3) is not used in the synthesis of polyamic acid (A), the compounds described in 1-1, 1-2 and 1-4; when the compound of formula (4) is not used, the compounds described in 1-1 to 1-3), the compound having a phenolic hydroxyl group is partially replaced with a compound having an amino group instead of the phenolic hydroxyl group, and a part of the compound having a carboxyl group is also used for a crosslinking bond other than the crosslinking bond based on an ester bond, that is, an amide bond. In the above case, in the structure of R 1 to R 4 in formulas (5) to (7) of the obtained polyamic acid (A) (when the molecular terminal group of formula (6) is not included in polyamic acid (A), it is R 1 , R 2 and R 4 in formulas (5) and (7); when the molecular terminal group of formula (7) is not included in polyamic acid (A), it is R 1 to R 3 in formulas (5) and (6)), a part of the carboxyl groups contained therein participates in forming a crosslinking bond based on an ester bond during heat treatment, and the rest participates in forming a crosslinking bond based on an amide bond.

[0203] When introducing a crosslinking bond based on an amide bond formed by an amino group and a carboxyl group as a combination of functional groups for forming a crosslinking bond other than the ester bond, the following method is adopted: during the synthesis of polyamic acid (A), among the compounds described in 1-1 to 1-4 (when the compound of formula (3) is not used in the synthesis of polyamic acid (A), the compounds described in 1-1, 1-2 and 1-4; when the compound of formula (4) is not used, the compounds described in 1-1 to 1-3), the compound having a phenolic hydroxyl group is partially replaced with a compound having an amino group instead of the phenolic hydroxyl group, and a part of the compound having a carboxyl group is also used for a crosslinking bond other than the crosslinking bond based on an ester bond, that is, an amide bond. For example, a method such as using a method in which a part of the dicarboxylic anhydride (a11) having a phenolic hydroxyl group described in 1-3 but not having a carboxyl group is replaced with a compound having an amino group instead of the phenolic hydroxyl group can be used (limited to the case where the compound of formula (3) is used in the synthesis of polyamic acid (A)).

[0204] As specific examples of the dicarboxylic anhydride having an amino group that can be used in such examples, 3-aminooxolane-2,5-dione, L-asparagine anhydride, etc. can be cited, but are not limited to these.

[0205] The type of crosslinking bond other than the ester bond after heat curing is not limited to one type, and multiple types can also be contained simultaneously. Among them, from the viewpoint of reducing the linear thermal expansion coefficient of the cured product, the proportion of the ester bond in all the crosslinking bonds contained in the thermosetting resin composition after heat curing is preferably more than 50%, and more preferably more than 70%.

[0206] 1-6 Reaction solvent

[0207] The thermosetting resin composition of the present invention is preferably provided in a liquid state by adding a solvent as a reaction solvent when synthesizing the polyamic acid (A) contained in the composition or by appropriately adding a solvent after the synthesis of the polyamic acid (A).

[0208] The reaction solvent for synthesizing the polyamic acid (A) contained in the thermosetting resin composition of the present invention is not particularly limited as long as the polyamic acid (A) can be synthesized. Specifically, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc. can be cited.

[0209] Among these, from the aspect of dissolving the polyamic acid, N-methyl-2-pyrrolidone and 3-methoxy-N,N-dimethylpropionamide are preferred.

[0210] These reaction solvents can be used alone or as a mixed solvent of two or more. In addition, other solvents can also be mixed and used in addition to the reaction solvent.

[0211] If 100 parts by weight or more of the reaction solvent is used relative to 100 parts by weight in total of the solutes, the reaction proceeds smoothly, so it is preferred. The reaction is preferably carried out at 0°C to 120°C for 0.2 hours to 20 hours.

[0212] 1-7 Order of addition to the reaction system

[0213] In addition, the order of adding the reaction raw materials to the reaction system is not particularly limited. That is, any one of the following methods can be used: a method of adding a compound having two or more acid anhydride groups, a diamine compound, and a monoamine compound or a dicarboxylic anhydride to the reaction solvent at the same time; a method of dissolving the diamine compound and the dicarboxylic anhydride in the reaction solvent and then adding the compound having two or more acid anhydride groups and the monoamine compound; a method of dissolving the compound having two or more acid anhydride groups and the monoamine compound in the reaction solvent and then adding the diamine compound after pre-reacting the dicarboxylic anhydride; a method of pre-reacting the compound having two or more acid anhydride groups and the diamine compound to synthesize a copolymer and then adding the dicarboxylic anhydride to the copolymer, etc.

[0214] 1-8 Structure of polyamic acid

[0215] The polyamic acid contained in the thermosetting resin composition of the present invention has, for example, a structural unit represented by the formula (5) and has one or more molecular terminal groups selected from the group consisting of the molecular terminal groups represented by the formula (6) and the formula (7).

[0216] The polyamic acid can be synthesized, for example, by reacting the dicarboxylic anhydride or monoamine compound, the compound having two or more acid anhydride groups, and the diamine compound. That is, the formula (5) as the structural unit of the polyamic acid can be obtained by the reaction of a compound having two or more polymerization groups and two or more acid anhydride groups with a diamine compound having two polymerization groups. On the other hand, since the dicarboxylic anhydride and the monoamine compound have only one polymerization group, these compounds form molecular terminal groups in the polyamic acid. That is, R in the formula (6) 3 is the residue of the dicarboxylic anhydride, and R in the formula (7) 4 is the residue of the monoamine compound.

[0217] In addition, when only the dicarboxylic anhydride represented by the formula (3) is used in the reaction, at least one of R 1 to R 3 contains a carboxyl group and at least one of R 1 to R 3 contains a phenolic hydroxyl group.

[0218] In addition, when only the monoamine represented by the formula (4) is used in the reaction, at least one of R 1 , R 2 and R 4 contains a carboxyl group and at least one of R 1 , R 2 and R 4 contains a phenolic hydroxyl group.

[0219] Thus, in the thermosetting resin composition, a carboxyl group and a phenolic hydroxyl group coexist, and crosslinking bonds are formed based on ester bonds during heat curing.

[0220] The relationship between the structure of the polyamic acid and the monomers is merely an example. Additionally, the manufacturing method of the polyamic acid (A) is not limited to the described method.

[0221] 1-9 Weight-average molecular weight of polyamic acid

[0222] If the molecular weight of the polyamic acid contained in the thermosetting resin composition of the present invention is too low, a strong cured film cannot be produced due to curing shrinkage. Additionally, if the molecular weight is too high, the thermosetting resin composition becomes too viscous and loses fluidity, making it impossible to coat on a substrate. Therefore, it needs to be diluted with a solvent, and it is difficult to coat a thick film in one go and multiple coatings are required, resulting in a cumbersome process. That is, if it is within an appropriate viscosity range, it is easy to further increase the concentration of the polyamic acid in the thermosetting resin composition, which is advantageous in the coating process. For these reasons, the weight average molecular weight Mw of the polyamic acid contained in the thermosetting resin composition of the present invention is preferably 3000 ≤ Mw ≤ 150000, more preferably 5000 ≤ Mw ≤ 80000.

[0223] The weight average molecular weight of the polyamic acid is determined as follows: The obtained polyamic acid is diluted with dimethylformamide (containing phosphoric acid) to a polyamic acid concentration of approximately 1 wt%, and using a gel permeation chromatograph (GPC) device: manufactured by JASCO Corporation, JASCO GULLIVER 1500 (intelligent differential refractive index meter RI - 1530), with the diluted solution as the eluent, measured by the GPC method, and converted to polystyrene equivalent. Four columns manufactured by Tosoh Corporation, G4000HXL, G3000HXL, G2500HXL, and G2000HXL, are connected in series in sequence, and the measurement is carried out under the conditions of a column temperature of 40 °C and a flow rate of 1.0 ml / min.

[0224] 2 Additives

[0225] The thermosetting resin composition of the present invention can optionally select and add additives such as solvents, surfactants, antistatic agents, coupling agents, fillers, silicon compounds, pH adjusters, rust inhibitors, preservatives, fungicides, antioxidants, reduction inhibitors, evaporation promoters, chelating agents, etc., and these are uniformly mixed and dissolved for use.

[0226] 2-1 Solvent

[0227] The thermosetting resin composition of the present invention is obtained, for example, by dissolving polyamic acid in a solvent. Therefore, the solvent contained in the thermosetting resin composition of the present invention is not particularly limited as long as it can dissolve polyamic acid. In addition, even a solvent that does not dissolve polyamic acid alone can be used as the solvent contained in the thermosetting resin composition by mixing it with other solvents.

[0228] Specific examples of the solvent contained in the thermosetting resin composition of the present invention include: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc.

[0229] Among these, from the aspect of dissolving polyamic acid, N-methyl-2-pyrrolidone and 3-methoxy-N,N-dimethylpropionamide are preferred.

[0230] The amount of the solvent used is not particularly limited. For example, from the viewpoints of coatability or dispersibility when adding the fillers described below, the total amount of the solvent and the reaction solvent is preferably 10% by weight to 85% by weight, more preferably 15% by weight to 80% by weight, and still more preferably 25% by weight to 75% by weight, based on the total amount of the thermosetting resin composition.

[0231] 2-2 Surfactant

[0232] As the surfactant that can be added to the thermosetting resin composition of the present invention, from the viewpoint of improving coatability, for example, there can be mentioned: silicone surfactants such as the trade names "BYK-300", "BYK-306", "BYK-335", "BYK-310", "BYK-341", "BYK-344", "BYK-370" (manufactured by BYK-Chemie Co., Ltd.); acrylic surfactants such as the trade names "BYK-354", "BYK-358", "BYK-361" (manufactured by BYK-Chemie Co., Ltd.); fluorine surfactants such as the trade names "DFX-18", "Ftergent 250", "Ftergent 251" (manufactured by NEOS Co., Ltd.).

[0233] These surfactants can be used alone, or two or more of them can be mixed and used.

[0234] Surfactants are used to improve the wettability, leveling property, or coatability of the substrate. Preferably, 0.01 to 1 part by weight is added and used relative to 100 parts by weight of the thermosetting resin composition.

[0235] 2-3 Antistatic agent

[0236] The antistatic agents that can be added to the thermosetting resin composition of the present invention are not particularly limited, and known antistatic agents can be used. Specifically, metal oxides such as tin oxide, tin oxide - antimony oxide composite oxide, tin oxide - indium oxide composite oxide, or quaternary ammonium salts, etc. can be cited.

[0237] These antistatic agents can be used alone, or two or more of them can be mixed and used.

[0238] Antistatic agents are used to prevent charging. Preferably, 0.01 to 1 part by weight is added and used relative to 100 parts by weight of the thermosetting resin composition.

[0239] 2-4 Coupling agent

[0240] Coupling agents that can be added to the thermosetting resin composition of the present invention can use known coupling agents within the scope of achieving the object of the present invention. Among them, for example, trialkoxysilane compounds or dialkoxysilane compounds can be cited. Preferably, for example, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane, etc. Among these, silane coupling agents such as γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane are preferred.

[0241] The coupling agent is preferably used in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of the thermosetting resin composition. In addition, these coupling agents can be used alone, or two or more of them can be mixed and used.

[0242] 2-5 Filler

[0243] The thermosetting resin composition of the present invention can also be mixed and used with a filler component within the range that does not impair the characteristics of the present invention. As fillers, they are classified into inorganic fillers and organic fillers, etc. Among them, as inorganic fillers, silica, alumina, metals, and metal oxides can be cited.

[0244] Among the inorganic fillers, in terms of further reducing the linear thermal expansion coefficient of the cured film and reducing the residual stress when the thermosetting resin composition is coated on a substrate with a low thermal expansion coefficient and cured, it is preferably to contain a low-expansion filler.

[0245] The hot linear expansion coefficient of the low-expansion filler is preferably 1×10 -5 / °C or less, more preferably 7×10 -6 / °C or less, particularly preferably having a negative hot linear expansion coefficient. Further, it is preferably not to decompose when the resin composition is thermally cured.

[0246] Specifically, for example, it may include: silica, alumina, titanium oxide, zinc oxide, boron nitride, aluminum nitride, beryllium oxide, silicon carbide, silicon nitride, zirconium phosphate, zirconium tungstate, zirconium phosphotungstate, graphene, etc. From the viewpoints of acquisition and manufacture, silica, alumina, and zirconium phosphotungstate are preferred.

[0247] From the viewpoints of coatability, dispersibility, and manufacture, the content of the low-expansion filler in the thermosetting resin composition is preferably 10 vol% to 90 vol%, more preferably 30 vol% to 70 vol% in terms of volume% based on the total solid content of the resin composition.

[0248] The average particle size of the low-expansion filler is preferably 1 nm to 10,000 nm. From the viewpoints of dispersibility, viscosity, and fluidity, it is preferably 1 nm to 2,000 nm, and further preferably 1 nm to 700 nm.

[0249] The shape of the filler is not particularly limited and may be any of spherical, amorphous, scaly, etc. From the viewpoints of dispersibility and fluidity, it is preferably spherical. In addition, when the shape of the nano-silica filler is other than spherical, the average particle size of the nano-silica filler refers to the average maximum diameter of the filler.

[0250] The low-expansion filler may also be surface-treated. Commercially available products of the low-expansion filler that have been surface-treated in advance may be used, or substances obtained by treating the low-expansion filler with an untreated surface using a silane coupling agent or a titanate coupling agent may be used.

[0251] As specific examples (trade names) of the low-expansion filler that has been surface-treated in advance, for example, it may include:

[0252] Sansil SP-01MS, SP-03MS, SP-04MS, SP-07MS, SP-10MS, SP-15MS, SP-01P, SP-03P, SP-04P, SP-07P, SP-10P, SP-15P (manufactured by Tokuyama Corporation),

[0253] Silfil NHM-5N, NHM-4N, NHM-3N, NHM-24D, NHM-40D, NP-5N, NP-4N, NP-3N, NP-24D, NP-40D,

[0254] Reolosil MT-10, MT-10C, DM-10, DM-10C, DM-20, DM-30 (manufactured by Tokuyama Corporation),

[0255] Admafine SE1030-SP, SE2030-SP, SE1050-SP, SE2050-SP, SE4050-SP, SE1030-SX, SE2030-SX, SE1050-SX, SE2050-SX, SE4050-SX, SE1030-SM, SE2030-SM, SE1050-SM, SE2050-SM, SE4050-SM, AC2050-SP, AC2050-SX, AC2050-SM, AG2050-SP, AG2050-SX, AG2050-SM (manufactured by Admatechs Corporation),

[0256] Admanano YA010C-SP3, YA050C-SP3, YC100C-SP3, YA010C-SM1, YA050C-SM1, YC100C-SM1, YA010C-SV1, YA050C-SV2, YC100C-SV2 (manufactured by Admatechs Corporation).

[0257] As specific examples (trade names) of low-expansion fillers with untreated surfaces, for example, the following can be cited:

[0258] Sansil SS-01, SS-03, SS-04, SS-07, SS-10, SS-15 (manufactured by Tokuyama Corporation),

[0259] Silfil NSS-5N, NSS-4N, NSS-3N, NSS-24D, NSS-40D (manufactured by Tokuyama Corporation),

[0260] Excelica SE-8, SE-15, SE-30, SE-40, SE-15K, SE-30K, UF-305, UF-310, UF-320, UF-345, UF-725 (manufactured by Tokuyama Corporation, silica),

[0261] Reolosil QS-09, QS-10, QS-102, CP-102, QS-20, QS-20L, QS-30, QS-40 (manufactured by Tokuyama Corporation, silica),

[0262] Admafine SO-C1, SO-C2, SO-C4, SO-C5, SO-E1, SO-E2, SO-E4, SO-E5, SO-E6, AO-502, AO-506, AO-509 (manufactured by Admatechs Corporation, silica), AG2050, AG9200 (manufactured by Admatechs Corporation, alumina),

[0263] SFP-30M, SFP-130M (manufactured by Denka Company Limited, silica),

[0264] DAW-01, ASFP-20, ASFP-40, ASFP-03S, ASFP-05S, ASFP-07S (manufactured by Denka Company Limited, alumina),

[0265] Cerafit (manufactured by Nippon Chemical Industry Co., Ltd., zirconium phosphotungstate),

[0266] ULTEA WH-2 (manufactured by Toagosei Co., Ltd., zirconium phosphate),

[0267] MGP, GP, HGP, SP-2, SP-3 (manufactured by Denka Company Limited, boron nitride),

[0268] AP-10S, AP-20S, AP-100S (manufactured by MARIKA Co., Ltd., boron nitride),

[0269] SHO-BN UHP-S2, UHP-1K, UHP-2 (manufactured by Showa Denko K.K., boron nitride),

[0270] Fine-ZWO-01 (manufactured by Furuchi Chemical Co., Ltd., zirconium tungstate).

[0271] In the case of treating a low-expansion filler with an untreated surface, specific examples of silane coupling agents or titanate coupling agents, etc. include, for example: vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 1,1,1,3,3,3-hexamethyldisilazane, tetra-isopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetraoctyl titanate.

[0272] In order to improve the dispersibility of the low-expansion filler in the thermosetting resin composition, a dispersant can also be used. With respect to 100% by weight of the thermosetting resin composition, the dispersant is usually added and used in an amount of 0.1% to 90% by weight, preferably 0.1% to 25% by weight. The dispersant can be a single compound or two or more compounds can be used in combination.

[0273] Specific examples of the dispersant include, for example: ANTI-TERRA (registered trademark)-U, ANTI-TERRA (registered trademark)-U 100, 204, DISPERBYK (registered trademark)-102, 103, 106, 108, 109, 110, 111, 118, 140, 142, 145, 161, 162, 163, 164, 167, 168, 170, 171, 174, 180, 182, 184, 185, 2000, 2001, 2008, 2009, 2013, 2022, 2025, 2050, 2055, 2096, 2150, 2152, 2155, 2163, 2164, 2200, BYK (registered trademark)-P104, P104S, P105, 9076, 9077, 220S (manufactured by BYK-Chemie Japan Co., Ltd.),

[0274] Flowlen AF-1000, AF-1005, D-90, DOPA-15B, DOPA-15BHFS, DOPA-17HF, DOPA-22, DOPA-35, DOPA-100, G-700, G-820XF, GW-1500, KDG-2400 (manufactured by Kyoeisha Chemical Co., Ltd.),

[0275] TEGO (registered trademark) Dispers 610, 610S, 630, 650, 651, 652, 655, 660C, 662C, 670, 685, 700, 710, 715W, 740W, 750W, 752W, 755W, 760W (manufactured by Evonik Corporation), etc.

[0276] In order to impart dispersion stability or thixotropy to the low-expansion fillers in the thermosetting resin composition, a thickener can also be used. Relative to 100% by weight of the thermosetting resin composition, the thickener is usually added and used in an amount of 0.01% to 15% by weight, preferably 0.1% to 5% by weight. The thickener can be a single compound or two or more compounds can be used in combination. Furthermore, by using in combination with fillers having a primary average particle size of about several nanometers such as fumed silica, dispersion stability or thixotropy can be more effectively imparted.

[0277] 3 Viscosity and concentration of the thermosetting resin composition

[0278] The viscosity of the thermosetting resin composition in the present invention is not particularly limited. For example, in the case of coating by the dispenser printing method, it is 0.5 Pa·s to 15 Pa·s at room temperature (25 °C), more preferably 1 Pa·s to 10 Pa·s.

[0279] 4 Polyimide film forming method

[0280] The thermosetting resin composition of the present invention is coated on the surface of the substrate by various coating methods, and heat drying treatment is carried out using a hot plate or an oven, etc. to vaporize and remove the solvent, whereby a polyamic acid film having a full surface or a specified pattern shape (for example, linear shape) can be formed. As various coating methods, known methods such as the dispenser printing method, spin coating method, roll coating method, dipping method, flexographic method, spraying method, slot coating method, and inkjet method can be used. The heat drying conditions vary depending on the types and blending ratios of the respective components. Usually, when using an oven, a polyamic acid film is formed within 5 minutes to 15 minutes at 70 °C to 120 °C, and when using a hot plate, a polyamic acid film is formed within 1 minute to 5 minutes.

[0281] Next, after forming the polyamic acid film, in order to imidize the polyamic acid and to form crosslinking bonds based on ester bonds in the polyamic acids with each other, further heating is carried out. The heating conditions vary depending on the types and blending ratios of the respective components, but by performing a heat treatment at 200 °C to 400 °C for 30 minutes to 60 minutes using an oven, a thermoset polyimide film can be obtained.

[0282] 5 Substrate having a cured film

[0283] A substrate having the cured film of the present invention is obtained, for example, by coating the thermosetting resin composition of the present invention over the entire surface or in a specified pattern (such as a line pattern) on a substrate such as a polyimide film on which wiring is formed by a method such as dispenser printing method, followed by drying the substrate and further heating to form a polyimide film.

[0284] The polyimide film that can be used in the present invention is preferably formed on a substrate such as the polyimide film, but is not particularly limited thereto and can be formed on a known substrate.

[0285] Examples of the substrate applicable to the present invention include glass epoxy substrates, glass composite substrates, phenolic paper substrates, epoxy paper substrates, green epoxy substrates, or bismaleimide triazine (BT) resin substrates that conform to various specifications such as FR-1, FR-3, FR-4, CEM-3, or E668.

[0286] In addition, as other substrates that can be applied to the present invention, for example, the following can be cited: substrates containing metals such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, or stainless steel (substrates having the surfaces of these metals are also acceptable); or substrates containing ceramics such as alumina (alumina), aluminum nitride, zirconia (zirconia), zirconium silicate (zircon), magnesia (magnesia), aluminum titanate, barium titanate, lead titanate (PT), lead zirconate titanate (PZT), lanthanum lead zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia), silicon dioxide (silica), silicon carbide (silicon carbide), silicon nitride (silicon nitride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, forsterite, spinel, or spodumene (substrates having the surfaces of these ceramics are also acceptable); or substrates containing resins such as polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polycyclohexylenedimethylene terephthalate (PCT) resin, polyphenylene sulfide (PPS) resin, polycarbonate resin, polyacetal resin, polyphenylene ether resin, polyamide resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer, or liquid crystal polymer (substrates having the surfaces of these resins are also acceptable); or semiconductor substrates such as silicon, germanium, or gallium arsenide; or glass substrates; or substrates having electrode materials such as tin oxide, zinc oxide, indium tin oxide (ITO), or antimony tin oxide (ATO) formed on their surfaces; or gel sheets such as αGEL, βGEL, θGEL, or γGEL (the above are registered trademarks of Taica Corporation).

[0287] 6 Electronic parts

[0288] For example, the thermosetting resin composition of the present invention is coated on a film substrate such as a polyimide film on which wiring has been previously formed, and then the film substrate is dried and further heated to obtain a flexible electronic component covered with an insulating polyimide film.

[0289] Examples

[0290] Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited to these examples.

[0291] The names of compounds having two or more acid anhydride groups, diamine compounds, dicarboxylic anhydrides, monoamine compounds, and reaction solvents used in the examples and comparative examples are represented by abbreviations. The following description uses these abbreviations.

[0292] Compound having two or more acid anhydride groups

[0293] <Compound (a1) having neither a carboxyl group nor a phenolic hydroxyl group among compounds having two or more acid anhydride groups>

[0294] TAHQ: 1,4-Phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate)

[0295] BP-TME: 4,4'-Bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl

[0296] 26DHN-TME: Naphthalene-2,6-diylbis(1,3-dihydroisobenzofuran-5-carboxylate)

[0297] PMDA: Pyromellitic dianhydride

[0298] sBPDA: 4,4'-Bis(phthalic anhydride)

[0299] TMPBP-TME: 2,2',3,3',5,5'-Hexamethyl[1,1'-biphenyl]-4,4'-diyl bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate)

[0300] Diamine compound

[0301] <Diamine compound (a5) having neither a carboxyl group nor a phenolic hydroxyl group>

[0302] DABA: 4,4'-Diaminobenzanilide

[0303] DAAB: 4,4'-Diaminoazobenzene

[0304] DAPBI: 5,4'-Diamino-2-phenylbenzimidazole

[0305] PDA: p-Phenylenediamine

[0306] ODA: 4,4'-Diaminodiphenyl ether

[0307] <Diamine compound (a6) having a carboxyl group but not having a phenolic hydroxyl group>

[0308] DABzA: 3,5-Diaminobenzoic acid

[0309] Dicarboxylic anhydride

[0310] <Dicarboxylic anhydride (a9) not having either a carboxyl group or a phenolic hydroxyl group>

[0311] PAH: Phthalic anhydride

[0312] 4-EPA: 4-Ethynylphthalic anhydride

[0313] MAH: Maleic anhydride

[0314] Monoamine compound

[0315] <Monoamine compound (a14) having a carboxyl group but not having a phenolic hydroxyl group>

[0316] AIPA: 5-Aminoisophthalic acid

[0317] <Monoamine compound (a15) having a phenolic hydroxyl group but not having a carboxyl group>

[0318] APhOH: 4-Aminophenol

[0319] ANPhOH: 5-Amino-1-naphthol

[0320] Reaction solvent

[0321] NMP: N-Methyl-2-pyrrolidone

[0322] [Synthesis Example 1] Synthesis of polyamic acid (E1)

[0323] In a 50 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, the raw materials were charged as shown in Table 1, and the mixture was stirred at 25°C for 1 hour under a dry nitrogen stream, and then heated to 80°C and reacted for 6 hours to obtain a pale yellow transparent polyamic acid solution (20 wt%). The viscosity of the solution was 1.5 Pa·s (25°C). The weight average molecular weight measured by GPC was 21,000.

[0324] The viscosity of the solution was measured using an E-type viscometer (VISCONIC ELD manufactured by TOKYO KEIKI INC.).

[0325] The weight-average molecular weight of the polyamic acid was determined as follows. The obtained polyamic acid was diluted with dimethylformamide (containing phosphoric acid) to a polyamic acid concentration of about 1% by weight, and using a GPC device: JASCO GULLIVER 1500 (intelligent differential refractive index meter RI-1530) manufactured by JASCO Corporation, the diluted solution was used as the eluent, and the determination was carried out by the GPC method and converted to polystyrene equivalent. Four columns, namely TSKgel G4000HXL, TSKgel G3000HXL, TSKgel G2500HXL, and TSKgel G2000HXL, manufactured by Tosoh Corporation, were connected in series in turn, and the determination was carried out under the conditions of a column temperature of 40 °C and a flow rate of 1.0 ml / min.

[0326] [Synthesis Examples 2 to 11] Synthesis of Polyamic Acids (E2) to (E11)

[0327] As shown in Table 1, the raw materials were charged, and in addition, polyamic acid solutions were prepared under the same conditions as in Synthesis Example 1 and used as polyamic acids (E2) to (E11) respectively.

[0328] [Table 1]

[0329]

[0330] [Comparative Synthesis Example 1] Synthesis of Polyamic Acid (C1)

[0331] Using the same method as in Synthesis Example 1, the raw materials were charged as described in Table 2, stirred at 25 °C for 1 hour under a dry nitrogen stream, and then the temperature was raised to 80 °C and stirred for 6 hours to obtain a pale yellow transparent polyamic acid solution (8 wt%). The viscosity of the solution was 12 Pa·s (25 °C). The weight-average molecular weight determined by GPC was 160,000.

[0332] [Comparative Synthesis Examples 2 to 8] Synthesis of Polyamic Acids (C2) to (C8)

[0333] As shown in Table 2, the raw materials were charged, and in addition, polyamic acid solutions were prepared under the same conditions as in Comparative Synthesis Example 1 and used as polyamic acids (C2) to (C8).

[0334] [Table 2]

[0335]

[0336] [Example 1]

[0337] The polyamic acid (E1) synthesized in Synthesis Example 1 was directly used as the thermosetting resin composition (E1), and the following evaluations of residual stress, heat resistance, and toughness were carried out.

[0338] [Evaluation of Residual Stress]

[0339] When forming a cured film on a glass substrate, warping occurs on the substrate due to the generated stress. In order to quantitatively evaluate the degree, the residual stress generated between the substrate and the cured film was evaluated. First, a long strip glass substrate with a size of 10 cm × 2 cm and a thickness of 0.7 mm (hereinafter referred to as the long strip substrate) was prepared, and its initial radius of curvature Rb was measured by long-distance scanning with a stylus profilometer (trade name: P-16+, manufactured by KLA-Tencor Corporation). Then, the thermosetting resin composition (E1) was coated on the long strip substrate at 1500 rpm for 30 seconds using a spin coater, dried on a hot plate at 80 °C for 5 minutes, and then heat-treated in an oven at 350 °C for 60 minutes to produce a long strip substrate with a cured film. After that, the radius of curvature R of the long strip substrate with the cured film was measured using a stylus profilometer. a .

[0340] Based on the radius of curvature R a and R b , according to the Inoue-Kohata method, the residual stress on the long strip substrate was calculated according to the following formula (8).

[0341]

[0342] (E s , d s , d f are the Young's modulus of the substrate, the thickness of the substrate, and the thickness of the thin film, respectively). Regarding the evaluation results, when the residual stress is less than 10 MPa, it is designated as ◎, when the residual stress is 10 MPa or more and less than 20 MPa, it is designated as △, and when the residual stress is 20 MPa or more, it is designated as ×.

[0343] [Evaluation of Heat Resistance]

[0344] The heat resistance was evaluated based on the glass transition temperature (Tg).

[0345] The thermosetting resin composition (E1) cast on a substrate was heat-treated at 80 °C for 60 minutes, at 130 °C for 30 minutes, at 175 °C for 30 minutes, and at 350 °C for 60 minutes to produce a film (film thickness: 30 μm to 50 μm). The obtained film was measured using DMA (trade name: RSA-G2, manufactured by TA Instruments Co., Ltd.) at a frequency of 1 Hz in the temperature range of 20 °C to 500 °C. Tg was calculated based on the onset of the storage elastic modulus E'.

[0346] Regarding the evaluation results, ◎ was set when Tg was 400 °C or higher, × was set when Tg was less than 400 °C, and - was set when cracks occurred during the heat treatment and the film could not be produced.

[0347] [Evaluation of toughness]

[0348] Using the thermosetting resin composition (E1), a film heat-treated under the same conditions as in the evaluation of heat resistance was produced. Subsequently, the SS curve of the film was measured using a tensile testing machine (trade name: EZ-Graph, manufactured by Shimadzu Corporation), and the area was calculated and used as the toughness value (toughness). Regarding the evaluation results, ◎ was set when the toughness value was 5 MJ / m 3 or higher, × was set when it was below that, and - was set when cracks occurred during the heat treatment and the film could not be produced.

[0349] [Examples 2 to 11]

[0350] The polyamic acids (E2) to polyamic acids (E11) obtained in Synthesis Examples 2 to 11 were directly used as the thermosetting resin compositions (E2) to thermosetting resin compositions (E11), and the evaluations of residual stress, heat resistance, and toughness were carried out under the same conditions as in Example 1.

[0351] [Comparative Examples 1 to 8]

[0352] The polyamic acids (C1) to polyamic acids (C8) obtained in Comparative Synthesis Examples 1 to 8 were directly used as the thermosetting resin compositions (C1) to thermosetting resin compositions (C8), and the evaluations of residual stress, heat resistance, and toughness were carried out under the same conditions as in Example 1.

[0353] The results of Examples 1 to 11 and Comparative Examples 1 to 8 were summarized in Table 3.

[0354] [Table 3]

[0355]

[0356] As shown in Table 1 and Table 2, in Synthesis Examples 1 to 11, compared with the compositions with unsealed ends in Comparative Synthesis Examples 1 to 4, they have the same level of viscosity and a high concentration. On this basis, as shown in Table 3, all of the Examples are results with good residual stress, heat resistance, and toughness.

[0357] On the other hand, as shown in Table 3, it can be seen that in the Comparative Examples, the cured films do not fully satisfy the residual stress, heat resistance, and toughness. In the case of low residual stress, the film is brittle and lacks toughness, or in the case of high toughness, the residual stress becomes high. In particular, in Comparative Examples 5 and 6 where the ends are sealed with non-thermoreactive phthalic anhydride (PAH), although the weight average molecular weight of the polyamic acid (A) contained in the thermosetting resin composition used in the production of these cured films is at the same level as that of the polyamic acid (A) contained in the thermosetting resin composition used in the production of the cured films in the Examples, the film becomes very brittle. In addition, it can be seen that in Comparative Examples 7 and 8 where end compounds (4-EPA, MAH) with thermoreactivity but not ester crosslinked ends are introduced, although the weight average molecular weight of the polyamic acid (A) contained in the thermosetting resin composition used in the production of these cured films is at the same level as that of the polyamic acid (A) contained in the thermosetting resin composition used in the production of the cured films in the Examples, the residual stress becomes high and the toughness also decreases, making it less durable.

[0358] Industrial Applicability

[0359] As an application method of the present invention, for example, an insulating film for a flexible printed circuit board and electronic parts using the same can be cited.

Claims

1. A thermosetting resin composition comprising a polyamic acid (A) obtained by reacting a compound having two or more acid anhydride groups represented by formula (1), a diamine compound represented by formula (2), and at least one of a dicarboxylic anhydride represented by formula (3) and a monoamine compound represented by formula (4); by heating, ester bonds can be formed between polyamic acids (A); 1. A thermosetting resin composition comprising a polyamic acid (A) obtained by reacting a compound having two or more acid anhydride groups represented by formula (1), a diamine compound represented by formula (2), and at least one of a dicarboxylic anhydride represented by formula (3) and a monoamine compound represented by formula (4); by heating, ester bonds can be formed between polyamic acids (A); a diamine compound represented by formula (2), and at least one of a dicarboxylic anhydride represented by formula (3) and a monoamine compound represented by formula (4) reaction; by heating, ester bonds can be formed between polyamic acids (A); H2N-R 2 -NH2 (2) H2N—R 4 (4) (R 1 to R 4 are each independently an organic group having 1 to 100 carbon atoms which may contain Si. In at least one of R 1 to R 4 , at least one hydrogen in at least one hydrocarbon group contained in the organic group is substituted with a carboxyl group. In at least one of R 1 to R 4 , at least one hydrogen in at least one hydrocarbon group contained in the organic group is substituted with a phenolic hydroxyl group).

2. The thermosetting resin composition according to claim 1, wherein, The R 1 and R 2 are wholly aromatic amide structures or wholly aromatic ester structures, and R 3 and R 4 contain aromatic rings.

3. A cured film obtained from the thermosetting resin composition according to claim 1.

4. A substrate having the cured film according to claim 3.

5. An electronic component using the cured film according to claim 3 or the substrate according to claim 4.

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