Polyimide resin precursor composition and polyimide film

Abstract

Disclosed are: a polyimide resin precursor composition which contains a polyimide resin precursor (X) that has an amic acid structure, and a compound (Y) that has three to five amic acid structures and three or more oxysilyl groups; and a polyimide film which is obtained by applying the polyimide resin precursor composition onto a support and heating the applied polyimide resin precursor composition. The polyimide resin precursor composition has excellent stability and excellent film formability, and enables the achievement of a polyimide film that has excellent heat resistance and excellent adhesion. The polyimide film has excellent heat resistance and excellent adhesion.

Description

Polyimide resin precursor composition and polyimide film

[0001] This invention relates to a polyimide resin precursor composition and a polyimide film.

[0002] Due to its excellent heat resistance and mechanical properties, polyimide resins are being considered for various applications in fields such as electrical and electronic components. Among electrical and electronic components, polyimide resins with heat resistance and transparency are used in the display field. For example, Patent Document 1 discloses a polyimide precursor containing a tetracarboxylic acid and an amine compound having three or more amino groups, with the aim of obtaining a crosslinked polyimide with excellent heat resistance and dimensional stability at high temperatures.

[0003] International Publication No. 2017 / 069165

[0004] Polyimide resins are used not only in the display field but also as insulating film materials in the semiconductor field. Polyimide resins used in the semiconductor field require heat resistance to withstand higher temperature processes. Specifically, with the advancement of 3D packaging technology, processes such as CVD and hybrid bonding require heat resistance of at least 300°C, and the miniaturization of semiconductors requires resins with even greater heat resistance. In addition, silicon wafers used in the semiconductor field have few functional groups on their surface, making it difficult to achieve adhesion with resins. Furthermore, when using polyimide resin as a material in the semiconductor field, it is necessary to form a coating (film) of a certain thickness, but as the film thickness increases, the curing shrinkage stress increases, leading to cracks and surface roughness, and a deterioration in film formation performance. Also, in order to make the coating thicker, it is usually necessary to increase the solid content concentration in the polyimide resin precursor solution (varnish), which leads to a decrease in the stability of the solution. The present invention has been made in view of these circumstances, and the object of the present invention is to provide a polyimide resin precursor composition that can be obtained with excellent heat resistance and adhesion, and has excellent stability and film-forming properties, as well as a polyimide film with excellent heat resistance and adhesion properties.

[0005] The present inventors have found that a polyimide resin precursor composition comprising a polyimide resin precursor having an amidic acid structure and a specific compound having an amidic acid structure and an alkoxysilyl group can solve the above problems, and have completed the invention.

[0006] In other words, the present invention relates to the following [1], [1a], [2] to

[11] . [1] A polyimide resin precursor composition comprising a polyimide resin precursor (X) having an amidic acid structure and a compound (Y) having an amidic acid structure and three or more oxysilyl groups. [1a] A polyimide resin precursor composition comprising a polyimide resin precursor (X) having an amidic acid structure and a compound (Y) having three to five amidic acid structures and three or more oxysilyl groups. [2] The polyimide resin precursor composition according to [1] or [1a], wherein compound (Y) comprises a compound (Y) having three to five oxysilyl groups. [3] The polyimide resin precursor composition according to [1], [1a] or [2], wherein compound (Y) is a compound represented by the following general formula (y1). (In the formula, A 1 is a trivalent or tetravalent hydrocarbon group, B 1 C is a divalent hydrocarbon group which may have a single bond or an ether group, carbonyl group, ester group, amide group, or thiol group as a bond, 1R is a single bond, or a divalent hydrocarbon group which may have an ether group, carbonyl group, ester group, amide group, or thiol group as a bond; R is independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms; and n is 3 or 4. ) [4] The polyimide resin precursor composition according to [1], [1a], [2] or [3], wherein the polyimide resin precursor (X) has constituent units A derived from a tetracarboxylic dianhydride and constituent units B derived from a diamine, wherein constituent unit A includes at least one selected from the group consisting of constituent units (A1) derived from a compound represented by the following formula (a1), constituent unit (A2) derived from a compound represented by the following formula (a2), constituent unit (A3) derived from a compound represented by the following formula (a3), and constituent unit (A4) derived from a compound represented by the following formula (a4), and constituent unit B includes at least one selected from the group consisting of constituent units (B1) derived from a compound represented by the following formula (b1) and constituent unit (B2) derived from a compound represented by the following formula (b2). (In the formula, L is independently at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, an amide group, and a thiol group, and k is 0 or 1.) [5] The polyimide resin precursor composition according to [4], wherein the constituent unit (A3) comprises at least one selected from the group consisting of a constituent unit (A31) derived from a compound represented by the following formula (a31) and a constituent unit (A32) derived from a compound represented by the following formula (a32). [6] The polyimide resin precursor composition according to [4] or [5], wherein the constituent unit (B2) comprises at least one selected from the group consisting of constituent units (B21) derived from a compound represented by the following formula (b21) and constituent units (B22) derived from a compound represented by the following formula (b22). [7] The polyimide resin precursor composition according to any one of [1], [1a], [2] to [6], wherein the compound (Y) is a compound represented by the following general formula (y11). (wherein R is independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms, and n is 3 or 4.) [8] The polyimide resin precursor composition according to any one of [1], [1a], [2] to [6], wherein the compound (Y) is a compound obtained by the reaction of an amine compound with a compound having a carboxyl group and an oxysilyl group, and the amine compound is a compound represented by the following formula (d1). (wherein M is independently at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, an amide group, and a thiol group.) [9] The polyimide resin precursor composition according to [8], wherein the amine compound is a compound represented by the following formula (d11).

[10] A polyimide resin precursor composition according to any one of [1], [1a], [2] to [9], further comprising a solvent.

[11] A polyimide film obtained by coating the polyimide resin precursor composition according to any one of [1], [1a], [2] to

[10] onto a support and heating it.

[0007] This invention provides a polyimide resin precursor composition with excellent heat resistance and adhesion, as well as a polyimide film with excellent stability and film-forming properties. Because the polyimide resin precursor varnish of this invention possesses these properties, it is useful as a raw material in the semiconductor field.

[0008] [Polyimide Resin Precursor Composition] The polyimide resin precursor composition of the present invention is a polyimide resin precursor composition comprising a polyimide resin precursor (X) having an amide acid structure and a compound (Y) having an amide acid structure and three or more oxysilyl groups. A more preferred polyimide resin precursor composition of the present invention is a polyimide resin precursor composition comprising a polyimide resin precursor (X) having an amide acid structure and a compound (Y) having three to five amide acid structures and three or more oxysilyl groups.

[0009] The reason why the polyimide resin precursor composition of the present invention exhibits excellent stability and film-forming properties, and why a polyimide film with excellent heat resistance and adhesion can be obtained by using the polyimide resin precursor composition of the present invention, is not entirely clear, but it is thought to be as follows. The polyimide resin precursor composition of the present invention is thought to exhibit good stability and film-forming properties by using a linear structure precursor as the polyimide resin precursor having an amidic acid structure, and a polyfunctional compound as the compound having an oxysilyl group, and mixing them. Furthermore, the resulting polyimide film is thought to have excellent heat resistance due to having an imide skeleton and a crosslinked structure by -Si-O- bonds, and excellent adhesion due to containing alkoxysilyl groups in the resin skeleton. As described above, the polyimide resin precursor composition of the present invention is thought to be able to obtain a polyimide film with excellent heat resistance and adhesion, and is thought to have excellent stability and film-forming properties.

[0010] <Polyimide Resin Precursor (X)> The polyimide resin precursor (X) contained in the polyimide resin precursor composition of the present invention may have any amide acid structure, but preferably has the following configuration. The polyimide resin precursor (X) contained in the polyimide resin precursor composition of the present invention has a constituent unit A derived from a tetracarboxylic dianhydride and a constituent unit B derived from a diamine, wherein constituent unit A includes at least one selected from the group consisting of constituent unit (A1) derived from a compound represented by the following formula (a1), constituent unit (A2) derived from a compound represented by the following formula (a2), constituent unit (A3) derived from a compound represented by the following formula (a3), and constituent unit (A4) derived from a compound represented by the following formula (a4), and constituent unit B includes at least one selected from the group consisting of constituent unit (B1) derived from a compound represented by the following formula (b1) and constituent unit (B2) derived from a compound represented by the following formula (b2). By making the polyimide resin precursor having such a bent structure or a structure with high steric hindrance an amide acid structure into a linear structure, good stability and film-forming properties are exhibited, and furthermore, the obtained polyimide film is considered to have excellent heat resistance due to having an imide skeleton. (In the formula, L is independently selected from the group consisting of an ether group, a carbonyl group, an ester group, an amide group, and a thiol group, and k is 0 or 1.)

[0011] The polyimide resin precursor (X) may have any amidic acid structure, but preferably has a polyamidic acid structure, and more preferably is a polyamidic acid.

[0012] The number-average molecular weight of the polyimide resin precursor (X) is preferably 1,000 to 500,000, from the viewpoint of film-forming properties, adhesion, heat resistance, and mechanical strength of the resulting polyimide film. Similarly, the weight-average molecular weight (Mw) is more preferably 2,000 to 500,000, even more preferably 3,000 to 300,000, and even more preferably 3,000 to 100,000. The number-average molecular weight and weight-average molecular weight of the polyimide resin precursor (X) can be determined from the standard polymethyl methacrylate (PMMA) equivalent values ​​obtained by gel filtration chromatography.

[0013] The molar ratio (B / A) of the amount of constituent unit B derived from diamine to the amount of constituent unit A derived from tetracarboxylic dianhydride is preferably 0.70 or more, more preferably 0.75 or more, even more preferably 0.80 or more, even more preferably 0.85 or more, even more preferably 0.88 or more, and even more preferably 0.90 or more. Also, it is preferably 0.70 to 1.00, more preferably 0.70 to 0.95, even more preferably 0.75 to 0.95, even more preferably 0.80 to 0.95, even more preferably 0.85 to 0.95, even more preferably 0.88 to 0.95, and even more preferably 0.90 to 0.95. By setting the molar ratio within the above range, the stability of the polyimide resin precursor composition can be improved. Furthermore, film-forming properties can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0014] The polyimide resin precursor (X) content in the polyimide resin precursor composition of the present invention is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass. By having the polyimide resin precursor (X) content within the above range, the resulting polyimide resin precursor composition exhibits excellent stability and film-forming properties, and a polyimide film with excellent heat resistance and adhesion can be obtained.

[0015] (Constituent Unit A) Constituent unit A is a constituent unit derived from tetracarboxylic dianhydride in the polyimide resin precursor. Preferably, constituent unit A includes at least one selected from the group consisting of constituent unit (A1) derived from a compound represented by the following formula (a1), constituent unit (A2) derived from a compound represented by the following formula (a2), constituent unit (A3) derived from a compound represented by the following formula (a3), and constituent unit (A4) derived from a compound represented by the following formula (a4). By including the above constituent unit in constituent unit A, the stability and film formation properties, as well as the heat resistance and adhesion of the polyimide film, can be improved. (In the formula, L is independently selected from the group consisting of an ether group, a carbonyl group, an ester group, an amide group, and a thiol group, and k is 0 or 1.)

[0016] The compound represented by formula (a1) is 4,4'-oxydiphthalic anhydride (ODPA). By including constituent unit (A1) in constituent unit A, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved. The compound represented by formula (a2) is pyromellitic anhydride (PMDA). By including constituent unit (A2) in constituent unit A, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved. The compound represented by formula (a4) is spiro[11H-difluoro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetron (SFDA). By including constituent unit (A4) in constituent unit A, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0017] In formula (a3), L is independently at least one selected from the group consisting of an ether group (-O-), a carbonyl group (-CO-), an ester group (-COO- or -OCO-), an amide group (-CONH- or -NHCO-), and a thiol group (-S-), but is preferably an ether group. In formula (a3), k is 0 or 1, but is preferably 0. Therefore, the compound represented by formula (a3) ​​is preferably at least one selected from the group consisting of the compound represented by the following formula (a31) and the compound represented by the following formula (a32), and more preferably the compound represented by formula (a31). In other words, the constituent unit (A3) preferably includes at least one selected from the group consisting of a constituent unit (A31) derived from the compound represented by the following formula (a31) and a constituent unit (A32) derived from the compound represented by the following formula (a32), and more preferably includes a constituent unit (A31) derived from the compound represented by the following formula (a31).

[0018] The compound represented by formula (a31) is 9,9-bis(3,4-dicarboxyphenyl)fluorenodioanhydride (BPAF). By including constituent unit (A31) in constituent unit A, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved. The compound represented by formula (a32) is 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorenodioanhydride (BPF-PA). By including constituent unit (A32) in constituent unit A, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0019] The ratio of constituent unit (A1) in constituent unit A is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and constituent unit A may consist only of constituent unit (A1). By having the ratio of constituent unit (A1) within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0020] The ratio of constituent unit (A3) in constituent unit A is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and constituent unit A may consist only of constituent unit (A3). By having the ratio of constituent unit (A3) within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0021] The ratio of constituent unit (A4) in constituent unit A is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and constituent unit A may consist only of constituent unit (A4). By having the ratio of constituent unit (A4) within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0022] In component unit A, two or more components may be included from component unit (A1), component unit (A2), component unit (A3), and component unit (A4). In particular, it is preferable to include component unit (A1) and one or more of component units (A2), component unit (A3), and component unit (A4). The molar ratio of component unit (A1) to the total of component units (A2), component units (A3), and component unit (A4) in component unit A [(A1) / ((A2)+(A3)+(A4))] is preferably 30 / 70 to 100 / 0, more preferably 40 / 60 to 100 / 0, and especially from the viewpoint of heat resistance, even more preferably 40 / 60 to 90 / 10, even more preferably 40 / 60 to 80 / 20, and even more preferably 40 / 60 to 60 / 40. If the molar ratio of constituent unit (A1) to the total of constituent units (A2), (A3), and (A4) is 100 / 0, then constituent unit A does not contain constituent units (A2), (A3), and (A4).

[0023] The molar ratio [(A1) / (A2)] of constituent units (A1) to constituent units (A2) in constituent unit A is preferably 30 / 70 to 100 / 0, more preferably 40 / 60 to 100 / 0, and especially from the viewpoint of heat resistance, even more preferably 40 / 60 to 90 / 10, even more preferably 40 / 60 to 80 / 20, and even more preferably 40 / 60 to 60 / 40. When the molar ratio of constituent units (A1) to constituent units (A2) is 100 / 0, constituent unit A does not contain constituent unit (A2). By having the constituent units constituting constituent unit A in the above molar ratio, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and in particular the heat resistance and adhesion of the resulting polyimide film can be enhanced.

[0024] Constituent unit A may include constituent units other than constituent units (A1), (A2), (A3), and (A4). Examples of tetracarboxylic dianhydrides that provide such constituent units are not particularly limited, but include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides, excluding the compound represented by formula (a1), formula (a2), formula (a3), and formula (a4). When constituent unit A includes constituent units other than (A1), (A2), (A3), and (A4), it is preferable that it includes aromatic tetracarboxylic dianhydrides among the tetracarboxylic dianhydrides excluding the compound represented by formula (a1), formula (a2), formula (a3), and formula (a4).

[0025] Examples of aromatic tetracarboxylic dianhydrides include 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 2,3,6,7-naphthalenetetracarboxylic 2,3:6,7-dianhydride (NTCDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl] Hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic acid dianhydride (a-BPDA), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis(trimellitate) dianhydride (TMEG), p-phenylene bis(trimellitate) dianhydride (TAHQ), 9,9-bis[4-(3,4-dicarboxyphenyl] Cyphenoxy)phenyl]fluorenidioanhydride (BPF-PA), 2,3,6,7-naphthalenetetracarboxylic acid 2,3:6,7-dianhydride (NTCDA), 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA), 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid dianhydride (6FCDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 2,2-bis(3,4- Examples include dicarboxyphenyl)-propane dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic acid dianhydride (a-BPDA), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), hydroquinone diphthalic anhydride (HQDPA), ethylene glycol bis(trimellitate) dianhydride (TMEG), p-phenylene bis(trimellitate) dianhydride (TAHQ), and the like.Examples of alicyclic tetracarboxylic dianhydrides include cyclohexane-1,2,4,5-tetracarboxylic dianhydride (HPMDA), cyclohexane-1,2,3,4-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5',6,6'-tetracarboxylic dianhydride (CpODA), 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2,3,4-cyclop Examples include tetratetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic acid dianhydride, 2,2-propyridene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, and bicyclo[4.4.0]decane-2,3,6,7-tetracarboxylic acid dianhydride. Examples of aliphatic tetracarboxylic acid dianhydrides include 1,2,3,4-butanetetracarboxylic acid dianhydride. In this specification, aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings, alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more alicyclic rings but no aromatic rings, and aliphatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing neither aromatic nor alicyclic rings. The constituent unit A may consist of one type or two or more types.

[0026] (Constituent Unit B) Constituent unit B is a constituent unit derived from diamine in the polyimide resin precursor. Preferably, constituent unit B contains at least one selected from the group consisting of constituent units (B1) derived from a compound represented by the following formula (b1) and constituent units (B2) derived from a compound represented by the following formula (b2). In particular, constituent unit B preferably contains constituent unit (B1) derived from a compound represented by the following formula (b1). By including the above constituent unit in constituent unit B, the stability and film-forming properties of the polyimide resin precursor composition and the heat resistance and adhesion of the polyimide film can be improved. (In the formula, L is independently selected from the group consisting of an ether group, a carbonyl group, an ester group, an amide group, and a thiol group, and k is 0 or 1.)

[0027] The compound represented by formula (b1) is 4,4'-diaminodiphenyl ether (ODA). By including constituent unit (B1) in constituent unit B, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be enhanced.

[0028] In formula (b2), L is independently at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, an amide group, and a thiol group, but is preferably an ether group. In formula (b2), k is 0 or 1, but is preferably 0. Therefore, the compound represented by formula (b2) is preferably at least one selected from the group consisting of the compound represented by the following formula (b21) and the compound represented by the following formula (b22), and more preferably the compound represented by formula (b21). In other words, the constituent unit (B2) preferably includes at least one selected from the group consisting of a constituent unit (B21) derived from the compound represented by the following formula (b21) and a constituent unit (B22) derived from the compound represented by the following formula (b22), and more preferably includes a constituent unit (B21) derived from the compound represented by the following formula (b21).

[0029] The compound represented by formula (a31) is 9,9-bis(4-aminophenyl)fluorene (BAFL). By including constituent unit (B31) in constituent unit B, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved. The compound represented by formula (a32) is 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene (BPF-AN). By including constituent unit (B32) in constituent unit B, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0030] The ratio of constituent unit (B1) in constituent unit B is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and constituent unit B may consist only of constituent unit (B1). By having the ratio of constituent unit (B1) within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0031] The ratio of constituent unit (B2) in constituent unit B is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and constituent unit B may consist only of constituent unit (B2). By having the ratio of constituent unit (B2) within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0032] Constituent unit B may include constituent units other than constituent units (B1) and (B2). Diamines that provide such constituent units are not particularly limited, but include aromatic diamines, alicyclic diamines, and aliphatic diamines, excluding the compound represented by formula (b1) and the compound represented by formula (b2). Aromatic diamines include bis(4-aminophenyl) terephthalate (APTP), 1,4-bis(4-aminobenzoyloxy)benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-TFMB), 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-5,5'- Diaminobiphenyl, 2,2-bis(4-aminophenyl)hexafluoropropane (HFDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (DDM), 4,4'-diaminodiphenylsulfone (4,4'-DDS), 3,3'-diaminodiphenylsulfone Hon(3,3'-DDS), 4,4'-diamino-2,2'-dimethylbiphenyl(mTB), 4,4'-diaminobiphenyl(benzidine), 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 5-amino-1,3,3-trimethyl-1-(4-aminophenyl)-indan(5-TMD) M), 6-amino-1,3,3-trimethyl-1-(4-aminophenyl)-indan (6-TMDM), 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene (BisAM), 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene (BisAP), 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl (BODA), 1,1-Bis[4-(4-aminophenoxy)phenyl]cyclohexane, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 1,4-Bis(3-aminophenoxy)benzene, 1,4-Bis(4-aminophenoxy)benzene, 1,3-Bis(3-aminophenoxy)benzene, 1,3-Bis(4-aminophenoxy)benzene, Bis[4-(3-aminophenoxy)phenyl]ketone, Bis[4-(4-aminophenoxy)phenyl]ketone, Bis[4- Examples include (3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl] ether, bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] sulfone, bis[4-(4-aminophenoxy)phenyl] sulfone, 4,4-diaminobenzanilide, 4-aminobenzoic acid-4-aminophenyl, 3,4-diaminobenzanilide, etc. Examples of alicyclic diamines include 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, isophoronediamine, bis(aminomethyl)norbornane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, and 2,2-bis(4-aminocyclohexyl)propane. Examples of aliphatic diamines include ethylenediamine and hexamethylenediamine. In this specification, aromatic diamine means a diamine containing one or more aromatic rings, alicyclic diamine means a diamine containing one or more alicyclic rings but not aromatic rings, and aliphatic diamine means a diamine that does not contain either aromatic or alicyclic rings. The constituent units other than constituent units (B1) and (B2) that are optionally included in constituent unit B may be one type or two or more types. ,

[0033] <Method for Producing Polyimide Resin Precursor (X)> The polyimide resin precursor (X) may be produced by any method, but it is preferably produced by the following production method. The polyimide resin precursor (X) is produced by a method of reacting a tetracarboxylic acid component and a diamine component to obtain a polyimide resin precursor having a polyamic acid structure. Among these, it is preferable to use a compound that provides the above structural unit A as the tetracarboxylic acid component and a compound that provides the above structural unit B as the diamine component. More specifically, a preferable method for producing the polyimide resin precursor (X) is to react a tetracarboxylic acid component containing at least one selected from the group consisting of the compound represented by formula (a1), the compound represented by formula (a2), the compound represented by formula (a3), and the compound represented by formula (a4) with a diamine component containing at least one selected from the group consisting of the compound represented by formula (b1) and the compound represented by formula (b2) to obtain a polyimide resin precursor having a polyamic acid structure.

[0034] The molar ratio (diamine / tetracarboxylic acid) of the amount of the diamine component to the amount of the tetracarboxylic acid component used in the reaction is preferably 0.70 or more, more preferably 0.75 or more, still more preferably 0.80 or more, even more preferably 0.85 or more, even more preferably 0.88 or more, and even more preferably 0.90 or more. Also, it is preferably 0.70 to 1.00, more preferably 0.70 to 0.95, still more preferably 0.75 to 0.95, even more preferably 0.80 to 0.95, even more preferably 0.85 to 0.95, even more preferably 0.88 to 0.95, and even more preferably 0.90 to 0.95. By setting the molar ratio within the above range, the stability of the polyimide resin precursor composition can be particularly improved. Also, the film-forming property can be improved, and the heat resistance and adhesion of the obtained polyimide film can be improved.

[0035] There are no particular restrictions on the method of reacting the tetracarboxylic acid component with the diamine component in this manufacturing method, and known methods can be used. As a specific reaction method, a method in which a tetracarboxylic acid component, a diamine component, a solvent, and, if necessary, a terminal blocking agent are charged into a reactor and stirred at preferably 0 to 120°C, more preferably 5 to 80°C for 1 to 72 hours can be mentioned. Since the molecular weight of the polyimide resin precursor does not vary depending on the temperature history during polymerization and the progress of thermal imidization can also be suppressed, it is more preferable to react at 80°C or lower because a polyimide resin precursor having a polyamic acid structure can be stably produced.

[0036] By the above method, a solution in which a polyimide resin precursor having a polyamic acid structure is dissolved in a solvent is obtained. The concentration of the polyimide resin precursor in the resulting solution is preferably 1 to 50% by mass, more preferably 3 to 35% by mass, and still more preferably 5 to 30% by mass. Next, the raw materials and the like used in this manufacturing method will be described.

[0037] (Tetracarboxylic acid component) The tetracarboxylic acid component used as a raw material in this manufacturing method is preferably the tetracarboxylic dianhydride described in the section of (Structural unit A), and the preferred tetracarboxylic dianhydrides are the same as those described in the section of (Structural unit A). In addition, the tetracarboxylic dianhydride used as the tetracarboxylic acid component in this manufacturing method may be in any form of dianhydride, tetracarboxylic acid (free acid), or alkyl ester of tetracarboxylic acid, but dianhydride is preferred.

[0038] The tetracarboxylic acid component used as a raw material in this manufacturing method preferably contains at least one selected from the group consisting of the compound represented by the above formula (a1) (the compound that gives the structural unit (A1)), the compound represented by the above formula (a2) (the compound that gives the structural unit (A2)), the compound represented by the above formula (a3) (the compound that gives the structural unit (A3)), and the compound represented by the above formula (a4) (the compound that gives the structural unit (A4)).

[0039] The ratio of the compound represented by formula (a1) in the tetracarboxylic acid component is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and the tetracarboxylic acid component may consist only of the compound represented by formula (a1). By having the ratio of the compound represented by formula (a1) within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0040] The ratio of the compound represented by formula (a3) ​​in the tetracarboxylic acid component is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and the tetracarboxylic acid component may consist only of the compound represented by formula (a3). By having the ratio of the compound represented by formula (a3) ​​within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0041] The ratio of the compound represented by formula (a4) in the tetracarboxylic acid component is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and the tetracarboxylic acid component may consist only of the compound represented by formula (a4). By having the ratio of the compound represented by formula (a4) within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0042] The tetracarboxylic acid component may contain two or more compounds from among the compounds represented by formula (a1), formula (a2), formula (a3), and formula (a4). In particular, it is preferable to contain the compound represented by formula (a1) and one or more of the compounds represented by formula (a2), formula (a3), and formula (a4). The molar ratio of the compound represented by formula (a1) and the compounds represented by formula (a2), formula (a3), and formula (a4) in the tetracarboxylic acid component [(a1) / ((a2)+(a3)+(a4))] is preferably 30 / 70 to 100 / 0, more preferably 40 / 60 to 100 / 0, and especially from the viewpoint of heat resistance, even more preferably 40 / 60 to 90 / 10, even more preferably 40 / 60 to 80 / 20, and even more preferably 40 / 60 to 60 / 40. When the total molar ratio of the compound represented by formula (a1) to the compounds represented by formula (a2), formula (a3), and formula (a4) is 100 / 0, the tetracarboxylic acid component does not contain the compounds represented by formula (a2), formula (a3), and formula (a4).

[0043] The molar ratio [(a1) / (a2)] of the compound represented by formula (a1) to the compound represented by formula (a2) in the tetracarboxylic acid component is preferably 30 / 70 to 100 / 0, more preferably 40 / 60 to 100 / 0, and especially from the viewpoint of heat resistance, even more preferably 40 / 60 to 90 / 10, even more preferably 40 / 60 to 80 / 20, and even more preferably 40 / 60 to 60 / 40. When the molar ratio of the compound represented by formula (a1) to the compound represented by formula (a2) is 100 / 0, the tetracarboxylic acid component does not contain the compound represented by formula (a2). By having the compounds constituting the tetracarboxylic acid component in the above molar ratio, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and in particular the heat resistance and adhesion of the resulting polyimide film can be enhanced.

[0044] The tetracarboxylic acid component may include compounds other than the compound represented by formula (a1), the compound represented by formula (a2), the compound represented by formula (a3), and the compound represented by formula (a4) (dianhydrides). Such tetracarboxylic acid dianhydrides are not particularly limited, but include aromatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aliphatic tetracarboxylic acid dianhydrides, excluding the compound represented by formula (a1), the compound represented by formula (a2), the compound represented by formula (a3), and the compound represented by formula (a4). When tetracarboxylic acid component A includes compounds other than the compound represented by formula (a1), the compound represented by formula (a2), the compound represented by formula (a3), and the compound represented by formula (a4), it is preferable to include aromatic tetracarboxylic acid dianhydrides among the tetracarboxylic acid dianhydrides, excluding the compound represented by formula (a1), the compound represented by formula (a2), the compound represented by formula (a3), and the compound represented by formula (a4). Specific examples of preferred tetracarboxylic acid dianhydrides are the same as those described in the section on (constituent unit A) above. These tetracarboxylic dianhydrides may be used individually or in combination of two or more types.

[0045] (Diamine component) The diamine component used as a raw material in this manufacturing method is preferably the diamine described in the (Constituent unit B) section above, and the preferred diamine component is the same as that described in the (Constituent unit B) section above. The diamine used as a diamine component in this manufacturing method may be in the form of a diamine or a diisocyanate corresponding to a diamine, but it is preferably a diamine. The diamine component used as a raw material in this manufacturing method includes at least one selected from the group consisting of a compound represented by formula (b1) (a compound that gives constituent unit (B1)) and a compound represented by formula (b2) (a compound that gives constituent unit (B2)).

[0046] The ratio of the compound represented by formula (b1) in the diamine component is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and the diamine component may consist only of the compound represented by formula (b1). By having the ratio of the compound represented by formula (b1) within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0047] The ratio of the compound represented by formula (b2) in the diamine component is preferably 30 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, and may even be 100 mol%, and the diamine component may consist only of the compound represented by formula (b2). By having the ratio of the compound represented by formula (b2) within the above range, the stability and film-forming properties of the polyimide resin precursor composition can be improved, and the heat resistance and adhesion of the resulting polyimide film can be improved.

[0048] The diamine component may include diamine components other than the compound represented by formula (b1) and the compound represented by formula (b2). While not particularly limited, examples of diamines that provide such a structural unit include aromatic diamines, alicyclic diamines, and aliphatic diamines, excluding the compound represented by formula (b1) and the compound represented by formula (b2). Specific examples of preferred diamines are the same as those described in the section on (structural unit B). One type of diamine may be used, or two or more types may be used.

[0049] (End-Sealing Agent) In addition to the tetracarboxylic acid component and diamine component mentioned above, an end-sealing agent may also be used in the production of the polyimide resin precursor (X). Monoamines or dicarboxylic acids are preferred as the end-sealing agent, with dicarboxylic acids being more preferred. The amount of end-sealing agent to be introduced is preferably 0.0001 to 0.2 moles, more preferably 0.0001 to 0.1 moles, even more preferably 0.001 to 0.06 moles, and even more preferably 0.01 to 0.06 moles per mole of the diamine component. Examples of monoamine end-captives include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, o-aminophenol (2-aminophenol), m-aminophenol (3-aminophenol), p-aminophenol (4-aminophenol), o-aminobenzoic acid, m-aminobenzoic acid, and p-aminobenzoic acid. Of these, benzylamine, aniline, and p-aminophenol (4-aminophenol) are preferred, and p-aminophenol (4-aminophenol) is more preferred. Dicarboxylic acid end-captives are preferred, and some of them may be ring-closed. Examples include phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, and 4-cyclohexene-1,2-dicarboxylic acid. Of these, phthalic acid and phthalic anhydride are more preferred.

[0050] (Solvent (reaction solvent)) The solvent (reaction solvent) used in the production of the polyimide resin precursor may be any solvent capable of dissolving the resulting polyimide resin precursor, but preferably, the solvent contained in the polyimide resin precursor composition described later is used. Using the solvent contained in the polyimide resin precursor composition as the reaction solvent is convenient and preferable because the polyimide resin precursor solution itself after the production of the polyimide resin precursor, or the polyimide resin precursor composition itself, can be used simply by adding the solvent to adjust the concentration.

[0051] Examples of solvents (reaction solvents) include amide solvents, lactone solvents, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents, phenol solvents, ether solvents, and carbonate solvents. Ether solvents, amide solvents, or lactone solvents are preferred, and lactone solvents are more preferred.

[0052] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. At least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone and N-methyl-2-pyrrolidone is preferred, and 1,3-dimethyl-2-imidazolidinone is more preferred.

[0053] Examples of lactone-based solvents include γ-butyrolactone and γ-valerolactone, with γ-butyrolactone being preferred. Examples of phosphorus-containing amide-based solvents include hexamethylphosphoric amide and hexamethylphosphinetriamide. Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane. Examples of ketone-based solvents include acetone, methyl ethyl ketone, cyclohexanone, methylcyclohexanone, and cyclopentanone. Examples of ester-based solvents include acetic acid (2-methoxy-1-methylethyl).

[0054] Examples of phenolic solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol. Examples of etheric solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl] ether, tetrahydrofuran, 1,4-dioxane, and propylene glycol monomethyl ether, with propylene glycol monomethyl ether being preferred. Examples of carbonateic solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.

[0055] From the above, the solvent preferably contains at least one selected from the group consisting of propylene glycol monomethyl ether, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and γ-butyrolactone; more preferably contains at least one selected from the group consisting of propylene glycol monomethyl ether, 1,3-dimethyl-2-imidazolidinone, and γ-butyrolactone; even more preferably contains at least one selected from the group consisting of propylene glycol monomethyl ether and γ-butyrolactone; and even more preferably contains γ-butyrolactone. The above solvents may be used alone or in mixtures of two or more.

[0056] <Compound (Y)> The polyimide resin precursor composition of the present invention comprises a compound (Y) having an amide acid structure and three or more oxysilyl groups. A more preferred polyimide resin precursor composition of the present invention comprises a compound (Y) having three to five amide acid structures and three or more oxysilyl groups. Hereinafter, both "a compound (Y) having an amide acid structure and three or more oxysilyl groups" and "a compound (Y) having three to five amide acid structures and three or more oxysilyl groups" will be simply referred to as "compound (Y)". The compound (Y) is a compound having an amide acid structure and three or more oxysilyl groups or a compound having three to five amide acid structures and three or more oxysilyl groups, but it is preferably one of the compounds shown below.

[0057] The oxysilyl group of compound (Y) is preferably at least one selected from the group consisting of a hydrocarbyloxysilyl group and a silanol group, more preferably a hydrocarbyloxysilyl group, and even more preferably an alkoxysilyl group. The number of oxysilyl groups of compound (Y) is three or more, preferably three to five, more preferably three to four, and even more preferably three. It is believed that by compound (Y) being a compound (Y) having an amide acid structure and three or more oxysilyl groups, and furthermore the number of oxysilyl groups of compound (Y) being within the above range, a polyimide resin precursor composition can be obtained that does not undergo excessive reactions during storage, has excellent stability, and also has excellent adhesion. In addition, it is believed that the resulting polyimide film has excellent heat resistance.

[0058] The number of amide acid structures in compound (Y) is preferably three or more, more preferably three to five, even more preferably three to four, and even more preferably three. The number of amide acid structures in compound (Y) is preferably the same as the number of alkoxysilyl groups in compound (Y). The amide acid structures are preferably the bonding portions of the oxysilyl groups.

[0059] The compound (Y) is more preferably a compound represented by the following general formula (y1). (wherein, A 1 is a trivalent or tetravalent hydrocarbon group, B 1 is a single bond or a divalent hydrocarbon group which may have an ether group, a carbonyl group, an ester group, an amide group or a thiol group as a bonding moiety, C 1 is a single bond or a divalent hydrocarbon group which may have an ether group, a carbonyl group, an ester group, an amide group or a thiol group as a bonding moiety, R is each independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms, and n is 3 or 4.)

[0060] In formula (y1), A 1 is a trivalent or tetravalent hydrocarbon group, preferably a trivalent or tetravalent hydrocarbon group having 6 to 12 carbon atoms, more preferably a trivalent or tetravalent hydrocarbon group having 6 to 10 carbon atoms, still more preferably a trivalent or tetravalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a trivalent or tetravalent aromatic hydrocarbon group having 6 carbon atoms. B 1 is a single bond or a divalent hydrocarbon group which may have an ether group, a carbonyl group, an ester group, an amide group or a thiol group as a bonding moiety, preferably a divalent hydrocarbon group having an ether group. C 1is a single bond, or a divalent hydrocarbon group which may have an ether group, carbonyl group, ester group, amide group, or thiol group as a bond, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and even more preferably a divalent hydrocarbon group having 3 carbon atoms. R is independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, even more preferably a hydrocarbon group having 1 to 3 carbon atoms, even more preferably a hydrocarbon group having 1 or 2 carbon atoms (methyl group or ethyl group), and even more preferably a hydrocarbon group having 1 carbon atom (methyl group). n is 3 or 4, preferably 3. It is believed that by compound (Y) being a compound represented by formula (y1), and furthermore the structure of each part being within the above range, a polyimide resin precursor composition can be obtained that does not undergo excessive reactions during storage, has excellent stability, and also has excellent adhesion. Furthermore, the resulting polyimide film is expected to have excellent heat resistance.

[0061] The compound (Y) is more preferably a compound represented by the following general formula (y11). (In the formula, R is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms, and n is 3 or 4.) R is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, even more preferably a hydrocarbon group having 1 to 3 carbon atoms, even more preferably a hydrocarbon group having 1 or 2 carbon atoms (methyl group or ethyl group), and even more preferably a hydrocarbon group having 1 carbon atom (methyl group). n is 3 or 4, preferably 3. It is believed that by compound (Y) being a compound represented by formula (y11), and furthermore the structure of each part being within the above range, a polyimide resin precursor composition can be obtained that does not undergo excessive reactions during storage, has excellent stability, and also has excellent adhesion. Furthermore, it is believed that the resulting polyimide film has excellent heat resistance.

[0062] The compound (Y) may be any compound obtained by any method, as long as it is a compound having an amidic acid structure and three or more oxysilyl groups, or a compound having three to five amidic acid structures and three or more oxysilyl groups. Preferably, it is a compound obtained by the reaction of an amine compound with a compound having a carboxyl group and an oxysilyl group. More preferably, the compound (Y) is a compound obtained by the reaction of an amine compound with a compound having a carboxyl group and an oxysilyl group, wherein the amine compound is a compound represented by the following formula (d1). (In the formula, M is independently selected from the group consisting of an ether group, a carbonyl group, an ester group, an amide group, and a thiol group.) M is independently selected from the group consisting of an ether group, a carbonyl group, an ester group, an amide group, and a thiol group, and is preferably an ether group. Furthermore, M may be bonded to any position on the central benzene ring, but it is preferably bonded to the 1st, 3rd, or 5th position. In addition, three NH ２ The amino group may be attached to M at the ortho, meta, or para position, but it is preferable that it is attached at the para position.

[0063] Therefore, the amine compound is more preferably a compound represented by the following formula (d11).

[0064] There are no particular restrictions on the method of reacting an amine compound with a compound having a carboxyl group and an oxysilyl group, but the following method is preferred. A specific reaction method involves dissolving the amine compound in a solvent, adding dropwise a solution of the compound having a carboxyl group and an oxysilyl group, or a solution of the compound having a carboxyl group and an oxysilyl group dissolved in a solvent, and stirring.

[0065] The solvent is not particularly limited as long as it dissolves the amine compound, the compound having a carboxyl group and an oxysilyl group, and the product compound (Y). However, since the polyimide resin precursor composition can be obtained by directly mixing the solution of compound (Y) obtained after the above reaction with the polyimide resin precursor, it is preferable that the solvent is one of those contained in the polyimide resin precursor composition described later. Specifically, examples include amide solvents, lactone solvents, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents, phenol solvents, ether solvents, carbonate solvents, etc., with ether solvents, amide solvents, or lactone solvents being preferred, and lactone solvents being more preferred. Among these, it is preferable that the solvent be at least one selected from the group consisting of propylene glycol monomethyl ether, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and γ-butyrolactone.

[0066] The reaction temperature is preferably -20 to 30°C, more preferably 0 to 20°C. Since this reaction is exothermic, it is preferable to cool the reaction solution during the reaction to bring its temperature within the above range. The reaction time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 3 hours. The reaction time may be appropriately adjusted depending on the reaction temperature and scale. By the above method, a solution in which compound (Y) is dissolved in the solvent is obtained. The concentration of compound (Y) in the obtained solution is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass.

[0067] The content of compound (Y) in the polyimide resin precursor composition of the present invention is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass. By having a compound (Y) content within the above range, the resulting polyimide resin precursor composition exhibits excellent stability and film-forming properties, and a polyimide film with excellent heat resistance and adhesion can be obtained.

[0068] The mass ratio [(X) / (Y)] of the polyimide resin precursor (X) having an amide acid structure to the compound (Y) is preferably 20 / 80 to 90 / 10, more preferably 30 / 70 to 90 / 10, even more preferably 35 / 65 to 80 / 20, even more preferably 35 / 65 to 75 / 25, even more preferably 35 / 65 to 70 / 30, even more preferably 35 / 65 to 60 / 40, even more preferably 35 / 65 to 55 / 45, even more preferably 40 / 60 to 55 / 45, and even more preferably 45 / 55 to 55 / 45. By having the mass ratio [(X) / (Y)] within the above range, the resulting polyimide resin precursor composition exhibits excellent stability and film-forming properties, and a polyimide film with excellent heat resistance and adhesion can be obtained.

[0069] <Solvent> The polyimide resin precursor composition of the present invention further contains a solvent. The inclusion of a solvent in the polyimide resin precursor composition facilitates application to a substrate and improves adhesion and film-forming properties. Preferably, the solvent contained in the polyimide resin precursor composition contains the solvent (reaction solvent) used in the production of the polyimide resin precursor described above. By using the reaction solvent as part or all of the solvent contained in the polyimide resin precursor composition, the polyimide resin precursor solution itself after the production of the polyimide resin precursor can be used, or the polyimide resin precursor composition can be used simply by adding a solvent to adjust the concentration, which is convenient and preferable.

[0070] Solvents included in the polyimide resin precursor composition include amide solvents, lactone solvents, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents, phenol solvents, ether solvents, and carbonate solvents. Ether solvents, amide solvents, or lactone solvents are preferred, and lactone solvents are more preferred.

[0071] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. At least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone and N-methyl-2-pyrrolidone is preferred, and 1,3-dimethyl-2-imidazolidinone is more preferred.

[0072] Examples of lactone-based solvents include γ-butyrolactone and γ-valerolactone, with γ-butyrolactone being preferred. Examples of phosphorus-containing amide-based solvents include hexamethylphosphoric amide and hexamethylphosphinetriamide. Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane. Examples of ketone-based solvents include acetone, methyl ethyl ketone, cyclohexanone, methylcyclohexanone, and cyclopentanone. Examples of ester-based solvents include acetic acid (2-methoxy-1-methylethyl).

[0073] Examples of phenolic solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol. Examples of etheric solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl] ether, tetrahydrofuran, 1,4-dioxane, and propylene glycol monomethyl ether, with propylene glycol monomethyl ether being preferred. Examples of carbonateic solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.

[0074] From the above, the solvent preferably contains at least one selected from the group consisting of propylene glycol monomethyl ether, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and γ-butyrolactone; more preferably contains at least one selected from the group consisting of propylene glycol monomethyl ether, 1,3-dimethyl-2-imidazolidinone, and γ-butyrolactone; even more preferably contains at least one selected from the group consisting of propylene glycol monomethyl ether and γ-butyrolactone; and even more preferably contains γ-butyrolactone. The above solvents may be used alone or in mixtures of two or more.

[0075] The polyimide resin precursor composition of the present invention may be the polyimide resin precursor solution itself after the production of the polyimide resin precursor, or it may be a solution of the polyimide resin precursor solution that has been further diluted by mixing in a solvent.

[0076] The solvent content in the polyimide resin precursor composition of the present invention is preferably 20 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 70% by mass. By having the solvent content within this range, the resulting polyimide resin precursor composition exhibits excellent stability and film-forming properties.

[0077] <Other Components> In addition to the polyimide resin precursor (X), compound (Y), and solvent, the polyimide resin precursor composition of the present invention may contain other components, to the extent that they do not impair the required properties of the resulting polyimide film and polyimide resin precursor composition. Examples of other components include imidation catalysts, dehydration catalysts, inorganic fillers, adhesion promoters, release agents, flame retardants, UV stabilizers, surfactants, leveling agents, defoaming agents, fluorescent whitening agents, crosslinking agents, polymerization initiators, and photosensitive agents.

[0078] Imidation catalysts and dehydration catalysts can be included from the viewpoint of efficiently promoting the imidation of the polyamic acid portion of the polyimide resin precursor. As the imidation catalyst, an imidation catalyst with a boiling point of 40°C or higher is preferred. An imidation catalyst with a boiling point of 40°C or higher allows for sufficient imidation before volatilization. Examples of imidation catalysts include amine compounds such as pyridine and picoline; imidazole compounds such as imidazole, 1,2-dimethylimidazole, 1-benzylimidazole, 1-benzyl-2-methylimidazole, and benzimidazole; and the like. These imidation catalysts may be used individually or in combination of two or more. Examples of dehydration catalysts include acid anhydrides such as acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride; and carbodiimide compounds such as dicyclohexylcarbodiimide. These may be used individually or in combination of two or more.

[0079] Since the polyimide resin precursor contained in the polyimide resin precursor composition of the present invention is solvent-soluble, a high-concentration polyimide resin precursor composition can be obtained that is stable at room temperature. The viscosity of the polyimide resin precursor composition is preferably 0.1 to 100 Pa·s, and more preferably 0.1 to 20 Pa·s. The viscosity of the polyimide resin precursor composition is the value measured at 25°C using an E-type viscometer. The method for producing the polyimide resin precursor composition of the present invention is not particularly limited, and known methods can be applied. For example, it can be obtained by adding compound (Y) or a solution of compound (Y) to a solution of the polyimide resin precursor obtained by the above-described production method, and further mixing in additional solvents as needed to adjust the concentration.

[0080] [Polyimide Film] The polyimide film of the present invention is preferably manufactured using the polyimide resin precursor composition described above. The polyimide film of the present invention is obtained by imidizing the polyimide resin precursor (X) described above.

[0081] There are no particular limitations on the method for producing a polyimide film using the polyimide resin precursor composition of the present invention, and known methods can be used. However, it is preferable to obtain the film by coating the polyimide resin precursor composition onto a support and heating it. That is, the polyimide film of the present invention is preferably a polyimide film obtained by coating the polyimide resin precursor composition onto a support and heating it.

[0082] For example, the polyimide resin precursor composition of the present invention can be applied to a smooth support such as a glass plate, metal plate, or plastic, or formed into a film. Then, organic solvents such as reaction solvents and diluents contained in the polyimide resin precursor composition can be removed by heating to obtain a polyamic acid film. The polyamic acid in the polyamic acid film can then be imidized (dehydrated and cyclized) by heating to produce a polyimide film. The polyimide film of the present invention can be suitably used as an insulating film in the semiconductor field. Therefore, silicon, silicon nitride, silicon oxide, etc., are preferred as the support, with silicon being more preferred. When used in applications such as the semiconductor field, it is preferable to use it as a laminate together with the support in the product. When used in applications where only the polyimide film is used or where the polyimide film is used as a substrate, it is preferable to peel it from the support to obtain the polyimide film.

[0083] The heating temperature when drying the polyimide resin precursor composition to obtain a polyimide resin precursor (polyamic acid) film is preferably 50 to 150°C. The heating temperature when imidizing the polyimide resin precursor by heating is preferably 300 to 420°C, more preferably 330 to 400°C. The heating time is preferably 1 minute to 6 hours, more preferably 10 minutes to 4 hours, and even more preferably 30 minutes to 3 hours. By using these temperatures and times, the physical properties of the resulting polyimide film will be good. Examples of heating atmospheres include air, nitrogen gas, oxygen gas, hydrogen gas, and nitrogen / hydrogen mixed gas. However, in order to suppress discoloration of the resulting polyimide resin, nitrogen gas with an oxygen concentration of 100 ppm or less, and nitrogen / hydrogen mixed gas containing hydrogen at a concentration of 0.5% or less are preferred. Note that the imidization method is not limited to thermal imidization, and chemical imidization can also be applied.

[0084] The thickness of the polyimide film of the present invention can be appropriately selected depending on the application, but is preferably 0.1 μm or more, more preferably 1 μm or more, even more preferably 5 μm or more, even more preferably 7 μm or more, and even more preferably 10 μm or more. Also, is preferably 250 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and even more preferably 40 μm or less. A thickness within the above range makes it possible to use it practically as an insulating film. The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the polyimide resin precursor composition.

[0085] The preferred physical properties of the polyimide film of the present invention are as follows. By satisfying the following physical properties, the polyimide film of the present invention exhibits excellent heat resistance. The glass transition temperature (Tg) is preferably 300°C or higher, more preferably 330°C or higher, even more preferably 350°C or higher, and even more preferably 400°C or higher.

[0086] The temperature at which the 1% weight loss occurs is preferably 430°C or higher, more preferably 440°C or higher, even more preferably 450°C or higher, and even more preferably 460°C or higher.

[0087] The weight loss rate when stored at 350°C for 3 hours is preferably 1.0% or less, more preferably 0.7% or less, even more preferably 0.6% or less, and even more preferably 0.4% or less. Specifically, the glass transition temperature, the 1% weight loss temperature, and the weight loss rate when stored at 350°C for 3 hours in this invention can be measured by the method described in the examples.

[0088] Because the polyimide film of the present invention possesses the excellent properties described above, it can be used in various applications, but it is particularly suitable as a film for various components of semiconductor parts. In particular, it is suitable as an insulating film for semiconductors.

[0089] The present invention will be specifically described below with reference to examples. However, the present invention is not limited in any way by these examples.

[0090] [Evaluation of Polyimide Resin Precursor Compositions and Polyimide Films] (1) Stability of Polyimide Resin Precursor Compositions Approximately 30 mL of the polyimide resin precursor composition obtained in the examples and comparative examples was placed in a 50 mL wide-mouth polypropylene bottle, the lid was closed, and the bottle was left standing at 23°C for one week. The stability was evaluated visually according to the following criteria. Those that maintained fluidity after one week had excellent stability. (Evaluation Criteria) ○: Fluid. ×: Not fluid.

[0091] (2) Film-forming properties of the polyimide resin precursor composition After drying, the polyimide resin precursor composition obtained in the examples and comparative examples was applied to a 4-inch silicon wafer by spin coating so that the thickness after drying was 30 μmt. Then, it was dried on a hot plate at 100°C for 10 minutes, and then heated in a hot air dryer under a nitrogen atmosphere at a heating rate of 5°C / min to 350°C, and heated at 350°C for 120 minutes to evaporate the solvent and further thermal imide formation, thereby forming a polyimide film (polyimide film) on the silicon wafer. Film-forming properties were evaluated visually according to the following criteria. Polyimide films without cracks or roughness have excellent film-forming properties. (Evaluation criteria) ○: No cracks or roughness. ×: Cracks or roughness are present.

[0092] (3) A cross-cut adhesion test was performed on the polyimide film to evaluate its adhesion. A 30 μm thick polyimide film was deposited on a 4-inch silicon wafer in the same manner as in the evaluation of film formation described above. Using a cutter guide and a cutter knife, 10 x 10 (100 squares (1 mm x 1 mm square size)) cuts were made in the polyimide film, reaching the silicon wafer layer. Tape (Sellotape®, CT-24, manufactured by Nichiban Co., Ltd.) was applied flat to the grid (cross-cut) area, extending 20 mm beyond the grid, ensuring that no air bubbles were trapped. The applied tape was peeled off within 0.5 to 1 second, the state of the grid was observed, and the number of squares that remained intact was counted. A higher number of remaining squares indicates higher adhesion. The evaluation criteria were as follows. (Evaluation Criteria) ◎: 90 or more squares remaining out of 100 squares 〇: 80 to 89 squares remaining out of 100 squares △: 70 to 79 squares remaining out of 100 squares ×: 69 or fewer squares remaining out of 100 squares

[0093] (4) Glass transition temperature (Tg) (Examples 1-24) Using a thermomechanical analyzer (TMA 7100C, Hitachi High-Tech Science Co., Ltd.), TMA measurements were performed on a sample of 4 mm x 20 mm in tensile mode, with a load of 50 mN and a heating rate of 10°C / min, heating from 40°C to 400°C. The point where an inflection point was observed was extrapolated to determine the glass transition temperature (Tg). A higher glass transition temperature (Tg) indicates superior heat resistance. In Table 1, samples with no inflection point up to 400°C and a glass transition temperature exceeding 400°C are indicated as ">400°C".

[0094] (5) Glass transition temperature (Tg) (Comparative Example 1) Using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., product name "DSC7000X"), 10 mg of the sample was packed tightly into the bottom of an aluminum measuring container, an aluminum lid was placed over it, and the temperature was raised from 40°C to 240°C at a heating rate of 10°C / min under conditions of a nitrogen gas flow of 100 mL / min. Next, the sample was cooled to 40°C at a cooling rate of 40°C / min, and then the temperature was raised again to 260°C at a heating rate of 10°C / min to obtain a DSC curve. The intersection of the baseline and the tangent at the inflection point (the point where an upward-convex curve changes to a downward-convex curve) in the DSC curve observed during the second heating process was defined as the glass transition temperature (Tg).

[0095] (6) 1% weight loss temperature (Td1%) A differential thermogravimetric analyzer ("NEXTA STA200RV", manufactured by Hitachi High-Tech Science Corporation) was used. The sample was heated from 40°C to 150°C at a heating rate of 10°C / min, held at 150°C for 30 minutes to remove moisture, and then heated to 480°C. The temperature at which the weight decreased by 1% compared to the weight after holding at 150°C for 30 minutes was defined as the 1% weight loss temperature. A higher value for the weight loss temperature indicates better heat resistance.

[0096] (7) Weight loss rate (350°C, 3 hours) A differential thermogravimetric analyzer ("NEXTA STA200RV", manufactured by Hitachi High-Tech Science Corporation) was used. The sample was heated from 40°C to 150°C at a heating rate of 10°C / min, held at 150°C for 30 minutes to remove moisture, and then heated to 350°C. The weight at 350°C was used as the baseline, and the weight loss rate was defined as the percentage of weight lost during the 180 minutes held at 350°C. A smaller weight loss rate indicates better heat resistance.

[0097] The raw materials used in the manufacturing example are as follows: <Tetracarboxylic acid components> ODPA: 4,4'-oxydiphthalic anhydride (compound represented by formula (a1), manufactured by Manac Co., Ltd.) PMDA: pyromellitic anhydride (compound represented by formula (a2), manufactured by Tokyo Chemical Industry Co., Ltd.) BPAF: 9,9-bis(3,4-dicarboxyphenyl)fluorendioanhydride (compound represented by formula (a31), manufactured by JFE Chemical Corporation) SFDA: spiro[11H-difluoro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetron (compound represented by formula (a4), manufactured by Air Water Performance Chemical Co., Ltd.) <Diamine components> ODA: 4,4'-diaminodiphenyl ether (compound represented by formula (b1), manufactured by Tokyo Chemical Industry Co., Ltd.) BPF-AN: 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene (compound represented by formula (b22), manufactured by JFE Chemical Corporation) <Amine compound> TAPOB: 1,3,5-tris(4-aminophenoxy)benzene (manufactured by Seika Co., Ltd.) <Compound having a carboxyl group and an oxysilyl group> X-12-967C: 3-trimethoxysilylpropyl succinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd.) <Solvent> GBL: γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) PGME: 1-methoxy-2-propanol (propylene glycol monomethyl ether) (manufactured by Kanto Chemical Co., Ltd.)

[0098] [Production of Polyimide Resin Precursors] Production Example 1 A 300 mL five-necked round-bottom flask equipped with a stainless steel crescent-shaped stirring blade, nitrogen inlet tube, condenser, thermometer, and glass end cap contained 18.422 g (0.092 mol) of ODA and 73.458 g of GBL. The mixture was stirred at 200 rpm under a nitrogen atmosphere at a system temperature of 60°C to obtain a solution. To this solution, 31.021 g (0.100 mol) of ODPA and 18.365 g of GBL were added all at once. The mixture was stirred for 1 hour while maintaining the temperature at 60°C with a mantle heater to obtain a polyimide resin precursor (polyamic acid) solution PAA-1 with a solid content of 35% by mass.

[0099] Production Examples 2-13 A polyimide resin precursor (polyamic acid) solution was obtained in the same manner as in Production Example 1, except that the tetracarboxylic acid component and the diamine component were changed as shown in Table 1.

[0100] [Preparation of Compounds Having an Amido Acid Structure and Three Alkoxysilyl Groups (Compounds Having an Amido Acid Structure and Three or More Oxysilyl Groups)] Preparation Example 14 In a 300 mL five-necked round-bottom flask equipped with a stainless steel crescent-shaped stirring blade, nitrogen inlet tube, exhaust tube, thermometer, and glass end cap, 40.025 g (0.100 mol) of TAPOB and 94.915 g of PGME were added and stirred under a nitrogen atmosphere to obtain a solution. The solution was cooled with ice to bring the system temperature to 10°C or below, and then 78.699 g (0.300 mol) of X-12-967C and 18.365 g of PGME were added dropwise so that the system temperature did not exceed 20°C. The mixture was stirred for 1 hour while cooling with ice to obtain a solution Si-1 of a compound having an amido acid structure and three alkoxysilyl groups with a solid content of 50% by mass.

[0101]

[0102] [Production of Polyimide Resin Precursor Composition and Polyimide Film] Example 1 30,000 g of the polyimide resin precursor solution PAA-1 obtained in Production Example 1 (10,500 g of polyimide resin precursor (polyamic acid)) and 21,000 g of the solution Si-1 of the compound having an amidic acid structure and three alkoxysilyl groups obtained in Production Example 14 (10,500 g of the compound) were weighed into a 150 mL polyethylene container, purged with nitrogen, and then mixed using a rotation-revolution type mixer ("Awatori Rentaro Atmospheric Pressure Type ARE-310", manufactured by Thinky Co., Ltd.) at a stirring condition of 2,000 rpm for 3 minutes, and then at a defoaming condition of 2,200 rpm for 90 seconds to obtain a polyimide resin precursor composition. The evaluation results of the polyimide resin precursor composition are shown in Table 2. Next, the obtained polyimide resin precursor composition was applied to a support substrate (colored polyimide film-deposited glass) by spin coating. It was then heated on a hot plate at 80°C for 10 minutes and then at 250°C for 5 minutes. After that, it was heated in a hot air dryer under a nitrogen atmosphere at a heating rate of 5°C / min to 350°C, and heated at 350°C for 120 minutes to evaporate the solvent and obtain a polyimide film. The evaluation results of the polyimide film are shown in Table 2.

[0103] Examples 2 to 24 Polyimide resin precursor compositions and polyimide films were obtained in the same manner as in Example 1, except that the type of polyimide resin precursor and the mass ratio of the polyimide resin precursor to the compound having an amide acid structure and three alkoxysilyl groups were changed as shown in Tables 2 and 3. The evaluation results of the polyimide resin precursor compositions and polyimide films are shown in Tables 2 and 3.

[0104] Comparative Example 1: The polyimide resin precursor solution PAA-4 obtained in Production Example 4 was applied to a support substrate (colored polyimide film-deposited glass) by spin coating, held on a hot plate at 80°C for 10 minutes, and then heated in a hot air dryer under a nitrogen atmosphere at a heating rate of 5°C / min to 350°C, where it was heated for 120 minutes to evaporate the solvent. The resulting film showed cracks all over, and no polyimide film was obtained. Therefore, evaluation of the polyimide film other than the glass transition temperature was not performed. The evaluation results of the glass transition temperatures of the polyimide resin precursor composition and the polyimide film are shown in Table 3.

[0105]

[0106]

[0107] As shown in Tables 2 and 3, the polyimide resin precursor compositions of the examples exhibit good film-forming properties and adhesion due to the inclusion of a compound having an amide acid structure and three or more oxysilyl groups. Furthermore, despite containing a compound having an amide acid structure and three or more oxysilyl groups, fluidity is maintained, and stability is also good. Thus, the polyimide resin precursor compositions of the examples demonstrate that the resulting polyimide film can achieve both adhesion and stability. In addition, as shown in Tables 2 and 3, the polyimide films of the examples exhibit excellent heat resistance, as evidenced by their high glass transition temperature (Td1%) and low weight loss rate. From the above, it can be seen that the polyimide resin precursor compositions of the present invention can be used as raw materials for polyimide films that are excellent in stability and film-forming properties, as well as excellent in heat resistance and adhesion. Furthermore, it can be seen that the polyimide films of the present invention exhibit excellent heat resistance. Therefore, the polyimide resin precursor compositions and polyimide films of the present invention are useful as raw materials in the semiconductor field.

Claims

A polyimide resin precursor composition comprising a polyimide resin precursor (X) having an amidic acid structure and a compound (Y) having three to five amidic acid structures and three or more oxysilyl groups. 　 The polyimide resin precursor composition according to claim 1, wherein compound (Y) comprises compound (Y) having three to five oxysilyl groups. 　 The polyimide resin precursor composition according to claim 1 or 2, wherein the compound (Y) is a compound represented by the following general formula (y1). (In the formula, A 1 is a trivalent or tetravalent hydrocarbon group, B 1 C is a divalent hydrocarbon group which may have a single bond or an ether group, carbonyl group, ester group, amide group, or thiol group as a bond, 1 (where R is a single bond, or a divalent hydrocarbon group which may have an ether group, carbonyl group, ester group, amide group, or thiol group as a bond; R is independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms; and n is 3 or 4.) The polyimide resin precursor (X) has a constituent unit A derived from a tetracarboxylic dianhydride and a constituent unit B derived from a diamine, Constituent unit A includes at least one selected from the group consisting of constituent unit (A1) derived from a compound represented by the following formula (a1), constituent unit (A2) derived from a compound represented by the following formula (a2), constituent unit (A3) derived from a compound represented by the following formula (a3), and constituent unit (A4) derived from a compound represented by the following formula (a4). The polyimide resin precursor composition according to any one of claims 1 to 3, wherein the constituent unit B comprises at least one selected from the group consisting of a constituent unit (B1) derived from a compound represented by the following formula (b1) and a constituent unit (B2) derived from a compound represented by the following formula (b2). (In the formula, L is independently selected from the group consisting of an ether group, a carbonyl group, an ester group, an amide group, and a thiol group, and k is 0 or 1.) 　 The polyimide resin precursor composition according to claim 4, wherein the constituent unit (A3) comprises at least one selected from the group consisting of constituent units (A31) derived from a compound represented by the following formula (a31) and constituent units (A32) derived from a compound represented by the following formula (a32). The polyimide resin precursor composition according to claim 4 or 5, wherein the constituent unit (B2) comprises at least one selected from the group consisting of constituent units (B21) derived from a compound represented by the following formula (b21) and constituent units (B22) derived from a compound represented by the following formula (b22). The polyimide resin precursor composition according to any one of claims 1 to 6, wherein the compound (Y) is a compound represented by the following general formula (y11). (In the formula, R is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms, and n is 3 or 4.) 　 The polyimide resin precursor composition according to any one of claims 1 to 6, wherein the compound (Y) is a compound obtained by the reaction of an amine compound with a compound having a carboxyl group and an oxysilyl group, and the amine compound is a compound represented by the following formula (d1). (In the formula, M is at least one independently selected from the group consisting of ether groups, carbonyl groups, ester groups, amide groups, and thiol groups.) 　 The polyimide resin precursor composition according to claim 8, wherein the amine compound is a compound represented by the following formula (d11). A polyimide resin precursor composition according to any one of claims 1 to 9, further comprising a solvent. 　 A polyimide film obtained by coating a polyimide resin precursor composition according to any one of claims 1 to 10 onto a support and heating it.

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