Photosensitive polyimide resin composition, resin film, and electronic device

Abstract

A photosensitive polyimide resin composition comprising a cyclic polyimide resin (A) and a multifunctional radical polymerizable compound (B), wherein the cyclic polyimide resin (A) has the structure shown in formula (1), and the multifunctional radical polymerizable compound (B) has radical polymerizable functional groups and oxoalkylene groups, wherein the number of radical polymerizable functional groups in the multifunctional radical polymerizable compound (B) is 3 or more and 100 or less, and the total molar number of oxoalkylene groups added in the multifunctional radical polymerizable compound (B) is 5 or more and 100 or less.

Description

Technical Field

[0001] This invention relates to photosensitive polyimide resin compositions, resin films, and electronic devices. Background Technology

[0002] As an insulating film constituting electronic devices, resin films with excellent heat resistance and insulation properties, obtained by exposing a photosensitive polyimide resin composition, are widely used.

[0003] As a technology related to this photosensitive polyimide resin composition, examples of the technologies described in Patent Documents 1 and 2 can be cited.

[0004] Patent Document 1 discloses a photosensitive polyimide composition comprising a photosensitive polyimide obtained by reacting a first polyimide having a closed-ring imide structure with an isocyanate compound having a carbon-carbon double bond.

[0005] Patent Document 2 discloses a photosensitive resin composition comprising a polyimide having alkoxymethyl or hydroxymethyl groups, a polybenzoxazole, a polyamide-imide, a precursor of any of them or a copolymer thereof, and a compound having at least two alkoxymethyl or hydroxymethyl groups.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2000-147761

[0009] Patent Document 2: Japanese Patent Application Publication No. 2010-229210 Summary of the Invention

[0010] The problem the invention aims to solve

[0011] In recent years, the requirements for miniaturization and high performance of electronic devices have shown a gradual increasing trend, leading to the development of photosensitive resin compositions that can form resist layers with thicker film thicknesses.

[0012] Here, the research of the inventors has made it clear that there is still room for improvement in the flexibility of existing photosensitive polyimide resin compositions obtained using closed-loop polyimide resins when forming thick films.

[0013] The present invention was made in view of the above circumstances, and provides a photosensitive polyimide resin composition with an excellent balance between thick film heat resistance and thick film flexibility.

[0014] Solution for solving the problem

[0015] The inventors conducted repeated and in-depth research to solve the aforementioned problems. Their findings revealed that by combining a closed-ring polyimide resin (A) with a specific structure with a polyfunctional radical polymerizable compound (B) having 3 or more but less than 100 free radical polymerizable functional groups and a total addition molar number of oxyalkylene groups of 5 or more but less than 100, the balance between the thick-film heat resistance and thick-film flexibility of the photosensitive polyimide resin composition can be improved, thus completing this invention.

[0016] That is, according to the present invention, the photosensitive polyimide resin composition, resin film and electronic device shown below can be provided. [1]

[0018] A photosensitive polyimide resin composition comprising a cyclic-closed polyimide resin (A) and a multifunctional radical polymerizable compound (B), wherein the cyclic-closed polyimide resin (A) has the structure shown in formula (1), and the multifunctional radical polymerizable compound (B) has a radical polymerizable functional group and an oxoalkylene group.

[0019] The number of the aforementioned free radical polymerizable functional groups in the above-mentioned multifunctional free radical polymerizable compound (B) is more than 3 and less than 100.

[0020] The total molar number of the above-mentioned oxanediols in the above-mentioned multifunctional free radical polymerizable compound (B) is 5 or more and 100 or less.

[0021]

[0022] [In formula (1) above, R is a tetravalent group having a cyclic structure, an acyclic structure, or a combination of cyclic and acyclic structures with 4 to 10 carbon atoms. A is a divalent group having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and organosiloxane groups, and having 2 to 39 carbon atoms. The main chain of A may optionally contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S-. n represents the number of repeating units. The end of formula (1) above is any of the groups or hydrogen atoms shown in formula (2) or formula (3) below, and at least one end is a group shown in formula (2) or formula (3) below.]

[0023]

[0024] In equations (2) and (3) above, X and X 2 Each is an independent group having 2 or more but less than 15 carbon atoms, and may be selected from at least one group consisting of ester bonds and double bonds. Y and Y 2Each can be independently a hydrogen atom or a methyl group.

[0025] [2] According to the photosensitive polyimide resin composition described in [1] above, wherein the weight-average molecular weight of the closed-ring polyimide resin (A) is 5,000 or more and 70,000 or less.

[0026] [3] According to the photosensitive polyimide resin composition described in [1] or [2] above, when all the solid components of the photosensitive polyimide resin composition are set to 100% by mass, the content of the closed-ring polyimide resin (A) is 30% by mass or more.

[0027] [4] The photosensitive polyimide resin composition according to any one of [1] to [3] above, wherein when the amount of the closed-ring polyimide resin (A) contained in the photosensitive polyimide resin composition is set to 100 parts by mass, the content of the multifunctional free radical polymerizable compound (B) is 20 parts by mass or more and 100 parts by mass or less.

[0028] [5] The photosensitive polyimide resin composition according to any one of [1] to [4] above, wherein the free radical polymerizable functional group comprises (meth)acryloyl group.

[0029] [6] The photosensitive polyimide resin composition according to any one of [1] to [5] above, wherein the oxyalkylene group comprises at least one selected from oxyethylene and oxypropylene.

[0030] [7] The photosensitive polyimide resin composition according to any one of [1] to [6] above, wherein the number of free radical polymerizable functional groups in the above-mentioned multifunctional free radical polymerizable compound (B) is 6 or more.

[0031] [8] The photosensitive polyimide resin composition according to any one of [1] to [7] above, wherein the number average molecular weight of the above-mentioned multifunctional free radical polymerizable compound (B) is 500 or more and 10,000 or less.

[0032] [9] The photosensitive polyimide resin composition according to any one of [1] to [8] above, wherein the elongation at break of the resin film with a film thickness of 30 μm is 8% or more, and the resin film with a film thickness of 30 μm is obtained as follows: the above photosensitive polyimide resin composition is pre-baked at 100°C for 5 minutes at 250 mJ / cm 2 Above 5,000 mJ / cm 2The product is obtained by irradiating the light from a high-pressure mercury lamp with wavelengths cut off below 365nm with the optimal exposure within the following range, followed by heat treatment at 200°C for 2 hours under a nitrogen atmosphere.

[0033]

[10] The photosensitive polyimide resin composition according to any one of [1] to [9] above, wherein the glass transition temperature of the resin film with a film thickness of 30 μm is 180°C or higher, and the resin film with a film thickness of 30 μm is obtained as follows: the above photosensitive polyimide resin composition is pre-baked at 100°C for 5 minutes, with a temperature of 250 mJ / cm 2 Above 5,000 mJ / cm 2 The product is obtained by irradiating the light from a high-pressure mercury lamp with wavelengths cut off below 365nm with the optimal exposure within the following range, followed by heat treatment at 200°C for 2 hours under a nitrogen atmosphere.

[0034]

[11] The photosensitive polyimide resin composition according to any one of [1] to

[10] above, wherein the closed-ring polyimide resin (A) has a transmittance of 80% or more at a wavelength of 365 nm when it is prepared as a solution with a solid content concentration of 3% by mass.

[0035]

[12] The photosensitive polyimide resin composition according to any one of [1] to

[11] above, wherein A in the above formula (1) contains an aromatic ring as an aromatic hydrocarbon group.

[0036]

[13] The photosensitive polyimide resin composition according to any one of [1] to

[12] above, wherein A of the above formula (1) comprises at least one selected from the group consisting of the structures shown below.

[0037]

[0038] [In the formula, * represents a connector.]

[0039]

[14] The photosensitive polyimide resin composition according to any one of [1] to

[13] above, wherein the closed-ring polyimide resin (A) comprises at least one unit composed of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 4,4'-oxybis[3-(trifluoromethyl)aniline] or 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene.

[0040]

[15] The photosensitive polyimide resin composition according to any one of [1] to

[14] above further comprises at least one selected from the group consisting of a photopolymerization initiator, a solvent, an adhesion improver, a surface conditioner and a sensitizer.

[0041]

[16] The photosensitive polyimide resin composition according to any one of [1] to

[15] above is used to form an insulating film.

[0042]

[17] A resin film formed from any one of the above-described [1] to

[16] photosensitive polyimide resin compositions or cured products of the above-described photosensitive polyimide resin compositions.

[0043]

[18] The resin film according to

[17] above has a film thickness of 20 μm or more.

[0044]

[19] An electronic device comprising the resin film described in

[18] above.

[0045] The effects of the invention

[0046] According to the present invention, a photosensitive polyimide resin composition that provides an excellent balance between thick film heat resistance and thick film flexibility can be provided. Detailed Implementation

[0047] The embodiments for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail below. The following embodiments are illustrative examples of the present invention and do not limit the scope of the invention. The present invention can be implemented with appropriate modifications within its scope. In this embodiment, preferred provisions can be arbitrarily adopted, and combinations of preferred provisions can be considered more preferred. In this embodiment, the term "XX~YY" refers to "XX or more and YY or less".

[0048] In this embodiment, "(meth)acrylate" refers to both "acrylate" and "methacrylate". The same applies to other similar terms ("(meth)acrylic acid", "(meth)acryloyl", etc.).

[0049] 1. Photosensitive polyimide resin composition

[0050] The photosensitive polyimide resin composition of this embodiment comprises a cyclic polyimide resin (A) and a multifunctional radical polymerizable compound (B). The cyclic polyimide resin (A) has the structure shown in formula (1). The multifunctional radical polymerizable compound (B) has radical polymerizable functional groups and oxoalkylene groups. The number of radical polymerizable functional groups in the multifunctional radical polymerizable compound (B) is 3 or more and 100 or less. The total number of moles of oxoalkylene groups added in the multifunctional radical polymerizable compound (B) is 5 or more and 100 or less.

[0051]

[0052] In formula (1) above, R is a tetravalent group having a cyclic structure, an acyclic structure, or a combination of cyclic and acyclic structures with 4 to 10 carbon atoms. A is a divalent group having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and organosiloxane groups, and having 2 to 39 carbon atoms. The main chain of A may optionally contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S-. n represents the number of repeating units. The end of formula (1) above is any of the groups or hydrogen atoms shown in formula (2) or formula (3) below, and at least one end is a group shown in formula (2) or formula (3) below.

[0053]

[0054] In equations (2) and (3) above, X and X 2 Each is an independent group having 2 or more but less than 15 carbon atoms, and may be selected from at least one group consisting of ester bonds and double bonds. Y and Y 2 Each can be a hydrogen atom or a methyl group independently.

[0055] The photosensitive polyimide resin composition described in this embodiment is a composition containing a closed-ring polyimide resin (A) and a multifunctional free radical polymerizable compound (B), and exhibits an excellent balance between thick-film heat resistance and thick-film flexibility. The closed-ring polyimide resin (A) has the structure shown in formula (1) above, and the multifunctional free radical polymerizable compound (B) has 3 or more and 100 or less free radical polymerizable functional groups and oxoalkylene groups with a total addition molar number of 5 or more and 100 or less. Furthermore, the photosensitive polyimide resin composition described in this embodiment exhibits an excellent balance between thick-film heat resistance and thick-film flexibility, thus effectively suppressing the occurrence of cracks, defects, and breakage in the resulting resin film.

[0056] In this embodiment, "excellent heat resistance of thick film" means that when a resin film with a thickness of, for example, 20 μm or more is formed, the glass transition temperature is high. Furthermore, in this embodiment, "excellent flexibility of thick film" means that when a resin film with a thickness of, for example, 20 μm or more is formed, the elongation at break is high.

[0057] The photosensitive polyimide resin composition described in this embodiment achieves an excellent balance between thick-film heat resistance and thick-film flexibility by containing a cyclic polyimide resin (A) and a multifunctional free radical polymerizable compound (B). The cyclic polyimide resin (A) has the structure shown in formula (1) above, and the multifunctional free radical polymerizable compound (B) has 3 or more and 100 or less free radical polymerizable functional groups and oxoalkylene groups with a total addition molar number of 5 or more and 100 or less. The reason for this is not yet certain, but the following can be considered.

[0058] It can be considered that: First, the closed-ring polyimide resin (A) with the structure shown in the above formula (1) has excellent transparency. Therefore, even if the resin film is thickened, the light during exposure can easily reach the lower part of the film, which can make the resin film crosslink more uniformly and the thick film has excellent curing properties. Furthermore, by combining it with a multifunctional free radical polymerizable compound (B), the crosslinking density of the resin film is increased, which can improve the heat resistance of the thick film.

[0059] Furthermore, the closed-ring polyimide resin (A) is a resin whose imidization is already complete, therefore a dehydration and ring-closure process is not required. Therefore, it can be considered that by combining it with a polyfunctional radical polymerizable compound (B) containing oxyalkylene groups, the curing shrinkage of the resin film during exposure can be suppressed, thereby improving the flexibility of the thick film. Here, while using a polyfunctional radical polymerizable compound containing oxyalkylene groups can improve the flexibility of the resulting resin film, there is a tendency for a decrease in the heat resistance of the resin film. However, it can be considered that by using a polyfunctional radical polymerizable compound (B) with radical polymerizable functional groups and a total addition molar number within the aforementioned range, the crosslinking structure of the resulting resin film becomes a structure that strikes a good balance between heat resistance and flexibility, thus both suppressing the decrease in the heat resistance of the resin film and improving its flexibility.

[0060] In summary, it can be concluded that the photosensitive polyimide resin composition according to this embodiment, by combining the closed-ring polyimide resin (A) with the multifunctional free radical polymerizable compound (B), can improve the balance between the heat resistance and flexibility of the thick film.

[0061] [Closed-ring polyimide resin (A)]

[0062] The closed-ring polyimide resin (A) described in this embodiment has the structure shown in the following formula (1).

[0063]

[0064] In formula (1) above, R is a tetravalent group having a cyclic structure, an acyclic structure, or a combination of cyclic and acyclic structures with 4 to 10 carbon atoms. A is a divalent group having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and organosiloxane groups, and having 2 to 39 carbon atoms. The main chain of A may optionally contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S-. n represents the number of repeating units. The end of formula (1) above is any of the groups or hydrogen atoms shown in formula (2) or formula (3) below, and at least one end is a group shown in formula (2) or formula (3) below.

[0065]

[0066] In equations (2) and (3) above, X and X 2 Each is an independent group having 2 or more but less than 15 carbon atoms, and may be selected from at least one group consisting of ester bonds and double bonds. Y and Y 2 Each can be a hydrogen atom or a methyl group independently.

[0067] R in formula (1) above preferably has at least a cyclic structure. Examples of such cyclic structures include tetravalent groups formed by removing four hydrogen atoms from cyclohexane, cyclopentane, cyclobutane, dicyclopentane, and their stereoisomers. More specifically, examples of such tetravalent groups include groups shown in the following structural formula.

[0068]

[0069] [In the formula, * represents a connector.]

[0070] Of the above, the preferred option is a tetravalent group formed by removing four hydrogen atoms from cyclohexane.

[0071] In formula (1) above, A is a divalent group having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and organosiloxane groups, and having 2 or more carbon atoms and 39 or fewer carbon atoms. The main chain of A may optionally contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S-.

[0072] More specifically, A may include divalent groups formed by removing two hydrogen atoms from the following: cyclohexane, dicyclohexylmethane, dimethylcyclohexane, isophorone, norbornene and their alkyl-substituted derivatives and their halogen-substituted derivatives; benzene, naphthalene, biphenyl, diphenylmethane, diphenyl ether, diphenyl sulfone, benzophenone and their alkyl-substituted derivatives and their halogen-substituted derivatives; organo(poly)siloxanes and other compounds. A preferably has a cyclic structure, more preferably has at least one selected from alicyclic hydrocarbon groups and aromatic rings. A more preferably has an aromatic ring as an aromatic hydrocarbon group. More specifically, divalent groups with 6 or more and 27 or fewer carbon atoms as shown in the following structural formulas may be preferred.

[0073]

[0074] In the formula, * represents a connector key.

[0075] As a divalent group having 2 or more and 39 or less carbon atoms as shown in A, it is more preferably to include at least one of the groups selected from the group consisting of the structures shown below.

[0076]

[0077] In the formula, * represents a connector key.

[0078] As a divalent group with 2 or more and 39 or fewer carbon atoms as shown in A, it is even more preferable to include at least one group (Ia) selected from the group consisting of the structures shown below.

[0079]

[0080] In the formula, * represents a connector key.

[0081] As a divalent group with 2 or more and 39 or fewer carbon atoms as shown in A, it is even more preferable to include at least one group (Ib) selected from the group consisting of the structures shown below.

[0082]

[0083] In the formula, * represents a connector key.

[0084] As a divalent group with 2 or more and 39 or less carbon atoms as shown in A, it is even more preferable to include the following formula (Ic).

[0085]

[0086] [In the formula, * represents a connector.]

[0087] From the viewpoint of solubility relative to the developer (hereinafter also simply referred to as "developer solubility"), in the closed-ring polyimide resin (A) described in this embodiment, the ratio of at least one structural unit selected from (Ia), (Ib) and (Ic) as A in the above formula (1) is preferably 60 mol% or more.

[0088] The ratio of at least one structural unit selected from (Ia), (Ib) and (Ic) in A of formula (1) above is more preferably 70 mol% or more, more preferably 80 mol% or more, more preferably 95 mol% or more, and more preferably 100 mol% in particular. Preferably, the structural unit derived from diamine shown in formula (Ic) is included in the above ratio.

[0089] Regarding n, which represents the number of repeating units of the structural unit shown in formula (1) above, from the viewpoint of further improving the mechanical properties of the obtained resin film, it is preferably 5 or more, more preferably 10 or more, and even more preferably 15 or more. From the viewpoint of further improving the developer solubility of the obtained photosensitive polyimide resin composition, it is preferably 250 or less, more preferably 200 or less, and even more preferably 150 or less.

[0090] The closed-ring polyimide resin (A) described in this embodiment has any of the groups or hydrogen atoms shown in formula (2) or formula (3) above at its ends, and at least one end is a group shown in formula (2) or formula (3) above. The closed-ring polyimide resin (A) may have the structure shown in formula (2) or formula (3) above at one end, or it may have the structure shown in formula (2) or formula (3) above at both ends.

[0091] X or X in equation (2) or equation (3) above 2 The indicated group is a group with 2 or more but less than 15 carbon atoms, and may be selected from at least one group consisting of ester bonds and double bonds. Y or Y 2 The groups shown are hydrogen atoms or methyl groups.

[0092] More specifically, the structures shown in formula (2) or (3) above are structures obtained by reacting the terminal amine of a polyimide resin with a compound containing a functional group. Examples of such compounds containing functional groups include compounds having an isocyanate group or an epoxy group and a (meth)acryloyl group. Examples of such compounds include, for instance, 2-isocyanoethyl methacrylate, 2-isocyanoethyl acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether. The structures shown in formula (2) or (3) above can be structures obtained by reacting the compound with the amine terminal of a polyimide resin.

[0093] Regarding the weight-average molecular weight of the ring-closed polyimide resin (A), from the viewpoint of further improving the developer solubility and thick film developability of the photosensitive polyimide resin composition, it is preferably 70,000 or less, more preferably 60,000 or less, more preferably 50,000 or less, further preferably 45,000 or less, further preferably 40,000 or less, and further preferably 35,000 or less. From the viewpoint of further improving the mechanical properties of the resulting resin film, it is preferably 5,000 or more, more preferably 10,000 or more, further preferably 13,000 or more, and further preferably 15,000 or more. By keeping the weight-average molecular weight of the ring-closed polyimide resin (A) within the above range, the developer solubility can be improved, thus further reducing the residual film rate of the unexposed portion and further improving the developability of the photosensitive polyimide resin composition. Here, the above-mentioned weight-average molecular weight is the weight-average molecular weight converted from polystyrene.

[0094] The photosensitive polyimide resin composition described in this embodiment exhibits an excellent balance of thick film developability, thick film heat resistance, and thick film flexibility by containing a cyclic polyimide resin (A) and a multifunctional free radical polymerizable compound (B). The cyclic polyimide resin (A) has the structure shown in formula (1) above and has a weight-average molecular weight of 70,000 or less. The multifunctional free radical polymerizable compound (B) has 3 or more and 100 or less free radical polymerizable functional groups and oxyalkylene groups with a total addition molar number of 5 or more and 100 or less. The reason for improved thick film developability is not yet certain, but the following can be considered.

[0095] First, the greater the difference in developer solubility between the exposed and unexposed areas, the better the development performance. To improve development performance, it is important to increase the difference in developer solubility between the exposed and unexposed areas.

[0096] It can be assumed here that the developer solubility of the closed-ring polyimide resin (A) with the structure shown in the above formula (1) and a weight average molecular weight of less than 70,000 is high. Therefore, even if the resin film is thickened, the developer solubility of the unexposed part is still high.

[0097] In addition, it can be considered that the closed-ring polyimide resin (A) with the structure shown in formula (1) above has excellent transparency. Therefore, even if the resin film is thickened, the exposure time can easily reach the lower part of the film, which can make the resin film crosslink more uniformly. Furthermore, by combining it with a multifunctional free radical polymerizable compound (B), the crosslink density of the resin film is increased, which can reduce the solubility of the developer in the exposed part.

[0098] In summary, it can be concluded that the photosensitive polyimide resin composition according to this embodiment, by combining the closed-ring polyimide resin (A) with the multifunctional free radical polymerizable compound (B), can increase the difference in developer solubility between the exposed and unexposed areas, thereby improving the developability of thick films.

[0099] The closed-ring polyimide resin (A) can be obtained by reacting the diamine component, as detailed below, with the tetracarboxylic acid component.

[0100] <Diamine component>

[0101] Examples of diamine components include diamines, diisocyanates, and diaminodisilanes, with diamines being preferred. The diamine content in the diamine component used as a raw material is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, even more preferably 95 mol% or more, and most preferably 100 mol% or less.

[0102] The aforementioned diamine can be any of aliphatic and aromatic diamines, or a mixture thereof. In this embodiment, "aromatic diamine" refers to a diamine with an amino group directly bonded to an aromatic ring, and a portion of its structure optionally includes an aliphatic group, an alicyclic group, or other substituents. "Aliphatic diamine" refers to a diamine with an amino group directly bonded to an aliphatic or alicyclic group, and a portion of its structure optionally includes an aromatic group or other substituents.

[0103] Generally, if aliphatic diamines are used as raw materials for polyimide resins, the polyamic acid, as an intermediate product, forms a strong complex with the aliphatic diamine, making it difficult to obtain high molecular weight polyimides. Therefore, improvements are needed, such as using solvents with high solubility for the complex, like cresol. If cyclohexanetetracarboxylic acid, cyclobutanetetracarboxylic acid, or their derivatives are used as the tetracarboxylic acid component, a weaker complex is formed between the polyamic acid and the aliphatic diamine, thus making it easier to achieve high molecular weight polyimides. As for the diamine, if a diamine with fluorinated substituents is selected as the raw material, the resulting polyimide resin exhibits excellent transparency and is therefore preferred.

[0104] Examples of aliphatic diamines include 4,4'-diaminodicyclohexylmethane, ethylenediamine, hexamethylenediamine, polyethylene glycol bis(3-aminopropyl) ether, polypropylene glycol bis(3-aminopropyl) ether, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, m-phenylenediamine, p-phenylenediamine, isophorone diamine, norbornene diamine, and siloxane diamines.

[0105] Examples of the aforementioned aromatic diamines include, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, diaminobenzophenone, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-oxybis[3-(trifluoromethyl)aniline], 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, and 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene.

[0106] The diamine component preferably includes at least one selected from 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 4,4'-oxybis[3-(trifluoromethyl)aniline] and 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene.

[0107] By including at least these diamines as diamine components, the transmittance and developer solubility of the resulting photosensitive polyimide resin composition at specific wavelengths can be further improved. Therefore, the curability of the exposed portion can be improved, and the residual film rate of the unexposed portion can be reduced, thus further improving the developability of the resulting photosensitive polyimide resin composition.

[0108] The closed-ring polyimide resin (A) described in this embodiment preferably comprises at least one unit selected from 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 4,4'-oxybis[3-(trifluoromethyl)aniline], or 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene.

[0109] <Tetracarboxylic acid component>

[0110] Examples of tetracarboxylic acid components include cyclohexanetetracarboxylic acid, cyclohexanetetracarboxylic acid esters, cyclohexanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid, cyclobutanetetracarboxylic acid esters, cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid, cyclopentanetetracarboxylic acid esters, cyclopentanetetracarboxylic acid dianhydride, and dicyclopentanetetracarboxylic acid dianhydride. Among these, the tetracarboxylic acid component preferably includes at least one selected from cyclohexanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, and cyclopentanetetracarboxylic acid dianhydride, and more preferably includes cyclohexanetetracarboxylic acid dianhydride. All of the above-mentioned tetracarboxylic acid components include positional isomers.

[0111] More preferred specific examples of the aforementioned tetracarboxylic acid components include 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid methyl ester, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid methyl ester, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid methyl ester, 1,2,4,5- Cyclopentanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, methyl 1,2,4,5-cyclopentanetetracarboxylic acid, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic methyl ester, dicyclohexyltetracarboxylic acid, dicyclohexyltetracarboxylic dianhydride, and dicyclohexyltetracarboxylic methyl ester, etc.

[0112] From the viewpoint that it is advantageous to easily achieve high molecular weight and obtain flexible resin films when manufacturing polyimide resins, the tetracarboxylic acid component preferably includes at least one selected from 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and methyl 1,2,4,5-cyclohexanetetracarboxylic acid.

[0113] The tetracarboxylic acid component may include other tetracarboxylic acids or their derivatives within a range that does not impair, for example, the flexibility or heat-pressurization properties of the resin film. Examples of such other tetracarboxylic acids or their derivatives include, for example, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(3,4-dicarboxyphenyl) At least one of the following: sulfone, bis(3,4-dicarboxyphenyl) ether, bis(2,3-dicarboxyphenyl) ether, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 4,4-(p-phenylenedioxy)bisphthalic acid, 4,4-(m-phenylenedioxy)bisphthalic acid, ethylenetetracarboxylic acid, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, and their derivatives.

[0114] From the viewpoint of enabling more uniform cross-linking of the resin film and further improving the curability and patternability of the thick film, the closed-ring polyimide resin (A) described in this embodiment, when prepared as a solution with a solid component concentration of 3% by mass, preferably has a transmittance of 80% or more at a wavelength of 365 nm, more preferably 85% or more, further preferably 88% or more, and even more preferably 90% or more.

[0115] <Manufacturing Method of Closed-Ring Polyimide Resin (A)>

[0116] The closed-loop polyimide resin (A) described in this embodiment can be obtained by, for example, a manufacturing method including the following steps (1) and (2).

[0117] Process (1): The tetracarboxylic acid component reacts with the diamine component to obtain a polyimide resin with amino groups at the ends.

[0118] Step (2): The polyimide resin with an amino group at the end obtained in step (1) above reacts with the above-mentioned compound containing a functional group (a compound having an isocyanate group or an epoxy group and a (meth)acryloyl group).

[0119] (Process (1))

[0120] In step (1), a tetracarboxylic acid is reacted with a diamine component to obtain a polyimide resin with an amino group at the end.

[0121] The organic solvent used to react the tetracarboxylic acid component with the diamine component is not particularly limited, but is preferably an organic solvent comprising, for example, at least one selected from the group consisting of cyclic ethers, cyclic ketones, cyclic esters, amides, and ureas. Specific examples of suitable solvents are not particularly limited, but include at least one selected from the group consisting of aprotic polar organic solvents such as γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentanone, cyclohexanone, 1,3-dioxane, 1,4-dioxane, tetramethylurea, and tetrahydrofuran. More preferably, it is one or more selected from the group consisting of γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone.

[0122] When reacting the tetracarboxylic acid component with the diamine component in step (1), an imidization catalyst may be used. The imidization catalyst is preferably a tertiary amine compound, and specifically, at least one selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, and isoquinoline may be used.

[0123] The reaction temperature in step (1) is, for example, in the range of 160°C or higher and 230°C or lower, preferably in the range of 170°C or higher and 210°C or lower, and more preferably in the range of 180°C or higher and 200°C or lower. If the reaction temperature in step (1) is above or above the lower limit mentioned above, imidization and molecular weight increase can be carried out more effectively. If the reaction temperature in step (1) is below or above the upper limit mentioned above, the solution viscosity can be maintained more appropriately, and adverse conditions such as resin scorching on the walls of the reaction vessel can be further avoided. Depending on the situation, azeotropic dehydrating agents such as toluene and xylene can be used. The reaction pressure is usually atmospheric pressure, but the reaction can also be carried out under pressure as needed. The holding time of the reaction temperature is preferably 1 hour or more, more preferably 3 hours or more. If the holding time of the reaction temperature is above or above the lower limit mentioned above, imidization and molecular weight increase can be carried out more effectively. Regarding the reaction time, there is no particular upper limit, and it can be carried out in the range of, for example, 10 hours or less.

[0124] In step (1), the reaction preferably occurs within a range of 0.80 ≤ A / B ≤ 0.99 for the tetracarboxylic acid component "A moles" and the diamine component "B moles", and more preferably within a range of 0.85 ≤ A / B ≤ 0.97. By setting A / B ≤ 0.99, the polyimide ends can exhibit an excess of diamine, resulting in a polyimide resin with amino groups at the ends, and a polyimide resin with a molecular weight that provides sufficient developer solubility. If the ratio is 0.80 ≤ A / B, a polyimide resin with a molecular weight exhibiting sufficient flexibility can be obtained.

[0125] Since a higher molecular weight polyimide resin can be obtained when the A / B ratio is closer to 1.0, the target molecular weight polyimide resin can be obtained by appropriately adjusting the A / B ratio.

[0126] <Process (2)>

[0127] Step (2) is a step of modifying the ends of the polyimide resin obtained in step (1) above. Specifically, as described above, the polyimide is reacted with the above-mentioned compound containing a functional group (a compound having an isocyanate group or an epoxy group and having a (meth)acryloyl group) to obtain a polyimide resin having a (meth)acryloyl group at the end.

[0128] Compounds containing functional groups that modify the ends of polyimide resins are compounds having isocyanate or epoxy groups and (meth)acryloyl groups. Specifically, examples include 2-isocyanoethyl methacrylate, 2-isocyanoethyl acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether. These functional group-containing compounds can be used alone or in combination of two or more. Preferably, the functional group-containing compound is used in a ratio of 0.1 to 30 molar times relative to the polyimide resin having an amino group at the end.

[0129] The reaction temperature in step (2) is preferably above 30°C and below 100°C, and the reaction time is preferably above 1 hour and below 10 hours.

[0130] When reacting the amino terminus of a polyimide resin with the isocyanate or epoxy groups of a functionalized compound, the reaction can be carried out directly or, if necessary, in the presence of a catalyst. Examples of catalysts include amine compounds such as triethylamine and organophosphorus compounds such as triphenylphosphine; these can be used alone or in combination of two or more. To suppress side reactions during the reaction, polymerization inhibitors can be used. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone; these can be used alone or in combination of two or more.

[0131] When the total solid content of the photosensitive polyimide resin composition is set to 100% by mass, from the viewpoint of further improving the patternability of thick films, the content of the closed-ring polyimide resin (A) in the photosensitive polyimide resin composition of this embodiment is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0132] In this embodiment, the term "all solid components" in the photosensitive polyimide resin composition refers to the components that remain as solid components when the photosensitive polyimide resin composition is cured, excluding components that evaporate upon heating, such as solvents. On the other hand, even liquid components include those that enter the resin film during heat curing, which are also included in the total solid components.

[0133] [Multifunctional free radical polymeric compound (B)]

[0134] The multifunctional free radical polymerizable compound (B) described in this embodiment has 3 or more and 100 or less free radical polymerizable functional groups and oxoalkylene groups with a total addition molar number of 5 or more and 100 or less.

[0135] In this embodiment, when the multifunctional radical polymerizable compound (B) contains two or more multifunctional radical polymerizable compounds with different numbers of radical polymerizable functional groups, the number of radical polymerizable functional groups in the multifunctional radical polymerizable compound (B) can be a weighted average of the number of radical polymerizable functional groups in each multifunctional radical polymerizable compound.

[0136] In addition, in this embodiment, when the multifunctional radical polymerizable compound (B) contains two or more multifunctional radical polymerizable compounds with different total molar additions of alkylene oxides, the total molar addition of alkylene oxides in the multifunctional radical polymerizable compound (B) can be the weighted average of the total molar additions of alkylene oxides in each multifunctional radical polymerizable compound.

[0137] The number of free radical polymerizable functional groups in the multifunctional free radical polymerizable compound (B) is 3 or more and 100 or less. From the viewpoint of further improving the balance between the heat resistance and flexibility of the thick film, it is preferred to have 4 or more, more preferably 5 or more, even more preferably 6 or more, and preferably 50 or less, even more preferably 30 or less, even more preferably 15 or less, even more preferably 10 or less, even more preferably 8 or less, and even more preferably 7 or less.

[0138] The total molar number of oxyalkylene additions in the multifunctional free radical polymerizable compound (B) is 5 or more and 100 or less. From the viewpoint of further improving the balance between the heat resistance and flexibility of the thick film, it is preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 90 or less, even more preferably 80 or less, even more preferably 70 or less, and even more preferably 65 or less.

[0139] From the viewpoint of further improving the balance between the heat resistance and flexibility of thick films, the oxoalkylene group of the multifunctional free radical polymerizable compound (B) preferably includes at least one selected from oxoethylene and oxopropylene, and more preferably includes oxoethylene.

[0140] From the viewpoint of further improving the balance between the heat resistance and flexibility of the thick film, the number average molecular weight of the multifunctional free radical polymerizable compound (B) is preferably 500 or more, more preferably 600 or more, even more preferably 800 or more, even more preferably 1,000 or more, and preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 5,000 or less.

[0141] Examples of free radical polymerizable functional groups include (meth)acryloyl and vinyl groups, with (meth)acryloyl being the most preferred.

[0142] Examples of multifunctional radical polymerizable compounds constituting the multifunctional radical polymerizable compound (B) include, for example, polypropylene glycol di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated tris(2-(meth)acryloyloxyethyl)isocyanurate, propoxylated tris(2-(meth)acryloyloxyethyl)isocyanurate, ethoxylated bis(trimethylolpropane tetra(meth)acrylate, propoxylated bis(trimethylolpropane tetra(meth)acrylate, ethoxylated bis(trimethylolpropane penta(meth)acrylate, and propoxylated bis(trimethylolpropane penta(meth)acrylate. (Meth)acrylates, ethoxylated bis(trimethylolpropane)hexa(meth)acrylate, propoxylated bis(trimethylolpropane)hexa(meth)acrylate, ethoxylated dipentaerythritol penta(meth)acrylate, propoxylated dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated tripentaerythritol (meth)acrylate, propoxylated tripentaerythritol (meth)acrylate, ethoxylated glycerol (meth)acrylate, propoxylated glycerol (meth)acrylate, ethoxylated diglycerol (meth)acrylate, propoxylated diglycerol (meth)acrylate, ethoxylated triglycerol (meth)acrylate, propoxylated triglycerol (meth)acrylate, ethoxylated polyglycerol (meth)acrylates, propoxylated polyglycerol (meth)acrylates, etc. These multifunctional free radical polymerizable compounds can be used alone or in combination of two or more. Alternatively, these multifunctional radical polymerizable compounds can be used individually to adjust the number of radical polymerizable functional groups and the total number of oxoalkylene addition moles to the ranges mentioned above, or two or more can be combined to adjust the number of radical polymerizable functional groups and the total number of oxoalkylene addition moles to the ranges mentioned above.

[0143] Here, ethoxylated or propoxylated polyglycerol (meth)acrylates refer to compounds having a polyglycerol backbone and (meth)acryloyl groups. Examples of ethoxylated or propoxylated polyglycerol (meth)acrylates include SA-TE6 and SA-TE60 manufactured by Sakamoto Pharmaceutical Co., Ltd.

[0144] Regarding the content of the multifunctional free radical polymerizable compound (B) in the photosensitive polyimide resin composition described in this embodiment, when the amount of the closed-ring polyimide resin (A) contained in the photosensitive polyimide resin composition is set to 100 parts by mass, from the viewpoint of further improving the balance between the heat resistance and flexibility of the thick film, it is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more. From the viewpoint of further improving the balance between the heat resistance and flexibility of the thick film and further suppressing the stickiness of the thick film pattern, it is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less.

[0145] [Other ingredients]

[0146] In the photosensitive polyimide resin composition described in this embodiment, as other components besides the closed-ring polyimide resin (A) and the multifunctional free radical polymerizable compound (B), it is preferable to also include at least one of the following: selected from the group consisting of a photopolymerization initiator, a solvent, an adhesion improver, a surface conditioner, and a sensitizer. More preferably, it also includes at least one of the following: selected from the group consisting of a photopolymerization initiator and a solvent.

[0147] (Photopolymerization initiator)

[0148] There are no particular limitations on the photopolymerization initiator; known substances can be used. Examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one, Examples of photopolymerization initiators include 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. These photopolymerization initiators can be used alone or in combination of two or more.

[0149] When the amount of closed-ring polyimide resin (A) contained in the photosensitive polyimide resin composition is set to 100 parts by mass, the content of photopolymerization initiator in the photosensitive polyimide resin composition described in this embodiment is, for example, 0.1 parts by mass or more and 10 parts by mass or less.

[0150] (solvent)

[0151] From a solubility perspective, non-protic polar solvents are desirable. Examples of suitable solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamine, N-acetyl-ε-caprolactam, dimethylimidazolium ketone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and γ-butyrolactone. These solvents can be used alone or in combination of two or more. To further improve coatability, solvents such as toluene, xylene, diethyl ketone, methoxybenzene, and cyclopentanone can be mixed within a range that does not adversely affect the solubility of the polymer.

[0152] By using a suitable solvent, the photosensitive polyimide resin composition described in this embodiment can be used in a solution (varnish) state, thereby improving film-forming properties.

[0153] (Adhesion improver)

[0154] There are no particular limitations on the adhesion improver; any known substance can be used, such as silane coupling agents containing amino groups, silane coupling agents containing epoxy groups, silane coupling agents containing mercapto groups, silane coupling agents containing (meth)acryloyl groups, and other known coupling agents; titanate coupling agents, aluminate coupling agents, and other known coupling agents. Examples of coupling agents include KP-390, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, and KBE-9007 (all trade names; manufactured by Shin-Etsu Chemical Co., Ltd.). They can be used individually or in combination of two or more.

[0155] When the amount of closed-ring polyimide resin (A) contained in the photosensitive polyimide resin composition is set to 100 parts by mass, the content of the adhesion improver in the photosensitive polyimide resin composition of this embodiment is, for example, 0.0005 parts by mass or more and 20 parts by mass or less.

[0156] (Surface Conditioner)

[0157] There are no particular limitations on the surface modifier; any known substance can be used, such as silicon-based surface modifiers, acrylic-based surface modifiers, fluorinated surface modifiers, nonionic surface modifiers, cationic surface modifiers, anionic surface modifiers, and various other surface modifiers. They can be used alone or in combination of two or more.

[0158] When the amount of closed-ring polyimide resin (A) contained in the photosensitive polyimide resin composition is set to 100 parts by mass, the content of surface conditioner in the photosensitive polyimide resin composition described in this embodiment is, for example, 0.001 parts by mass or more and 20 parts by mass or less.

[0159] (Sensitizer)

[0160] The sensitizer is not particularly limited, and known substances can be used. Examples include sensitizers containing an amino group, and compounds having both an amino and a phenyl group within the same molecule are preferred. More specifically, examples include benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzo[4,5]benzo[5]benzo[6,7 ... Compounds containing p-dialkylaminophenyl groups, such as 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine, are used. These sensitizers can be used alone or in combination of two or more.

[0161] When the amount of closed-ring polyimide resin (A) contained in the photosensitive polyimide resin composition is set to 100 parts by mass, the content of sensitizer in the photosensitive polyimide resin composition described in this embodiment is, for example, 0.001 parts by mass or more and 10 parts by mass or less.

[0162] From the viewpoint of further improving the heat resistance of thick films, when the photosensitive polyimide resin composition described in this embodiment is used to form a resin film with a thickness of 30 μm, the elongation at break is preferably 8% or more, more preferably 10% or more, even more preferably 12% or more, and even more preferably 15% or more. The upper limit of the above elongation at break is not particularly limited, for example, it is 200% or less, preferably 150% or less, and even more preferably 100% or less.

[0163] Here, the 30μm thick resin film is obtained by the following method.

[0164] First, the photosensitive polyimide resin composition described in this embodiment is coated onto a substrate such as a silicon wafer to achieve a film thickness of 30 μm after solvent removal. Next, the photosensitive polyimide resin composition formed on the substrate is pre-baked (dried) at 100°C for 5 minutes. Then, the cumulative irradiation dose (calculated based on an illuminance of 365 nm) is 250 mJ / cm². 2 Above 5,000 mJ / cm 2 The optimal exposure range is achieved by irradiating the substrate with light from a high-pressure mercury lamp that has cut off wavelengths less than 365 nm. After standing at room temperature for 15 minutes, the substrate is immersed in water, and the resin film is peeled off from the substrate. The resulting product is then heat-treated at 200°C for 2 hours under a nitrogen atmosphere.

[0165] In this embodiment, the optimal exposure level refers to: 250 mJ / cm². 2 Above 5,000 mJ / cm 2 Within the following range, with multiple different cumulative radiation doses (250 mJ / cm²) 2 1,500 mJ / cm 2 2,000 mJ / cm 2 4,000 mJ / cm 2 and 5,000 mJ / cm 2 When these five points are exposed, the cumulative irradiation dose that achieves the best balance between thick film curability, thick film flexibility, and thick film heat resistance is obtained. Here, in this embodiment, "excellent thick film curability" means that when a resin film with a thickness of, for example, 20 μm or more is formed, a self-standing film can be obtained, and the solubility of the developer (e.g., γ-butyrolactone) is low.

[0166] From the viewpoint of further improving the heat resistance of thick films, the glass transition temperature when the photosensitive polyimide resin composition described in this embodiment is formed into a resin film with a thickness of 30 μm is preferably 180°C or higher, more preferably 190°C or higher, even more preferably 200°C or higher, even more preferably 210°C or higher, and even more preferably 230°C or higher. The upper limit of the above glass transition temperature is not particularly limited, for example, it is 300°C or lower, preferably 280°C or lower. The above glass transition temperature can be obtained by thermomechanical analysis (TMA).

[0167] Here, the 30μm thick resin film is obtained by the following method.

[0168] First, the photosensitive polyimide resin composition described in this embodiment is coated onto a substrate such as a silicon wafer to achieve a film thickness of 30 μm after solvent removal. Next, the photosensitive polyimide resin composition formed on the substrate is pre-baked (dried) at 100°C for 5 minutes. Then, the cumulative irradiation dose (calculated based on an illuminance of 365 nm) is 250 mJ / cm². 2 Above 5,000 mJ / cm 2 The optimal exposure range is achieved by irradiating the substrate with light from a high-pressure mercury lamp that has cut off wavelengths less than 365 nm. After standing at room temperature for 15 minutes, the substrate is immersed in water, and the resin film is peeled off from the substrate. The resulting product is then heat-treated at 200°C for 2 hours under a nitrogen atmosphere.

[0169] In this embodiment, the optimal exposure level refers to: 250 mJ / cm². 2 Above 5,000 mJ / cm 2 Within the following range, with multiple different cumulative radiation doses (250 mJ / cm²) 2 1,500 mJ / cm 2 2,000 mJ / cm 2 4,000 mJ / cm 2 and 5,000 mJ / cm 2 When these 5 points are exposed, the cumulative irradiation dose achieves the best balance between thick film curing properties, thick film flexibility, and thick film heat resistance.

[0170] The photosensitive polyimide resin composition described in this embodiment is not particularly limited and can be obtained, for example, by mixing at least one of the group consisting of a photopolymerization initiator, a solvent, an adhesion improver, a surface conditioner, and a sensitizer as needed into a closed-ring polyimide resin (A) and a multifunctional free radical polymerizable compound (B).

[0171] 2. Resin film

[0172] The photosensitive polyimide resin composition described in this embodiment can be used to form resin films, such as resist layers used in the manufacture of electronic devices, and permanent films (cured films) constituting electronic devices. That is, the resin film described in this embodiment is formed from the photosensitive polyimide resin composition or a cured product of the photosensitive polyimide resin composition.

[0173] The aforementioned resist layer is composed of a resin film obtained, for example, by coating a substrate with the photosensitive polyimide resin composition described in this embodiment and removing the solvent as needed.

[0174] The aforementioned permanent film is composed of a cured film, which is obtained by exposing and developing the aforementioned resin film to form a desired shape and then curing it using heat treatment or the like.

[0175] Permanent films can be suitable for use as insulating films such as surface protective films and interlayer insulating films.

[0176] A surface protective film refers to an insulating film formed on the surface of an electronic component, electronic device, or wiring on a wiring substrate, and used to protect that surface. There is no particular limitation on the type of surface protective film. Examples of such surface protective films include passivation films or buffer coatings disposed on semiconductor elements, or top coatings disposed on flexible substrates.

[0177] Interlayer insulating film refers to an insulating film disposed in a multilayer structure, and its type is not particularly limited. Examples of interlayer films include interlayer insulating films constituting multilayer wiring structures of semiconductor devices, and interlayer films used in semiconductor device applications such as add-on layers or core layers constituting wiring substrates. Other examples of interlayer films used in display device applications include planarization films covering thin-film transistors in display devices, liquid crystal alignment films, protrusions disposed on color filter substrates of liquid crystal display devices, and separators used to form cathodes of organic EL elements.

[0178] There are no particular limitations on the method for coating the photosensitive polyimide resin composition described in this embodiment onto the substrate, and examples include inkjet printing, spin coating, casting, microgravure printing, gravure coating, bar coating, roller coating, wire bar coating, dip coating, spraying, screen printing, flexographic printing, and die coating.

[0179] When coating the substrate, it is preferable to adjust the concentration of the solids component of the photosensitive polyimide resin composition described in this embodiment to be in the range of 5% by mass or more and 50% by mass or less. From a solubility point of view, aprotic polar solvents are preferred as the solvent used during coating. Specifically, suitable examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamine, N-acetyl-ε-caprolactam, dimethylimidazolium ketone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyrolactone, etc. These solvents can be used alone or in combination of two or more. To further improve coatability, solvents such as toluene, xylene, diethyl ketone, methoxybenzene, and cyclopentanone can be mixed within a range that does not adversely affect the solubility of the polymer.

[0180] Examples of substrates include glass, silicon wafers, metal foils, and plastic films. Among these substrates, silicon wafers and copper foils are preferred.

[0181] Exposure of the film can be performed, for example, by irradiating a film formed of a photosensitive polyimide resin composition on a substrate with light (typically ultraviolet light) through a photomask with a predetermined pattern. The exposed film has portions where light is blocked by the photomask and portions where light is irradiated; in other words, it has exposed and unexposed portions. In the exposed portions of the exposed film, the polyimide resin in the photosensitive polyimide resin composition undergoes cross-linking to form a cross-linked polyimide film, which is then patterned through a subsequent development process. On the other hand, the polyimide resin in the unexposed portions does not undergo cross-linking, thus forming an uncross-linked polyimide film that is dissolved and removed during development.

[0182] After irradiation, the unexposed areas are dissolved and removed by the developing solution, thus obtaining the desired relief pattern.

[0183] The preferred cumulative ultraviolet radiation dose is 100 mJ / cm². 2 Above 8,000 mJ / cm 2 The following, and more preferably, is 200 mJ / cm 2 Above 6,000 mJ / cm 2 the following.

[0184] In the method for forming a resin pattern using the photosensitive polyimide resin composition described in this embodiment, an organic solvent is preferably used as the developing solution. The developing solution is not particularly limited as long as it can dissolve the photosensitive polyimide resin composition described in this embodiment. Specifically, suitable examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamine, N-acetyl-ε-caprolactam, dimethylimidazolium ketone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyrolactone, etc.

[0185] These developers can be used alone or in combination of two or more.

[0186] Next, the embossed pattern formed by development is cleaned using a rinse solution to remove the developer. Suitable examples of rinse solutions that are well miscible with the developer include methanol, ethanol, isopropanol, and water.

[0187] The embossed pattern obtained through the above treatment is heat-treated at a temperature selected from the range of 80°C to 250°C, and the solvent is dried, thereby obtaining a cured film (pattern) formed by curing the photosensitive polyimide resin composition described in this embodiment. According to this embodiment, a photosensitive polyimide resin composition with excellent developability, i.e., sufficient curing of the exposed areas and sufficient removal of the unexposed areas, is used; therefore, the obtained embossed pattern can be obtained at high resolution.

[0188] The film thickness of the resin film described in this embodiment is preferably 20 μm or more, more preferably 25 μm or more, further preferably 30 μm or more, and preferably 85 μm or less, more preferably 60 μm or less. If the film thickness is within the above range, it can be used as an excellent insulating film. The thicker the film (i.e., the greater the amount of photosensitive polyimide resin composition coated on the substrate), the more problems arise, especially regarding the solubility of the polyimide resin in the developer. However, according to this embodiment, by using a closed-ring polyimide resin (A) having a specific structure and a specific end structure and a specific molecular weight range, excellent developer solubility and transparency can be achieved even in the aforementioned case.

[0189] Therefore, the resin film described in this embodiment can be suitably used, for example, in applications where high voltage is to be applied as an insulating film. The resin film obtained from the photosensitive polyimide resin composition of this embodiment, which comprises a closed-ring polyimide resin (A) and a multifunctional free radical polymerizable compound (B), can effectively suppress the occurrence of cracks and the like, and has excellent physical properties.

[0190] 3. Electronic devices

[0191] The electronic device described in this embodiment includes the resin film described in this embodiment.

[0192] The electronic device described in this embodiment is not particularly limited as long as it includes a resin film formed from the photosensitive polyimide resin composition described in this embodiment. Examples include display devices that use the resin film described in this embodiment as a planarization film or a microlens; semiconductor devices that use the resin film described in this embodiment as an interlayer insulating film in a multilayer wiring structure; semiconductor devices that use the resin film described in this embodiment as a surface protective film for semiconductor elements or wiring substrates; and semiconductor devices that use the resin film described in this embodiment as an add-on layer or core layer constituting a wiring substrate. Among these, a semiconductor device is preferred as the electronic device described in this embodiment.

[0193] The electronic device described in this embodiment can be manufactured based on known information, except that it uses the resin film described in this embodiment.

[0194] The electronic device described in this embodiment has a resin film with an excellent balance between thick-film heat resistance and thick-film flexibility, thus it is not prone to insulation breakdown and has excellent reliability.

[0195] Example

[0196] The present invention will now be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples at all.

[0197] <Evaluation>

[0198] The evaluation methods used in this embodiment and the comparative example are as follows.

[0199] (1) Weight-average molecular weight (Mw)

[0200] Mw was determined using GPC analysis. The apparatus and analysis conditions used in the analysis are shown below.

[0201] Device: Ecosec Elite HLC8420GPC (manufactured by Tosoh Corporation)

[0202] Column: TSKGel super AWM-H (column size: 6.0mm × 15cm, filling gel particle size: 9μm) × 2 (manufactured by Tosoh Corporation)

[0203] Eluent: Contains dimethylformamide (20 mM lithium bromide and 100 mM phosphoric acid).

[0204] Standard polystyrene: PStQuick Kit-H (manufactured by Tosoh Corporation)

[0205] Flow rate: 0.6 mL / min

[0206] Column temperature: 40℃

[0207] Detector: RI (Refractive Index Detector)

[0208] (2) Patterning

[0209] In the examples and comparative examples described below, photosensitive polyimide resin composition varnishes were prepared. The varnishes obtained in each example and comparative example were coated onto a silicon wafer using a spin coater to achieve a film thickness of 30 μm after solvent removal. The solvent was then removed by heating at 100°C for 5 minutes. A predetermined amount of exposure was performed using a photolithography machine, followed by standing at room temperature for 15 minutes. Subsequently, unexposed areas were removed by blowing γ-butyrolactone as a developer for 30 seconds, followed by cleaning with methanol as a wetting solution, and solvent removal under air circulation.

[0210] The apparatus and conditions used during exposure are described below.

[0211] Photolithography machine: MA-10B (manufactured by MIKASA)

[0212] Light source: High-pressure mercury lamp

[0213] Illuminance: 12W / cm 2 (wavelength 365nm)

[0214] Cumulative exposure: 250–5,000 mJ / cm² 2

[0215] Developer: γ-Butyrolactone

[0216] Washing solution: methanol

[0217] Silicon wafer: 4-inch silicon wafer (manufactured by ADVANTEC)

[0218] (3) Evaluation of thick film developability

[0219] Cut the pattern (line / space = 30μm / 30μm or 30μm / 150μm) created by (2) above, and observe the cross-section using a SEM (TM3030plus (manufactured by Hitachi, Ltd.)) to confirm whether there is any residue in the unexposed area. Record "〇" for cases where there is no residue in the area and "×" for cases where there is residue in the area.

[0220] (4) Light transmittance

[0221] The ring-closed polyimide resin (A) obtained in the synthesis example was dissolved in γ-butyrolactone to obtain a polyimide resin solution with a solid content concentration of 3% by mass. Next, the transmittance of the polyimide resin solution at a wavelength of 365 nm was measured using a spectrophotometer (product name: U3900H) manufactured by Hitachi, Ltd. and a cuvette with a 10 mm path length.

[0222] (5) Elongation at break and glass transition temperature

[0223] In the examples and comparative examples described below, photosensitive polyimide resin composition varnishes were prepared. The varnishes obtained in each example and comparative example were coated onto a silicon wafer using a spin coater to a thickness of 30 μm after solvent removal, and then heated at 100°C for 5 minutes to remove the solvent. A specified amount of exposure was performed using a photolithography machine, and the wafer was allowed to stand at room temperature for 15 minutes. Subsequently, the wafer was immersed in water, and the resin film was peeled off from the silicon wafer and calcined at 200°C for 2 hours under a nitrogen atmosphere. The elongation at break and glass transition temperature (Tg) of the resulting resin film were measured under the following conditions.

[0224] The apparatus and conditions used in the determination of elongation at break are shown below.

[0225] Universal testing machine: Autograph AGS-X10kN (manufactured by Shimadzu Corporation)

[0226] Stretching speed: 1mm / minute

[0227] Test piece dimensions: dumbbell shape, size 6 (JIS K6251:2017), thickness 30μm

[0228] The apparatus and conditions used in determining the glass transition temperature are shown below.

[0229] The inflection point during the second heating in the TMA measurement is taken as Tg.

[0230] Thermomechanical analysis apparatus: TMASS6100 (manufactured by Hitachi High Technology Co., Ltd.)

[0231] Load: 100mN

[0232] Temperature conditions: 30℃→220~300℃→30℃→300℃

[0233] Heating rate: 5-10℃ / minute

[0234] <Manufacturing of closed-ring polyimide resin (A)>

[0235] Synthesis example 1

[0236] Under nitrogen atmosphere, 215.8492 g (0.642 mol) of 4,4'-oxybis[3-(trifluoromethyl)aniline], 3.083 g (0.030 mol) of triethylamine, and 430.5 g of γ-butyrolactone (hereinafter referred to as GBL) were added to a 500 ml five-necked flask equipped with a nitrogen inlet tube, a stirrer, a thermometer, and a condenser. The mixture was heated to 70 °C while stirring. 136.6360 g (0.609 mol) of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride was then added, and the mixture was reacted at 190 °C for 5 hours. The mixture was diluted with 339.1 g of GBL to obtain 1069 g of polyimide varnish with a solid content of 30% by mass. According to GPC measurements, the polyimide obtained had a polystyrene equivalent weight-average molecular weight of 34,046.

[0237] Next, 300.56 g of the obtained polyimide varnish and 7.7102 g of 2-isocyanoethyl acrylate (manufactured by Showa Denko Co., Ltd., Karenz AOI) were added to a 500 mL four-necked flask equipped with a stirrer, thermometer, and condenser, and the mixture was reacted at 50 °C for 5 hours. Afterward, the reaction solution was added dropwise to water to precipitate the polyimide, and then dried at 70 °C overnight to obtain the ring-closed polyimide resin (A1). The obtained ring-closed polyimide resin (A1) had a polystyrene equivalent weight-average molecular weight of 34,664. Furthermore, the obtained ring-closed polyimide resin (A1) had a transmittance of 92.0% at a wavelength of 365 nm.

[0238] <Examples and Comparative Examples>

[0239] Example 1

[0240] 8.1 g of the closed-ring polyimide resin (A1) obtained in Synthesis Example 1 was dissolved in 10.0 g of GBL. 4.065 g of ethoxylated polyglycerol acrylate (SA-TE60 manufactured by Sakamoto Pharmaceutical Co., Ltd.), 0.122 g of 1-hydroxycyclohexylphenyl ketone (Omnirad 184 manufactured by BASF), 0.285 g of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819 manufactured by BASF) and 0.008 g of a silicone-containing polymer (LE-304, silicone-based surface conditioner manufactured by Kyoeisha Chemical Co., Ltd.) as a surface conditioner were added and stirred until dissolved to obtain a photosensitive polyimide resin composition varnish. This photosensitive polyimide resin composition varnish was coated onto a silicon wafer to a dry film thickness of 30 μm and dried at 100°C for 5 minutes. Next, using a lithography machine (MIKASA MA-10B), the cumulative irradiation dose (calculated based on an illuminance of 365nm) was 250mJ / cm². 2The film was exposed to light from a high-pressure mercury lamp with wavelengths cut off below 365 nm and allowed to stand for 15 minutes. The cured resin film was then peeled off from the silicon wafer, and the elongation at break and Tg were measured. Here, when evaluating the developability of the thick film, 0.004 g of KP-390 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., a coating additive) was further added to the above-mentioned photosensitive polyimide resin composition varnish as an adhesion improver. The results are shown in Table 1.

[0241] Examples 2-7 and Comparative Examples 1-3

[0242] The types of multifunctional radical polymerizable compounds were changed to those shown in Table 1 below, and the cumulative irradiation dose was further changed to the values ​​shown in Table 1 below. Otherwise, the photosensitive resin composition was prepared in the same manner as in Example 1 above, and its properties were evaluated. The results are combined and shown in Table 1.

[0243] In the embodiments and comparative examples, the cumulative exposure dose (exposure dose) was calculated as follows: at 250 mJ / cm². 2 Above 5,000 mJ / cm 2 Within the following range, with multiple different cumulative radiation doses (250 mJ / cm²) 2 1,500 mJ / cm 2 2,000 mJ / cm 2 4,000 mJ / cm 2 and 5,000 mJ / cm 2 When these five points are exposed, the optimal cumulative irradiation dose achieves the best balance between thick film curability, thick film flexibility, and thick film heat resistance.

[0244] [Table 1]

[0245]

[0246] As shown in Table 1, using the photosensitive polyimide resin composition of the examples yields a resin film with a thickness of 30 μm, a high glass transition temperature, and high elongation at break. Furthermore, using the photosensitive polyimide resin composition of the examples results in a pattern free of residue in the spatial portions, and the photosensitive polyimide resin composition of the examples exhibits excellent thick-film developability. In other words, the photosensitive polyimide resin composition of the examples demonstrates an excellent balance between thick-film heat resistance, thick-film flexibility, and thick-film developability.

[0247] On the other hand, the photosensitive polyimide resin compositions of Comparative Examples 1 to 3 are thick films with a thickness of 30 μm, low elongation at break, and poor flexibility.

Claims

1. A photosensitive polyimide resin composition comprising a cyclic-closed polyimide resin (A) and a multifunctional radical polymerizable compound (B), wherein the cyclic-closed polyimide resin (A) has the structure shown in formula (1), and the multifunctional radical polymerizable compound (B) has a radical polymerizable functional group and an oxoalkylene group. The number of free radical polymerizable functional groups in the multifunctional free radical polymerizable compound (B) is more than 3 and less than 100. The total molar number of oxoalkylene additions in the polyfunctional radical polymerizable compound (B) is 5 or more and 100 or less. The oxoalkylene group comprises at least one selected from oxoethylene and oxopropylene. In formula (1), R is a tetravalent group formed by removing four hydrogen atoms from cyclohexane, cyclopentane, cyclobutane, dicyclopentane and their stereoisomers; A is a divalent group having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and organosiloxane groups, and having 2 or more and 39 or less carbon atoms, and the main chain of A may optionally contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O- and -S-; n represents the number of repeating units; the end of formula (1) is any of the groups or hydrogen atoms shown in formula (2) or formula (3) below, and at least one end is a group shown in formula (2) or formula (3) below. In equations (2) and (3), X and X 2 Each is an independent group having 2 or more but less than 15 carbon atoms, and may be selected from at least one group consisting of ester bonds and double bonds; Y and Y 2 Each can be a hydrogen atom or a methyl group independently.

2. The photosensitive polyimide resin composition according to claim 1, wherein, The closed-ring polyimide resin (A) has a weight-average molecular weight of 5,000 or more and 70,000 or less.

3. The photosensitive polyimide resin composition according to claim 1 or 2, wherein, When the total solid content of the photosensitive polyimide resin composition is set to 100% by mass, the content of the closed-ring polyimide resin (A) is 30% by mass or more.

4. The photosensitive polyimide resin composition according to claim 1 or 2, wherein, When the amount of the closed-ring polyimide resin (A) in the photosensitive polyimide resin composition is set to 100 parts by mass, the content of the multifunctional free radical polymerizable compound (B) is 20 parts by mass or more and 100 parts by mass or less.

5. The photosensitive polyimide resin composition according to claim 1 or 2, wherein, The free radical polymerizable functional group includes (meth)acryloyl.

6. The photosensitive polyimide resin composition according to claim 1 or 2, wherein The number of free radical polymerizable functional groups in the multifunctional free radical polymerizable compound (B) is 6 or more.

7. The photosensitive polyimide resin composition according to claim 1 or 2, wherein The number-average molecular weight of the polyfunctional free radical polymeric compound (B) is 500 or more and 10,000 or less.

8. The photosensitive polyimide resin composition according to claim 1 or 2, wherein The resin film with a thickness of 30 μm has an elongation at break of 8% or more. The 30 μm thick resin film is obtained as follows: the photosensitive polyimide resin composition is pre-baked at 100°C for 5 minutes at a temperature of 250 mJ / cm². 2 Above 5,000 mJ / cm 2 The product is obtained by irradiating the light from a high-pressure mercury lamp with wavelengths cut off below 365nm with the optimal exposure within the following range, followed by heat treatment at 200°C for 2 hours under a nitrogen atmosphere.

9. The photosensitive polyimide resin composition according to claim 1 or 2, wherein, The glass transition temperature of the 30 μm thick resin film is above 180°C. The 30 μm thick resin film is obtained as follows: the photosensitive polyimide resin composition is pre-baked at 100°C for 5 minutes at a temperature of 250 mJ / cm². 2 Above 5,000 mJ / cm 2 The product is obtained by irradiating the light from a high-pressure mercury lamp with wavelengths cut off below 365nm with the optimal exposure within the following range, followed by heat treatment at 200°C for 2 hours under a nitrogen atmosphere.

10. The photosensitive polyimide resin composition according to claim 1 or 2, wherein The closed-ring polyimide resin (A) has a transmittance of over 80% at a wavelength of 365 nm when prepared as a solution with a solid content concentration of 3% by mass.

11. The photosensitive polyimide resin composition according to claim 1 or 2, wherein In formula (1), A contains an aromatic ring as an aromatic hydrocarbon group.

12. The photosensitive polyimide resin composition according to claim 1 or 2, wherein In the formula (1), A comprises at least one of the structures selected from the group consisting of the structures shown below. In the formula, * represents a connector key.

13. The photosensitive polyimide resin composition according to claim 1 or 2, wherein, The closed-ring polyimide resin (A) comprises at least one unit selected from 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 4,4'-oxybis[3-(trifluoromethyl)aniline], or 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene.

14. The photosensitive polyimide resin composition according to claim 1 or 2, further comprising at least one selected from the group consisting of a photopolymerization initiator, a solvent, an adhesion improver, a surface conditioner, and a sensitizer.

15. The photosensitive polyimide resin composition according to claim 1 or 2, used to form an insulating film.

16. A resin film formed from any one of the photosensitive polyimide resin compositions according to claims 1 to 15 or a cured product of the photosensitive polyimide resin composition.

17. The resin film according to claim 16, wherein the film thickness is 20 μm or more.

18. An electronic device comprising the resin film of claim 17.

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