Photosensitive resin composition, method for producing a cured film, and method for producing a cured relief pattern

Abstract

The objective is to provide a photosensitive resin composition that exhibits excellent resolution and reduces copper voids upon contact with copper, even when using a polymer with high absorbance that gives a high glass transition temperature (Tg); a method for producing a cured film containing a polyimide obtained by curing the photosensitive resin composition; and a method for producing a cured relief pattern using the photosensitive resin composition. [Solution] A photosensitive resin composition, (A)(A1) A polymer which is a soluble polyimide or (A2) a polyimide precursor, (B) Photopolymerization initiator, N-ethyl-2-pyrrolidone and, (E) Photopolymerizable unsaturated monomers, (X) At least one selected from the group consisting of toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone, Includes, A photosensitive resin composition in which the content of (X) relative to the total mass of the photosensitive resin composition is 1 ppm or more and 10,000 ppm or less.

Description

Technical Field

[0001] The present disclosure relates to a photosensitive resin composition, a method for manufacturing a cured film, a method for manufacturing a cured relief pattern, and the like.

Background Art

[0002] Conventionally, polyimide resins having excellent heat resistance, electrical properties, and mechanical properties have been used for insulating materials of electronic components and for passivation films, surface protection films, interlayer insulating films, etc. of semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor composition can easily form a heat-resistant relief pattern film by coating, exposing, developing, and heat imidization treatment by curing of the composition. Such a photosensitive polyimide precursor composition has a feature that it enables a significant reduction in the manufacturing process compared to conventional non-photosensitive polyimide materials.

[0003] By the way, semiconductor devices (hereinafter also referred to as "devices") are mounted on printed boards by various methods according to the purpose. Conventionally, devices have generally been manufactured by a wire bonding method in which thin wires are used to connect from the external terminals (pads) of the device to the lead frame. However, with the progress of the high-speed operation of devices and the operating frequency reaching gigahertz (GHz), the difference in the wiring length of each terminal in the mounting has come to affect the operation of the device. Therefore, in the mounting of high-end devices, it has become necessary to accurately control the length of the actual wiring, and it has become difficult to meet this requirement with wire bonding.

[0004] Therefore, flip-chip mounting has been proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on top of it, and then the chip is flipped over and directly mounted on a printed circuit board. Because this flip-chip mounting allows for precise control of the wiring distance, it has been adopted for high-end devices that handle high-speed signals, and because of its small mounting size, it has been adopted for mobile phones and the like, and demand is rapidly expanding. Furthermore, recently, a semiconductor chip mounting technology called fan-out wafer-level packaging (FOWLP) has been proposed, in which individual chips are manufactured by dicing a wafer that has undergone pre-processing, the individual chips are reconstructed on a support and sealed with molding resin, and then the redistribution layer is formed after peeling off the support (for example, Patent Document 1). FOWLP has the advantage of being able to reduce the height of the package and achieve high-speed transmission or cost reduction. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2005-167191 [Overview of the project] [Problems that the invention aims to solve]

[0006] Recently, with the increasing size of semiconductor packages, high glass transition temperatures (Tg) are required for the insulating films that make up the redistribution layers. Increasing the concentration of imide groups is effective in raising the Tg of heat-resistant resins such as polyimide, but in that case, the absorbance of the polyimide resin tends to increase, and the resolution tends to deteriorate. Furthermore, when polyimide resins with a high concentration of imide groups come into contact with copper used in the redistribution layer, copper atoms diffuse into the polyimide, causing voids on the copper surface, which poses a problem of poor conductivity, especially in the case of fine wiring.

[0007] Therefore, the present disclosure aims to provide a photosensitive resin composition that exhibits excellent resolution and reduces copper voids when in contact with copper, even when using a polymer with high absorbance that gives a high glass transition temperature (Tg); a method for producing a cured film containing a polyimide obtained by curing the photosensitive resin composition; and a method for producing a cured relief pattern using the photosensitive resin composition. [Means for solving the problem]

[0008] Examples of embodiments of this disclosure are listed below. [1] A photosensitive resin composition, (A)(A1) A polymer which is a soluble polyimide or (A2) a polyimide precursor, (B) Photopolymerization initiator, N-ethyl-2-pyrrolidone and, (E) Photopolymerizable unsaturated monomers, (X) At least one selected from the group consisting of toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone, Includes, A photosensitive resin composition in which the content of (X) relative to the total mass of the photosensitive resin composition is 1 ppm or more and 10,000 ppm or less. [2] The photosensitive resin composition according to [1], wherein (X) comprises at least one selected from the group consisting of toluene and tetrahydrofuran. [3] The photosensitive resin composition according to [1] or [2], comprising 5% by mass or more of the N-ethyl-2-pyrrolidone based on the total mass of the photosensitive resin composition. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the i-line absorbance is 0.05 to 1.3 when the absorbance is measured with an N-ethyl-2-pyrrolidone solution having a concentration of polymer (A) of 0.1% by mass. [5] The photosensitive resin composition according to [4], wherein the i-line absorbance is 0.7 to 1.2. [6] The soluble polyimide (A1) is represented by the following general formula (1): [Chemical Formula] {In formula (1), X represents a tetravalent organic group having 4 to 32 carbon atoms, Y is a divalent organic group having 4 to 40 carbon atoms, and n2 represents an integer of 2 to 150.} The photosensitive resin composition according to any one of [1] to [5], comprising a structural unit represented by the above formula. [7] X is represented by the following general formulas (2) to (7): [Chemical Formula] [Chemical Formula] [Chemical Formula]<00000​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ A photosensitive resin composition according to any one of [1] to [8], comprising a structural unit represented by {formula (1'), where X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R1 and R2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms}.

[10] The above X1 is given by the following general formulas (13) to (15): [ka] [ka] [ka] The photosensitive resin composition according to [9], wherein at least one structure is selected from those represented by [9].

[11] The above Y1 is given by the following general formulas (16) to (18): [ka] [ka] [ka] A photosensitive resin composition according to [9] or

[10] , wherein the structure is selected from at least one of the structures represented by [1].

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

[11] , wherein the (B) photopolymerization initiator is an oxime compound.

[13] The aforementioned (B) photopolymerization initiator is defined by the following general formulas (19) to (21): [ka] {In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents a monovalent organic group with 1 to 20 carbon atoms. Rc represents a monovalent organic group with 1 to 10 carbon atoms. Rd represents a monovalent organic group with 1 to 10 carbon atoms. [ka] {In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, Rf represents a monovalent organic group with 1 to 10 carbon atoms. [ka] {In the formula, Rg represents a monovalent organic group having 1 to 20 carbon atoms, Rh represents a monovalent organic group with 1 to 10 carbon atoms. Ri represents a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms. A photosensitive resin composition according to any one of [1] to

[12] , wherein the structure is selected from at least one of the structures represented by [1].

[14] (D) A photosensitive resin composition according to any one of [1] to

[13] , further comprising a nitrogen-containing heterocyclic compound.

[15] The photosensitive resin composition according to

[14] , wherein the (D) nitrogen-containing heterocyclic compound is at least one selected from triazole compounds, tetrazole compounds, and purine compounds.

[16] A method for producing a cured film containing polyimide, comprising the step of curing a photosensitive resin composition described in any of [1] to

[15] to form a cured film containing polyimide.

[17] The following steps: (1) A step of applying a photosensitive resin composition described in any of [1] to

[15] to a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including [the specified element]. [Effects of the Invention]

[0009] This disclosure provides a photosensitive resin composition that exhibits excellent resolution and reduces copper voids upon contact with copper, even when using a polymer with high absorbance that gives a high glass transition temperature (Tg); a method for producing a cured film containing a polyimide obtained by curing the photosensitive resin composition; and a method for producing a cured relief pattern using the photosensitive resin composition. [Modes for carrying out the invention]

[0010] <Photosensitive resin composition> The photosensitive resin composition of this disclosure is (A)(A1) A polymer that is a soluble polyimide or (A2) a polyimide precursor (hereinafter referred to as (A) polymer), (B) Photopolymerization initiator, N-ethyl-2-pyrrolidone and, (E) Photopolymerizable unsaturated monomers, (X) At least one selected from the group consisting of toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone. Including, The photosensitive resin composition is one in which the content of (X) relative to the total mass of the photosensitive resin composition is 1 ppm or more and 10,000 ppm or less. The photosensitive resin composition of this embodiment can be used as a negative-type photosensitive resin composition.

[0011] At least one polymer selected from (A1) soluble polyimide and (A2) polyimide precursor according to this embodiment will be described. In this embodiment, the (A1) soluble polyimide and (A2) polyimide precursor ((A) polymer) preferably have an i-line absorbance of 0.05 to 1.3, and more preferably 0.7 to 1.2, when the absorbance is measured with a 0.1% by mass N-ethyl-2-pyrrolidone solution of (A) polymer. If the i-line absorbance is 0.05 or higher, the Tg of the cured film tends to be sufficiently high, and if it is 1.3 or lower, light reaches the bottom of the film during development, and the resolution tends to be good. The lower limit of the i-line absorbance is preferably 0.1 or higher, more preferably 0.3 or higher, particularly preferably 0.5 or higher, and even more preferably 0.7 or higher. The upper limit of the i-line absorbance is preferably 1.25 or lower, more preferably 1.2 or lower, particularly preferably 1.15 or lower, and even more preferably 1.1 or lower. The absorbance of an N-ethyl-2-pyrrolidone solution having a concentration of 0.1% by mass of (A1) soluble polyimide or (A2) polyimide precursor according to this embodiment is measured by the method described in the examples.

[0012] The photosensitive resin composition of this embodiment comprises (A) a polymer (in one embodiment, (A1) a soluble polyimide or (A2) a polyimide precursor).

[0013] (A1) Soluble polyimide The (A1) soluble polyimide in this embodiment is not limited as long as it can be dissolved in a general organic solvent, but it is preferable that it dissolves in N-ethyl-2-pyrrolidone used in this embodiment at a concentration of 5% by mass or more.

[0014] The (A1) soluble polyimide in this embodiment is not limited as long as it can dissolve in a general organic solvent, but from the viewpoint of chemical resistance and elongation, it is preferable that it does not contain fluorine atoms.

[0015] In this embodiment, the (A1) soluble polyimide preferably has photopolymerizable functional groups at the ends of the main chain and / or side chains from the viewpoint of chemical resistance. The presence of photopolymerizable functional groups in the (A1) soluble polyimide can improve resolution.

[0016] Here, the term "photopolymerizable functional group" is not limited to any functional group that can be polymerized by light irradiation. Examples of such functional groups include methacryloyl groups, acryloyl groups, methacrylamide groups, acrylamide groups, and styryl groups. From the viewpoint of resolution, at least one selected from methacryloyl groups, acryloyl groups, and styryl groups is preferred.

[0017] In this embodiment, the main chain end refers to the terminal structure of a soluble polyimide main chain composed of an acidic dianhydride and a diamine. The method for introducing photopolymerizable functional groups to the polyimide main chain ends is not particularly limited. Photopolymerizable functional groups can be introduced to the acidic dianhydride and / or diamine before polycondensation of the acidic dianhydride and diamine, or photopolymerizable functional groups can be introduced to the main chain end structure after obtaining a soluble polyimide.

[0018] In this embodiment, the side chain terminus refers to the side chain structure of a soluble polyimide main chain composed of an acidic dianhydride and a diamine. The method for introducing photopolymerizable functional groups to the polyimide side chain terminus is not particularly limited. Photopolymerizable functional groups can be introduced to the acidic dianhydride and / or diamine before polycondensation of the acidic dianhydride and diamine, or photopolymerizable functional groups can be introduced to the side chain structure after obtaining a soluble polyimide.

[0019] The (A1) soluble polyimide according to this embodiment is given by the following general formula (1): [ka] The structure may include the structural unit represented by {In formula (1), X represents a tetravalent organic group having 4 to 32 carbon atoms, Y represents a divalent organic group having 4 to 40 carbon atoms, and n² represents an integer from 2 to 150.}. In general formula (1), n2 is not limited to any integer between 2 and 150, but from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition, an integer between 3 and 100 is preferred, and an integer between 5 and 70 is more preferred.

[0020] In general formula (1), X is not limited to any tetravalent organic group having 4 to 32 carbon atoms, but from the viewpoint of chemical resistance, it is preferable that X has 6 or more carbon atoms, more preferably 8 or more, and particularly preferable 10 or more. From the viewpoint of resolution, the number of carbon atoms in X is preferably 30 or less, more preferably 28 or less, and particularly preferable 26 or less.

[0021] In general formula (1), Y is not limited to any divalent organic group having 4 to 40 carbon atoms, but from the viewpoint of chemical resistance, the number of carbon atoms in Y is preferably 6 or more, more preferably 8 or more, and particularly preferably 10 or more. From the viewpoint of resolution, the number of carbon atoms in Y is preferably 30 or less, more preferably 28 or less, and particularly preferably 26 or less.

[0022] In this embodiment, X preferably contains an aromatic group, and is defined by the following general formulas (2) to (7): [ka] [ka] [ka] [ka] [ka] [ka] It is more preferable to include at least one selected from the structures represented by . From the viewpoint of the glass transition temperature (Tg) after heat curing, X in this embodiment preferably includes at least one selected from the group consisting of structures represented by the general formulas (3) and (4) above. From the viewpoint of the elongation of the cured film after heat curing, it is preferable to include at least one selected from the group consisting of structures represented by the general formulas (2) and (5). From the viewpoint of resolution, X in this embodiment preferably includes the structure represented by the general formula (7).

[0023] In this embodiment, Y preferably has an aromatic group, and is represented by the following general formulas (8), (9), and (30): [ka] [ka] [ka] It is more preferable to include at least one selected from the structures represented by .

[0024] (A1) Method for preparing soluble polyimide (A1) A method for preparing soluble polyimide is to polycondense a tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X with a diamine containing the aforementioned divalent organic group Y to obtain polyamic acid, and then heat-treat it to obtain (A1) soluble polyimide.

[0025] (Preparation of polyamic acid) (A1) A tetracarboxylic dianhydride containing a tetravalent organic group X is suitable for preparing polyamic acid, which is a precursor of soluble polyimide, and is given the following general formula (1T): [ka] A compound represented by {In the above formula (1T), X is as defined in the above general formula (1)} is preferred.

[0026] Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (also known as oxydiphthalic acid dianhydride, abbreviated as "ODPA"), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (abbreviated as "BPDA"), diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. Preferred tetracarboxylic dianhydrides include, but are not limited to, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, as well as tetracarboxylic dianhydrides represented by the following general formulas (2T) to (7T). These may be used individually or in combination of two or more. Among these, the following general formulas (2T) to (7T): [ka] [ka] [ka] [ka] [ka] [ka] Tetracarboxylic acid dianhydrides represented by are preferred.

[0027] Diamines containing a divalent organic group Y include those with the following general formula (1D): H2N-Y-NH2(1D) Compounds represented by {wherein Y is as defined in the general formula (1) above} are preferred.

[0028] Examples of diamines include p-phenylenediamine (abbreviated as "pPD"), m-phenylenediamine, 4,4'-diaminodiphenyl ether (abbreviated as "4,4'-DADPE", also known as 4,4'-oxydianiline, abbreviated as "ODA"), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, and 3,3'-diamine Nodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl (abbreviated as "m-TB"), 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3 -aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4- (Aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone and 9,9-bis(4-aminophenyl)fluorene, etc., and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., for example, 3,Examples include, but are not limited to, 3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethylthoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl, as well as diamines represented by the following general formulas (7D) to (9D). These can be used individually or in combination of two or more. Among these, the following general formulas (7D) to (9D): [ka] [ka] [ka] A diamine represented by is preferred.

[0029] Polyamic acid can be obtained by dissolving and mixing the above-mentioned tetracarboxylic dianhydride and the above-mentioned diamine in a solvent described later. For example, the reaction conditions involve stirring continuously for 4 to 10 hours at a temperature of 10 to 50°C. The resulting polyamic acid can be isolated and then subjected to an imidation reaction, or it can be subjected to the next imidation reaction without isolation.

[0030] (Preparation of soluble polyimides) The polyamic acid obtained above can be reacted at high temperature with an imidation catalyst added as needed to obtain soluble polyimide. Preferably, this can be carried out in a glass container equipped with a Dean-Stark apparatus by mixing toluene or xylene, which are azeotropic solvents with water. The reaction conditions are not limited as long as the desired soluble polyimide is obtained, but for example, stirring is continued for 4 to 10 hours at a reaction temperature of 150 to 230°C.

[0031] After the soluble polyimide reaction is complete and the mixture has cooled to near room temperature, the resulting polymer component can be added to a poor solvent to precipitate it. Furthermore, the polymer can be purified by repeating the redissolution and reprecipitation operations. After the purification of the polymer, the desired soluble polyimide can be isolated by vacuum drying. To improve the degree of purification, the solution of this polymer may be passed through a column packed with an anion exchange resin, a cation exchange resin, or both of these swollen with a suitable organic solvent, to remove ionic impurities.

[0032] (A1) The molecular weight of the soluble polyimide is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000, when measured by the weight-average molecular weight in terms of polystyrene by gel permeation chromatography. When the weight-average molecular weight is 8,000 or higher, the mechanical properties are good, and when the weight-average molecular weight is 150,000 or lower, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Furthermore, the weight-average molecular weight of (A1) soluble polyimide is measured by the method described in the examples.

[0033] The soluble polyimide according to this embodiment is given by the following general formulas (10) to (12): [ka] [ka] [ka] Examples include structures that include at least one of the structures represented by as a repeating unit.

[0034] (A2) Polyimide precursor The polyimide precursor in this embodiment is not limited to any precursor that becomes a polyimide upon cyclization, but the following general formula (1'): [ka] {In formula (1'), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R1 and R2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms.} It is preferable that the structural unit represented by [the symbol] is included.

[0035] The organic group in the above general formula (1') may be an organic group containing heteroatoms other than carbon and hydrogen, or an organic group consisting of carbon and hydrogen atoms. Examples of heteroatoms in this disclosure include nitrogen atoms, oxygen atoms, and sulfur atoms.

[0036] Preferably, at least one of R1 and R2 in general formula (1') is a group further comprising at least one polymerizable group selected from an acid polymerizable group, a base polymerizable group, and a radical polymerizable group. In this disclosure, an acid polymerizable group, a base polymerizable group, and a radical polymerizable group refer to a group that can be polymerized by the action of an acid, a base, or a radical, respectively. At least one of R1 and R2 in general formula (1') is given by the following general formula: [ka] It is preferable that the formula is a monovalent organic group represented by {wherein L1, L2, and L3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10.}. In general formula (1'), n1 is not limited to any integer between 2 and 150, but from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition, an integer between 3 and 100 is preferred, and an integer between 5 and 70 is more preferred.

[0037] (A2) Method for preparing polyimide precursors (A2) The polyimide precursor is obtained by reacting a tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X1 with photopolymerizable alcohols having unsaturated double bonds and optionally alcohols without unsaturated double bonds to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as the acid / ester), and then by amide polycondensation of this with diamines containing the aforementioned divalent organic group Y1.

[0038] (Preparation of acid / ester compounds) In this embodiment, the tetracarboxylic dianhydride containing the tetravalent organic group X1 that is suitably used to prepare the (A2) polyimide precursor is the aforementioned tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, and 2,2-bis(3) Examples of suitable dianhydrides include, but are not limited to, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride. These may be used individually or in combination of two or more. Among these, in terms of the Tg and resolution of the resulting polyimide, X1 is given by the following general formulas (13)~(15): [ka] [ka] [ka] It is preferable that the structure is selected from the structures represented by .

[0039] In this embodiment, suitable photopolymerizable alcohols having unsaturated double bonds for preparing (A2) polyimide precursors include, for example, 2-hydroxyethyl methacrylate, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples include 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0040] In addition to the above-mentioned photopolymerizable alcohols having unsaturated double bonds, alcohols without unsaturated double bonds, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol, can also be used in combination with a portion of these alcohols.

[0041] Furthermore, as a polyimide precursor, a non-photosensitive polyimide precursor prepared solely from alcohols that do not have the above-mentioned unsaturated double bonds may be used in combination with the photosensitive polyimide precursor. From the viewpoint of resolution, it is preferable that the non-photosensitive polyimide precursor be 200 parts by mass or less, based on 100 parts by mass of the photosensitive polyimide precursor.

[0042] By dissolving and mixing the above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohols in a solvent described later, in the presence of a basic catalyst such as pyridine, at a temperature of 20-50°C for 4-10 hours, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.

[0043] (Preparation of polyimide precursors) To the above acid / ester mixture (typically a solution in a solvent described later), a suitable dehydrating condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, is added and mixed under ice cooling to obtain a polyacid anhydride from the acid / ester mixture. To the polyacid anhydride, a diamine containing a divalent organic group Y1, which is preferably used in this embodiment, is added dropwise in a separate solvent, either dissolved or dispersed, and amide polycondensation is performed to obtain the desired polyimide precursor. Alternatively, the desired polyimide precursor can be obtained by acid-chloridizing the acid portion of the above acid / ester compound using thionyl chloride or the like, and then reacting it with a diamine compound in the presence of a base such as pyridine.

[0044] Examples of diamines containing the divalent organic group Y1 that are preferably used in this embodiment include the aforementioned diamines. Examples of diamines containing the divalent organic group Y1 include p-phenylenediamine (abbreviated as "pPD"), m-phenylenediamine, 4,4'-diaminodiphenyl ether (abbreviated as "4,4'-DADPE"), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl Nylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl (m-TB), 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminopheno Xy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-amino Phenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone and 9,Examples include, but are not limited to, 9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl, as well as mixtures thereof. Among these, from the viewpoint of improving the Tg and resolution of the resulting polyimide resin, Y1 is given by the following general formulas (16) to (18): [ka] [ka] [ka] It is preferable that the structure is selected from the structures represented by .

[0045] After the amide polycondensation reaction is complete, any water-absorbing by-products of the dehydrating condensation agent present in the reaction solution are filtered off as needed. Then, a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate it. Further purification of the polymer is performed by repeating the redissolution and reprecipitation operations. After the purification of the polymer, the target polyimide precursor is isolated by vacuum drying. To improve the degree of purification, the solution of this polymer may be passed through a column packed with anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0046] The molecular weight of the above (A2) polyimide precursor is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000, when measured by weight-average molecular weight in terms of polystyrene by gel permeation chromatography. When the weight-average molecular weight is 8,000 or more, the mechanical properties are good, and when the weight-average molecular weight is 150,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Furthermore, the weight-average molecular weight of the (A2) polyimide precursor is measured by the method described in the examples.

[0047] (B) Photopolymerization initiator The photosensitive resin composition of this embodiment contains (B) a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator or a photoacid generator.

[0048] Examples of photoradical polymerization initiators include benzophenone compounds such as benzophenone, o-benzoylmethyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; Acetophenone compounds such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; Thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; Benzyl compounds such as benzyl, benzyldimethyl ketal, and benzyl-β-methoxyethyl acetal; Benzoin compounds such as benzoin and benzoin methyl ether; Oxime compounds such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), and 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]propanone-1-(O-acetyloxime); Examples include N-arylglycine compounds such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazole compounds; titanocene compounds, etc.

[0049] Examples of preferred photoacid generators include α-(n-octanesulfonyloxyimino)-4-methoxybenzylcyanide.

[0050] (B) The photopolymerization initiator is not limited to the above examples. Among the above photopolymerization initiators, photoradical polymerization initiators are more preferred, and oxime compounds are even more preferred in terms of photosensitivity, with 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime) being particularly preferred.

[0051] (B) Among photopolymerization initiators, the oxime compounds are those with the following general formulas (19), (20), and (21) in terms of resolution: [ka] {In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents a monovalent organic group with 1 to 20 carbon atoms. Rc represents a monovalent organic group with 1 to 10 carbon atoms. Rd represents a monovalent organic group with 1 to 10 carbon atoms. [ka] {In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, Rf represents a monovalent organic group with 1 to 10 carbon atoms. [ka] {In the formula, Rg represents a monovalent organic group having 1 to 20 carbon atoms, Rh represents a monovalent organic group with 1 to 10 carbon atoms. Ri represents a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms. It is preferable that the structure is selected from the structures represented by .

[0052] In general formula (19), Ra is not limited to any monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of heat resistance, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group. Rb is not limited to any monovalent organic group having 1 to 20 carbon atoms, but from the viewpoint of resolution, it is preferable that it be a monovalent aromatic group having 6 to 20 carbon atoms, or a monovalent organic group derived from a heterocyclic compound having 5 to 20 carbon atoms. Rc is not limited to any monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of resolution, a monovalent organic group containing a saturated alicyclic structure having 3 to 10 carbon atoms is preferred. Rd is not limited to any monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of resolution, a monovalent organic group having 1 to 3 carbon atoms is preferred, and a methyl group, an ethyl group, or a propyl group is more preferred.

[0053] In general formula (20), Re is not limited to any monovalent organic group having 1 to 20 carbon atoms, but from the viewpoint of resolution, it is preferably a monovalent organic group having 5 to 20 carbon atoms, and more preferably a monovalent organic group having 6 to 15 carbon atoms. Rf is not limited to any monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of resolution, it is preferably a monovalent organic group having 1 to 3 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group.

[0054] In general formula (21), Rg is not limited to any monovalent organic group having 1 to 20 carbon atoms, but from the viewpoint of heat resistance, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, an ethyl group, or a propyl group is more preferred. Furthermore, Rg may be an organic group containing heteroatoms other than carbon and hydrogen, or an organic group consisting of carbon and hydrogen atoms. Examples of heteroatoms in this disclosure include nitrogen atoms, oxygen atoms, and sulfur atoms. Rh is not limited to any monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of resolution, a monovalent organic group having 2 to 9 carbon atoms or an aromatic group having 6 to 10 carbon atoms is preferred, a monovalent organic group having 2 to 8 carbon atoms is more preferred, and a phenyl group is particularly preferred. Furthermore, Rh may be an organic group containing heteroatoms other than carbon and hydrogen, or an organic group consisting of carbon and hydrogen atoms. Ri is not limited to a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of resolution, it is preferably a hydrogen atom or a monovalent organic group having 1 to 9 carbon atoms.

[0055] Among the structures represented by general formulas (19) to (21), the structure represented by general formula (21) is preferred from the viewpoint of resolution. In the structure represented by general formula (21), the following general formulas (22) to (24): [ka] [ka] [ka] It is particularly preferable that the structure includes at least one selected from the structures represented by .

[0056] (B) The content of the photopolymerization initiator is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the polymer (A). The above content is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or patternability, and preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition, based on 100 parts by mass of the polymer (A).

[0057] ·solvent The photosensitive resin composition according to this embodiment only needs to contain N-ethyl-2-pyrrolidone as a solvent, and its content is not particularly limited. The N-ethyl-2-pyrrolidone content is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 20% by mass or more, based on 100% by mass of the photosensitive resin composition of this embodiment (in one embodiment, the total mass of the photosensitive resin composition of this embodiment), from the viewpoint of dissolving polymers and additives. The N-ethyl-2-pyrrolidone content is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less, based on 100% by mass of the photosensitive resin composition of this embodiment.

[0058] The inventors of this embodiment speculate that the presence of N-ethyl-2-pyrrolidone as a solvent in the photosensitive resin composition provides the following effects. Conventionally, N-methyl-2-pyrrolidone and other solvents have been used for photosensitive resin compositions containing soluble polyimides or polyimide precursors. Although these solvents have high solubility, their hydrophilic nature, with a partition coefficient of -0.28 at 25°C, makes them less effective at dissolving nonpolar substances. On the other hand, photosensitive resin compositions containing soluble polyimides or polyimide precursors, by containing specific amounts of low-polarity toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone, exhibit remarkable effects such as excellent focus margin during development and the provision of a cured film with suppressed copper voids. However, because N-methyl-2-pyrrolidone is not very good at dissolving nonpolar substances for the reasons mentioned above, it was difficult to achieve both improved developability and copper void resistance. On the other hand, N-ethyl-2-pyrrolidone has a partition coefficient of 0.22 at 25°C and is hydrophobic, making it readily dissolves nonpolar substances. The photosensitive resin composition of this embodiment, by containing N-ethyl-2-pyrrolidone, can contain specific amounts of low-polarity toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone, making it possible to achieve both improved developability and copper void resistance. Here, the partition coefficient values ​​used in this disclosure are those calculated at 25°C using the ACD / LogP module of the ACD / Percepta platform from ACD / Labs (wherein the ACD / LogP module is an algorithmic method based on the QSPR (Quantitative Structure-Property Relationship) methodology using the 2D structure of the molecule).

[0059] The solvent in this embodiment may include other solvents as long as they do not adversely affect the performance. Examples of other solvents include amides, sulfoxides, ureas and their derivatives, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. Specifically, other solvents that can be used include, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, cyclohexanone, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, diethylene glycol dimethyl ether, 1,4-dichlorobutane, o-dichlorobenzene, anisole, xylene, and mesitylene.

[0060] From the viewpoint of copper adhesion, the other solvent is preferably at least one selected from the group consisting of ethyl lactate, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N,N-dimethylpropanamide. From the viewpoint of making it easier to achieve the effects of this embodiment, the content of other solvents is preferably 30% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total amount of solvent in the photosensitive resin composition of this embodiment as 100% by mass.

[0061] (D) Nitrogen-containing heterocyclic compound The photosensitive resin composition according to this embodiment may further contain (D) a nitrogen-containing heterocyclic compound. The inclusion of this compound improves copper adhesion.

[0062] The nitrogen-containing heterocyclic compound (D) in this embodiment is not limited to any heterocyclic compound containing a nitrogen atom, but from the viewpoint of improving copper adhesion, it is preferably at least one selected from triazole compounds, tetrazole compounds, and purine compounds, and a triazole compound (e.g., benzotriazole) is more preferred.

[0063] Specific examples of triazole compounds include, for example, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, and 2-(5-methyl-2-hydroxyphenyl)benzotriazole. Examples include 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, and 5-carboxy-1H-benzotriazole.

[0064] Specific examples of tetrazole compounds include, for example, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0065] Specific examples of purine compounds include, for example, purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminopurine. Examples include noadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, and 8-azahypoxanthine, as well as derivatives thereof.

[0066] When the photosensitive resin composition of this embodiment contains (D) a nitrogen-containing heterocyclic compound, the content is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of (A) polymer, and may be, for example, 0.01 to 5 parts by mass. When the content of (D) a nitrogen-containing heterocyclic compound is 0.01 parts by mass or more, based on 100 parts by mass of (A) polymer, the adhesion to copper is further improved when the photosensitive resin composition is formed on copper or a copper alloy, while when it is 20 parts by mass or less, the resolution is further improved.

[0067] (E) Photopolymerizable unsaturated monomer The photosensitive resin composition of this embodiment may contain (E) a photopolymerizable unsaturated monomer in order to improve the resolution of the relief pattern. In this disclosure, a photopolymerizable unsaturated monomer refers to a monomer having a photopolymerizable unsaturated bond that undergoes a radical polymerization reaction with a photopolymerization initiator. Such monomers are preferably (meth)acrylic compounds, but are not particularly limited. Examples of photopolymerizable unsaturated monomers include monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of ethylene glycol; Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of polyethylene glycol; Propylene glycol monoacrylate, diacrylate, monomethacrylate, and dimethacrylate; Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of polypropylene glycol; Glycerol monoacrylate, diacrylate, triacrylate, monomethacrylate, dimethacrylate, and trimethacrylate; Diacrylates and dimethacrylates of cyclohexane; Diacrylates and dimethacrylates of 1,4-butanediol; Diacrylates and dimethacrylates of 1,6-hexanediol; Neopentyl glycol diacrylates and dimethacrylates; Monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of bisphenol A; Benzene trimethacrylate; tris-(2-acryloxyethyl) isocyanurate; isobornyl acrylate and isoboronyl methacrylate; Acrylamide and its derivatives; methacrylamide and its derivatives; Trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; Examples include diacrylate, triacrylate, tetraacrylate, dimethacrylate, trimethacrylate, and tetramethacrylate of pentaerythritol; and compounds such as ethylene oxide adducts and propylene oxide adducts of these compounds. These can be used individually or in combinations of, for example, two to five types. Among the above (E) photopolymerizable unsaturated monomers, polyethylene glycol dimethacrylate or tris-(2-acryloxyethyl) isocyanurate is preferred.

[0068] (E) The content of the photopolymerizable unsaturated monomer is preferably 1 to 50 parts by mass based on 100 parts by mass of (A)(A1) soluble polyimide and (A2) polyimide precursor.

[0069] (X) At least one selected from the group consisting of toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone. The photosensitive resin composition according to this embodiment comprises (X)toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone, and preferably comprises toluene and at least one selected from the group consisting of tetrahydrofuran. The content of (X) in this embodiment is not limited as long as it is between 1 ppm and 10,000 ppm relative to the total mass of the photosensitive resin composition of this embodiment. The content is preferably 3 ppm or more, more preferably 5 ppm or more, and particularly preferably 10 ppm or more. The content is preferably 8,000 ppm or less, more preferably 5,000 ppm or less, particularly preferably 1,000 ppm or less, and most preferably 100 ppm or less.

[0070] In the photosensitive resin composition according to this embodiment, the reason why the resolution is improved and copper voids are suppressed by including a specific amount of at least one selected from the group consisting of (X)toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone is not clear, but the inventors believe it to be as follows. In other words, polyimide precursors and soluble polyimides that have a high Tg after curing tend to have a high concentration of imide groups in the polymer. Therefore, due to the high cohesive force of amide / imide groups, polyimide precursors and soluble polyimides tend to aggregate with each other. As a result, phase separation with photopolymerizable unsaturated monomers, which are important for negative patterning, is likely to occur, and crosslinking at the bottom is particularly insufficient, leading to a deterioration in resolution. In addition, when in contact with copper wiring, the contact area with polyimide, which is prone to copper atom diffusion, becomes large, making void formation more likely. On the other hand, by adding at least one substance selected from the group consisting of toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone according to this embodiment, it is presumed that these substances act as compatibilizers between the polyimide precursor / soluble polyimide and the photopolymerizable unsaturated monomer during pre-baking (solvent removal), resulting in a homogeneous film.

[0071] The content of (X) is such that if it is 1 ppm or more relative to the total mass of the photosensitive resin composition of this embodiment, it acts as a compatibilizer, and if it is 10,000 ppm or less, adverse effects such as pattern flow during development can be prevented. Furthermore, since (X) volatilizes during thermal curing at temperatures of 180°C to 230°C, it does not adversely affect the performance of the polyimide cured film. The content of (X) in the photosensitive resin composition of this embodiment can be adjusted by preparing a composition containing (A) polymer, (B) photopolymerization initiator, N-ethyl-2-pyrrolidone, and (E) photopolymerizable unsaturated monomer, and then adding (X) to achieve the desired concentration. Furthermore, if the concentration of (X) may change after the preparation of the photosensitive resin composition due to the inclusion of a solvent with a low boiling point, the content of (X) in the photosensitive resin composition may be quantified using gas chromatography or the like, and then the content of (X) may be adjusted by adding additional (X) to achieve the desired concentration.

[0072] • Hindered phenol compounds To suppress discoloration on the copper surface, the photosensitive resin composition of this embodiment may optionally contain a hindered phenol compound.

[0073] Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), trie Tylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4- Ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-Dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-Trione, 1,3,5-Tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(4-t-butyl-6-ethyl-3- Hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-( Examples include, but are not limited to, 1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0074] Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0075] The content of the hindered phenol compound in the photosensitive resin composition of this embodiment is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of polymer (A). When the content of the hindered phenol compound based on 100 parts by mass of polymer (A) is 0.1 parts by mass or more, for example, when the photosensitive resin composition of this disclosure is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented. On the other hand, when the content of the hindered phenol compound based on 100 parts by mass of polymer (A) is 20 parts by mass or less, the photosensitivity is excellent.

[0076] • Organic titanium compounds The photosensitive resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound, the photosensitive resin composition of this embodiment can form a photosensitive resin layer with excellent chemical resistance even when cured at low temperatures.

[0077] Examples of organotitanium compounds usable in this embodiment include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0078] Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the photosensitive resin composition of this embodiment and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxide bis(2,4-pentanedione), titanium diisopropoxide bis(tetramethylheptanedione), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, and titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}]. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium and bis(η 5 Examples include -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide and titanium tris(dodecylbenzenesulfonate) isopropoxide. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), and phthalocyanine titanium oxide. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0079] In particular, as an organotitanium compound, it is preferable that it be at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of achieving better chemical resistance. Especially titanium diisopropoxide bis(ethyl acetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium is preferred.

[0080] When the photosensitive resin composition of this embodiment contains an organic titanium compound, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of polymer (A). When the content is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance, while when it is 10 parts by mass or less, the photosensitive resin composition exhibits excellent storage stability.

[0081] • Adhesion aid To improve the adhesion between the film formed using the photosensitive resin composition of this embodiment and the substrate, the photosensitive resin composition of this embodiment may optionally contain an adhesive aid. Aluminum-based adhesives and silane coupling agents can be used as bonding aids.

[0082] Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0083] Examples of silane coupling agents include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, and N-(3-diethoxymethylsilyl Propyl) succinimide, N-[3-(triethoxysilyl)propyl]phthalamidic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, 3-Mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name KBM803, manufactured by Chisso Corporation: product name Cyra Ace S810), 3-Mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6475.0), 3-Mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, manufactured by Azmax Co., Ltd.: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyl Diethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS3610, manufactured by Azmax Co., Ltd.: product name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: product name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea , N-(3-ethoxydimethoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: product name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxy)silane, tetrakis(methoxy-n-propoxy)silane , tetrakis(ethoxyethoxy)silane, tetrakis(methoxyethoxyethoxy)silane, bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, Phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutyl Methylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethyl isopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, etc., as well as the following general formula (S-1): [ka] Examples of silane coupling agents include, but are not limited to, those represented by the respective terms.

[0084] Among these adhesive aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. As a silane coupling agent, from the viewpoint of storage stability, it is preferable to use one or more selected from the group consisting of phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the silane coupling agents represented by the above general formula (S-1).

[0085] If the photosensitive resin composition of this embodiment contains an adhesive aid, the content of the adhesive aid is preferably in the range of 0.01 to 25 parts by mass, and more preferably in the range of 0.5 to 20 parts by mass, based on 100 parts by mass of (A) polymer. If a silane coupling agent is used as the adhesive aid, its content is preferably 0.01 to 20 parts by mass, based on 100 parts by mass of (A) polymer.

[0086] • Sensitizer The photosensitive resin composition of this embodiment may optionally contain a sensitizer to improve light sensitivity. Examples of the sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamyridene indanone. p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl- Examples include 7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine (DEA), Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These can be used individually or in combinations of, for example, 2 to 5 types. Among the sensitizers mentioned above, N-phenyldiethanolamine (DEA) is preferred.

[0087] If the photosensitive resin composition of this embodiment contains a sensitizer to improve light sensitivity, the amount thereof is preferably 0.1 to 25 parts by mass based on 100 parts by mass of polymer (A).

[0088] • Thermal polymerization inhibitor The photosensitive resin composition of this embodiment may optionally contain a thermal polymerization inhibitor to improve the stability of viscosity and photosensitivity, especially when stored in a solvent-containing solution. Examples of thermal polymerization inhibitors that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0089] <Method for manufacturing hardened relief patterns> The method for manufacturing the cured relief pattern of this disclosure is: (1) A step of applying the photosensitive resin composition of the present disclosure described above to a substrate to form a photosensitive resin layer on the substrate (resin layer formation step), (2) A step of exposing the above photosensitive resin layer (exposure step), (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern (relief pattern formation step), (4) The process includes a step of heat-treating the relief pattern to form a hardened relief pattern (hardened relief pattern formation step).

[0090] (1) Resin layer formation process In this process, a photosensitive resin composition is applied to the surface of a substrate, and if necessary, it is then dried to form a photosensitive resin layer. Conventional application methods for photosensitive resin compositions can be used, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or spray coating using a spray coater.

[0091] If necessary, the coating containing the photosensitive resin composition can be dried. Drying methods include air drying, heating with an oven or hot plate, and vacuum drying. Specifically, in the case of air drying or heating, drying can be carried out at a temperature of 20°C to 150°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the surface of the substrate.

[0092] (2) Exposure process In this process, the photosensitive resin layer formed above is exposed to ultraviolet light or the like, either through a patterned photomask or reticle, or directly, using an exposure device such as a contact aligner, mirror projection, or stepper. This exposure causes the polymerizable groups of the soluble polyimide contained in the photosensitive resin composition and / or the polymerizable groups of (E) the photopolymerizable unsaturated monomer to crosslink due to the action of (B) the photopolymerization initiator. This crosslinking makes the layer insoluble in the developer used in the exposure area, as described later, thus enabling the formation of a relief pattern.

[0093] Subsequently, if necessary, post-exposure baking (PEB), pre-development baking, or both may be performed using any combination of temperature and time, for purposes such as improving photosensitivity. The baking conditions are preferably a temperature of 40°C to 120°C and a time of 10 to 240 seconds, but are not limited to this range as long as they do not impair the properties of the photosensitive resin composition of this embodiment.

[0094] (3) Relief pattern formation process In this process, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. The development method for developing the photosensitive resin layer after exposure (irradiation) can be selected from any of the conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment. After development, post-development baking may be performed using any combination of temperature and time, if necessary, for purposes such as adjusting the shape of the relief pattern.

[0095] As the developer used for development, for example, a good solvent for the photosensitive resin composition of this embodiment, or a combination of the good solvent and a poor solvent is preferred. Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition of this embodiment. Two or more solvents, for example, several types, can also be used in combination.

[0096] (4) Hardened relief pattern formation process In this process, the relief pattern obtained by the above development is heat-treated to volatilize the photosensitive component and convert it into a hardened relief pattern. Various methods can be selected for the heat treatment, such as using a hot plate, using an oven, or using a heating oven with a temperature programmable. The heat treatment can be carried out, for example, at 150°C to 350°C for 30 minutes to 5 hours. The heat treatment temperature is preferably 150°C to 250°C, more preferably 150°C to 230°C, and even more preferably 170°C to 230°C. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

[0097] <Method for producing a cured film containing polyimide> Another aspect of the present disclosure provides a method for producing a polyimide-containing cured film, comprising the step of curing the photosensitive resin composition described above to form a cured film containing polyimide. The curing conditions for the photosensitive resin composition in this embodiment may be, for example, the same as the baking conditions included in the method for producing a cured relief pattern described above, or the conditions for the cured relief pattern formation step (4).

[0098] <Semiconductor device> This disclosure also provides a semiconductor device having a cured relief pattern obtained from the above-described photosensitive resin composition. More specifically, a semiconductor device is provided having a substrate which is a semiconductor element and a cured relief pattern. The cured relief pattern may be manufactured using the above-described photosensitive resin composition by the above-described method for manufacturing a cured relief pattern.

[0099] This disclosure can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor element as a substrate and includes the method for manufacturing the cured relief pattern described above as part of the process. In this case, the cured relief pattern formed by the method for manufacturing the cured relief pattern of this disclosure can be formed as a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and can be manufactured by combining it with a known method for manufacturing a semiconductor device.

[0100] <Display device> This disclosure provides a display device comprising a display element and a cured film provided on the upper part of the display element, wherein the cured film is the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or it may be laminated with another layer in between. The cured film can be applied, for example, to surface protective films, insulating films, planarization films, etc., of TFT liquid crystal display elements and color filter elements; protrusions for MVA type liquid crystal display devices; partitions for the cathodes of organic EL elements; etc.

[0101] In addition to applications in semiconductor devices as described above, the photosensitive resin composition of this disclosure is also useful for applications such as interlayer insulation of multilayer circuits, cover coatings for flexible copper-clad sheets, solder resist films, and liquid crystal alignment films. [Examples]

[0102] <Measurement and Evaluation Methods> (1) Weight average molecular weight The weight-average molecular weight (Mw) of each resin was measured using gel permeation chromatography (on a standard polystyrene basis) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Columns: Showa Denko Corporation Shodex KD-805 / KD-804 / KD-803 in series Standard monodisperse polystyrene: Shodex STANDARD SM-105, manufactured by Showa Denko Corporation. Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min.

[0103] (2) Absorbance measurement The absorbances of (A)(A1) soluble polyimide and (A2) polyimide precursor (hereinafter referred to as (A) polymer) were measured as follows. (A) An N-ethyl-2-pyrrolidone solution with a polymer concentration of 0.1% by mass was prepared and packed into a 1 cm quartz cell. The absorbance at 365 nm was then measured using a Shimadzu UV-1800 device with a medium scan speed and a sampling pitch of 0.5 nm. In cases where two types of polymer (A) were mixed, the absorbance of the mixed polymer was measured according to their respective weight ratios.

[0104] (3) Resolution evaluation (evaluation by focus margin) A 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm) was sputtered with 200nm thick Ti and then 400nm thick Cu in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation) to prepare a sputtered Cu wafer substrate. Using a spin coating apparatus (D-spin60A model, manufactured by SOKUDO Corporation), the photosensitive resin compositions prepared in the examples and comparative examples described below were spin-coated onto the sputtered Cu wafer substrate, and the mixture was heated and dried at 110°C for 240 seconds to produce a spin-coated film with a thickness of 5 μm after heat curing. Using a reticle with a test pattern having a circular pattern with a mask size of 5 μm in diameter, the optimal exposure level (the amount that yielded the best resolution) was determined using an FPA-3030iWa (manufactured by Canon), and the film was irradiated. In this process, using the spin-coated film surface as a reference, the focus was moved 2 μm towards the top and bottom of the film for each exposure dose, and exposure was performed accordingly. Next, the coating film formed on the sputtered Cu wafer substrate was spray-developed using cyclopentanone in a developing machine (D-SPIN636, manufactured by Dainippon Screen Co., Ltd.), and then rinsed with propylene glycol methyl ether acetate to obtain a circular recessed relief pattern of the photosensitive resin composition. The development time for spray development was defined as 1.4 times the minimum time required for the unexposed areas of the photosensitive resin composition to develop in the spin-coated film described above. Using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh), sputtered Cu wafer substrates with circular recessed relief patterns were heat-treated in a nitrogen atmosphere by raising the temperature to 200°C at a heating rate of 5°C / min and holding at 200°C for 2 hours. This process yielded circular recessed cured relief patterns of polyimide with a mask size of 5 μm on the sputtered Cu wafer substrates. For each obtained pattern, the pattern shape and width of the pattern area were observed under an optical microscope, and the focus margin (depth of focus) was determined.

[0105] <Resolution evaluation criteria based on focus pattern> Regarding the feasibility of opening a circular recessed hardened relief pattern, focus patterns that met both of the following criteria (I) and (II) were deemed acceptable and used to evaluate the resolution using the following focus margin. (I) The area of ​​the pattern opening is at least half the area of ​​the corresponding pattern mask opening. (II) The pattern cross section is not tapered, and there is no undercutting, swelling, or bridging.

[0106] When the focus of a focus pattern that satisfies the above evaluation criteria was moved 2 μm in the thickness direction of the focus pattern under an optical microscope, the distance at which the focus pattern no longer satisfies the above evaluation criteria was measured. The distance the focus was moved was used as the resolution evaluation criterion based on the focus margin described below to evaluate the resolution of the photosensitive resin compositions prepared in the examples, etc.

[0107] <Resolution evaluation criteria based on focus margin> Excellent: Even with a focus travel distance of 10 μm or more, the above <Resolution Evaluation Criteria by Focus Pattern> was met. Good: When the focus movement distance was 6 μm or more and less than 10 μm, the above <Resolution Evaluation Criteria by Focus Pattern> was met. However, when the focus movement distance was 10 μm or more, the above <Resolution Evaluation Criteria by Focus Pattern> was not met. Acceptable: When the focus movement distance was 2 μm or more and less than 6 μm, the above <Resolution Evaluation Criteria by Focus Pattern> was met. However, when the focus movement distance was 6 μm or more, the above <Resolution Evaluation Criteria by Focus Pattern> was not met. Failure: Even if the focus travel distance was less than 2 μm, the above <Resolution Evaluation Criteria by Focus Pattern> was not met.

[0108] (4) High-temperature storage test and copper void area evaluation of hardened relief patterns on Cu substrates The sputtered Cu wafer substrate, on which a cured relief pattern was formed in the same manner as in (3) above, was heated in air at 150°C for 168 hours and stored under high temperature conditions. Subsequently, the photosensitive resin layer on the sputtered Cu wafer substrate was completely removed by plasma etching using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.). The plasma etching conditions were as follows. Output: 133W Gas type: O2 + CF4 Gas flow rate: O2: 40 mL / min, CF4: 1 mL / min Gas pressure: 50 Pa Mode: Hard Mode Etching time: 1800 seconds

[0109] The surface of the Cu layer, from which the photosensitive resin layer had been completely removed, was observed using an FE-SEM (S-4800 model, manufactured by Hitachi High-Technologies Corporation), and the area of ​​voids on the surface of the Cu layer was calculated using image analysis software (A-Image-kun, manufactured by Asahi Kasei Corporation). When the total area of ​​voids in the photosensitive resin composition of Comparative Example 1 was evaluated, it was set to 100%. Those with a total void area ratio of less than 50% are classified as "Excellent". A total void area ratio of 50% or more but less than 75% is considered "good". Voids with a total area ratio of 75% or more but less than 100% are considered "acceptable". We determined that samples with a total void area ratio of 100% or more were "unacceptable".

[0110] <Manufacturing Example 1> In a flask equipped with a stirrer and condenser, 12.4 g (40.0 mmol) of 4,4'-oxydiphthalic acid dianhydride (ODPA) was dissolved in 100 g of N-methylpyrrolidone at a temperature between 20°C and 30°C. Subsequently, 15.3 g (37.2 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was added, and the mixture was stirred for 1 hour. Then, while flowing nitrogen, the temperature was raised to 190°C, stirred for 5 hours, and cooled to below 30°C. Subsequently, the mixture was diluted with 50 g of tetrahydrofuran, precipitated in 2 L of methanol, filtered, and recovered. The solution was then vacuum-dried at 45°C for 1 day to obtain soluble polyimide resin (A-1). The weight-average molecular weight of the obtained soluble polyimide (A-1) was 17,000.

[0111] <Manufacturing Example 2> 155 g (0.5 mol) of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a 2-liter separable flask, and 135 g (1.04 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 79.1 g of pyridine was added while stirring, and the mixture was stirred for 16 hours. Next, under ice cooling, a solution of 203 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, 89 g (0.44 mol) of 4,4'-diaminodiphenyl ether (4,4'-DADPE) suspended in 280 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 4 hours, 40 ml of ethyl alcohol was added and stirred for 1 hour, and then 1 liter of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution. The resulting reaction solution was added to 4 liters of ethyl alcohol to produce a precipitate consisting of crude polymer. The crude polymer was filtered off and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 30 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polymer A-2). The molecular weight of polymer A-2 was measured by gel permeation chromatography (on a standard polystyrene basis), and the weight-average molecular weight (Mw) was found to be 24,000.

[0112] <Manufacturing Example 3> Polymer A-3 was obtained by carrying out the reaction in the same manner as described in Preparation Example 2, except that 147 g (0.5 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155 g of ODPA. The weight-average molecular weight (Mw) of polymer A-3 was measured by gel permeation chromatography (on a standard polystyrene basis) and found to be 20,000.

[0113] <Manufacturing Example 4> Polymer A-4 was obtained by carrying out the reaction in the same manner as described in Preparation Example 2, except that 46 g (0.44 mol) of p-phenylenediamine (pPD) was used instead of 89 g of DADPE. The weight-average molecular weight (Mw) of polymer A-4 was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 19,000.

[0114] <Manufacturing Example 5> Polymer A-5 was obtained by carrying out the reaction in the same manner as described in Preparation Example 1, except that 62 g (0.2 mol) of ODPA and 65 g (0.3 mol) of pyromellitic dianhydride (PMDA) were used instead of 155 g of ODPA, and 94 g (0.44 mol) of 2,2'-dimethyl-4,4-diaminobiphenyl (m-TB) was used instead of 89 g of DADPE. The molecular weight of polymer A-5 was measured by gel permeation chromatography (on a standard polystyrene basis), and the weight-average molecular weight (Mw) was 20,000.

[0115] <Example 1> A negative-type photosensitive resin composition was prepared using the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1, (B) 6 g of 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)(B-1) as a photopolymerization initiator, 200 g of N-ethyl-2-pyrrolidone as a solvent, (D) 0.4 g of benzotriazole(D-1) as a nitrogen-containing heterocyclic compound, and (E) 30 g of polyethylene glycol dimethacrylate(E-1) as a photopolymerizable unsaturated monomer were added and dissolved to prepare a composition. To this composition, (X) toluene was added to a concentration of 10 ppm, and the mixture was further stirred to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated according to the method described above. The results are shown in Table 1. Furthermore, when a fan-out type wafer-level chip-size package semiconductor device was fabricated using this composition, it operated without any problems.

[0116] <Examples 2-23> A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1, except for the composition shown in Table 1. Furthermore, when a fan-out type wafer-level chip-size package semiconductor device was fabricated using this composition, it operated without any problems.

[0117] <Comparative Examples 1-3> A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1, except for the composition shown in Table 1. Furthermore, when a fan-out type wafer-level chip-size package semiconductor device was fabricated using this composition, it did not function.

[0118] [Table 1-1] [Table 1-2]

[0119] The descriptions of the components in Table 1 (in Table 1, when there is no indication of the numerical value of each component in ppm, it represents grams (g)) are shown below. The numerical value of (X) in Table 1 indicates the content of (X) with respect to the total mass of the photosensitive resin composition).

[0120] (A) Polymer ((A1) Soluble polyimide and (A2) Polyimide precursor) Polymers A-1 to A-5 synthesized in the above production examples

[0121] (B) Photoinitiator B-1: 1,2-Propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) B-2: The following general formula:

Chemical formula

Chemical formula

Chemical formula

[0122] Solvent N-Ethyl-2-pyrrolidone (NEP) Ethyl lactate​​​​​​​​​​​​​​​​​​​​​toluene xylene Tetrahydrofuran γ-Butyrolactone γ-Valerolactone

[0126] Sensitizer N-phenyldiethanolamine (DEA)

Claims

1. A photosensitive resin composition, (A) (A1) A polymer which is a soluble polyimide or (A2) a polyimide precursor, (B) Photopolymerization initiator, N-ethyl-2-pyrrolidone and, (E) Photopolymerizable unsaturated monomers, (X) At least one selected from the group consisting of toluene, xylene, tetrahydrofuran, γ-butyrolactone, and γ-valerolactone, Includes, A photosensitive resin composition in which the content of (X) relative to the total mass of the photosensitive resin composition is 1 ppm or more and 10,000 ppm or less.

2. The photosensitive resin composition according to claim 1, wherein (X) comprises at least one selected from the group consisting of toluene and tetrahydrofuran.

3. The photosensitive resin composition according to claim 1 or 2, wherein the N-ethyl-2-pyrrolidone is contained in an amount of 5% by mass or more based on the total mass of the photosensitive resin composition.

4. The photosensitive resin composition according to claim 1 or 2, wherein the i-line absorbance is 0.05 to 1.3 when the absorbance is measured with an N-ethyl-2-pyrrolidone solution having a concentration of polymer (A) of 0.1% by mass.

5. The photosensitive resin composition according to claim 4, wherein the i-line absorbance is 0.7 to 1.

2.

6. The aforementioned (A1) soluble polyimide is defined by the following general formula (1): 【Chemistry 1】 {In formula (1), X represents a tetravalent organic group having 4 to 32 carbon atoms, and Y represents a divalent organic group having 4 to 40 carbon atoms, n ２ This represents an integer between 2 and 150. A photosensitive resin composition according to claim 1 or 2, comprising a structural unit represented by .

7. The above X is given by the following general formulas (2) to (7): 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 The photosensitive resin composition according to claim 6, comprising at least one selected from the structures represented by .

8. The above Y is given by the following general formulas (8), (9), and (30): 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 The photosensitive resin composition according to claim 6, comprising at least one selected from the structures represented by .

9. The (A2) polyimide precursor is given by the following general formula (1'): 【Chemistry 11】 {In formula (1'), X １ Y is a tetravalent organic group having 4 to 40 carbon atoms. １ It is a divalent organic group having 6 to 40 carbon atoms, n １ is an integer between 2 and 150, and R １ and R ２ Each of these independently represents a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. The photosensitive resin composition according to claim 1 or 2, comprising a structural unit represented by}.

10. The aforementioned X １ However, the following general formulas (13) to (15): 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 The photosensitive resin composition according to claim 9, wherein the structure is selected from at least one of the structures represented by .

11. The aforementioned Y １ However, the following general formulas (16) to (18): 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 The photosensitive resin composition according to claim 9, wherein the structure is selected from at least one of the structures represented by .

12. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photopolymerization initiator is an oxime compound.

13. The aforementioned (B) photopolymerization initiator is one of the following general formulas (19) to (21): [Chemistry 18] {In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents a monovalent organic group with 1 to 20 carbon atoms. Rc represents a monovalent organic group with 1 to 10 carbon atoms. Rd represents a monovalent organic group with 1 to 10 carbon atoms. 【Chemistry 19】 {In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, Rf represents a monovalent organic group with 1 to 10 carbon atoms. 【Chemistry 20】 {In the formula, Rg represents a monovalent organic group having 1 to 20 carbon atoms, Rh represents a monovalent organic group with 1 to 10 carbon atoms. Ri represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. The photosensitive resin composition according to claim 1 or 2, wherein the structure is selected from at least one of the structures represented by .

14. (D) The photosensitive resin composition according to claim 1 or 2, further comprising a nitrogen-containing heterocyclic compound.

15. The photosensitive resin composition according to claim 14, wherein the (D) nitrogen-containing heterocyclic compound is at least one selected from triazole compounds, tetrazole compounds, and purine compounds.

16. A method for producing a cured film containing polyimide, comprising the step of curing the photosensitive resin composition according to claim 1 or 2 to form a cured film containing polyimide.

17. The following steps: (1) A step of applying the photosensitive resin composition according to claim 1 or 2 to a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including [the specified element].

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