Photosensitive resin composition

Abstract

The photosensitive resin composition contains: 100 parts by mass of a polyimide precursor represented by the following general formula (1); 0.5 to 10 parts by mass of a photosensitizer; and 100 to 300 parts by mass of a solvent. The imidization rate, which is the value obtained by dividing the peak intensity near 1380 cm ‑1 in the infrared absorption spectrum of the photosensitive resin layer immediately before exposure, which is obtained by removing the solvent from the photosensitive resin composition, by the peak intensity near 1500 cm ‑1 in the infrared absorption spectrum of the photosensitive resin layer, and then dividing the resulting imidization index of the photosensitive resin layer by the imidization index of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 °C, is 15% to 50%. In the polyimide of the polyimide cured film, the proportion of imide groups in each repeating unit, that is, the imide group concentration, is 12 wt% to 30 wt%. In the formula, X1, Y1, n1, R1, and R2 are defined in claim 1.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to: a negative photosensitive resin composition that exhibits a low dielectric loss tangent, excellent storage stability, and can form a cured relief pattern with high resolution; a method for producing the same; and a method for producing a polyimide cured film using the negative photosensitive resin composition. Background Art

[0002] Conventionally, polyimide resins having excellent heat resistance, electrical properties, and mechanical properties have been used in insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, etc. of semiconductor devices. Among these polyimide resins, a polyimide resin provided in the form of a photosensitive polyimide precursor composition can easily form a heat-resistant cured relief pattern coating film through thermal imidization treatment based on coating, exposure, development, and curing of the composition. Such a photosensitive polyimide precursor composition has the characteristic of being able to significantly shorten the process compared to conventional non-photosensitive polyimide materials.

[0003] In addition, semiconductor devices (hereinafter also referred to as "components") are mounted on printed circuit boards by various methods according to the purpose. Conventional components are usually manufactured by a wire bonding method in which thin wires are connected from external terminals (pads) of the components to leads of a lead frame. However, recently, from the viewpoints of high-speed transmission and thinning of the package height, a semiconductor chip mounting technology called fan-out wafer-level packaging (FOWLP) has been proposed. FOWLP is a technology in which a wafer that has completed the previous process is cut to manufacture individual chips, a single chip is reconstructed on a support, and then sealed with a molding resin, and a redistribution layer is formed after peeling off the support.

[0004] In recent years, the development of packages for the new communication standard, the fifth-generation mobile communication system (5G), has become an urgent task. Different from the existing 4G technology, 5G can achieve high-speed large-capacity data transmission, low latency of signals, and simultaneous connection of multiple terminals that do not exist in conventional communications by using the millimeter wave (10 GHz to 80 GHz) band. For the millimeter wave band, the influence of transmission loss in signal wiring of printed circuit boards is large, and heat generation and transmission delay are a concern. Therefore, in order to reduce transmission loss, a packaged antenna (AiP) in which a front-end module (FEM) for transmitting and receiving radio waves is integrated with an antenna has been developed (for example, refer to Patent Document 1 below). Since the wiring length of AiP is short, it is possible to suppress the transmission loss that increases in proportion to the wiring length.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: US Patent Application Publication No. 2016 / 0104940 Specification SUMMARY OF THE INVENTION

[0008] Problems to be Solved by the Invention

[0009] On the other hand, there are also limits to the method of suppressing transmission loss through package design, and improvement in materials is also expected. When the dielectric constant and dielectric loss tangent (tanδ) of the insulating material used to form the wiring are high, the dielectric loss increases, and the overall transmission loss increases. Although polyimide has excellent insulation performance and film physical properties, the imide group itself is a polar functional group, and the photosensitive polyimide precursor composition contains a large number of polar compounds such as photoinitiators and crosslinking agents. Therefore, the values of the dielectric constant and dielectric loss tangent are high, and it is necessary to reduce the dielectric properties.

[0010] Solutions for Solving the Problems

[0011] In view of the above technical status, the problems to be solved by the present invention are to provide: a negative photosensitive resin composition that exhibits a low dielectric loss tangent, excellent storage stability, and can form a cured relief pattern with high resolution; a method for producing the same; a polyimide cured film using the photosensitive resin composition; a method for manufacturing a cured relief pattern; and a semiconductor device having the cured relief pattern.

[0012] The inventors of the present invention unexpectedly found that for a photosensitive resin composition containing a polyimide precursor, the above problems can be solved by adjusting the properties of the photosensitive resin composition, and thus completed the present invention.

[0013] That is, the present invention is as follows.

[0014] [1] A photosensitive resin composition, comprising:

[0015] (A) 100 parts by mass of a polyimide precursor represented by the following general formula (1):

[0016]

[0017] {In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. Among them, at least one of R1 and R2 is a group represented by the following general formula (2),

[0018]

[0019] (In the formula, R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.)};

[0020] (B) Photosensitizer: 0.5 to 10 parts by mass; and

[0021] (D) Solvent: 100 to 300 parts by mass,

[0022] The imidization rate b of the photosensitive resin composition is 15% to 50%. The imidization rate b is the value obtained by dividing the peak intensity near 1380 cm -1 in the infrared absorption spectrum of the photosensitive resin layer before exposure obtained by removing the solvent from the photosensitive resin composition by the ATR (Attenuated Total Reflection) method by the peak intensity near 1500 cm -1 and then dividing the imidization index of the photosensitive resin layer by the imidization index of the cured film obtained by heating and curing the photosensitive resin composition at 350°C. And in the polyimide of the polyimide cured film, the proportion of imide groups, that is, the imide group concentration a, relative to the molecular weight of the repeating unit containing the structure derived from the tetracarboxylic acid and the diamine is 12 wt% to 30 wt%.

[0023] [2] The photosensitive resin composition according to the above [1], wherein the imide group concentration a and the imidization rate b satisfy the following formula (1).

[0024] 0.10 ≤ a × (1 - b) ≤ 0.17...(1)

[0025] [3] The photosensitive resin composition according to the above [1] or [2], wherein in the polyimide of the polyimide cured film, the proportion of imide groups, that is, the imide group concentration a, relative to the molecular weight of the repeating unit containing the structure derived from the tetracarboxylic acid and the diamine is 12 wt% to 24 wt%.

[0026] [4] The photosensitive resin composition according to any one of the above [1] to [3], wherein the imidization index of the polyimide cured film obtained by heating and curing at 350°C is 0.10 to 0.54.

[0027] [5] The photosensitive resin composition according to any one of the above [1] to [4], wherein the absorbance at 365 nm per 1 μm of the photosensitive resin layer obtained by coating the photosensitive resin composition on quartz glass and heating at 110°C for 3 minutes is 0.02 to 0.09.

[0028] [6] The photosensitive resin composition according to any one of [1] to [5] above, wherein Y1 in the above general formula (1) is as shown in the following formula (Y1):

[0029]

[0030] {In the formula, each Rz is independently a monovalent organic group having 1 to 10 carbon atoms optionally containing a halogen atom, a is an integer of 0 to 4, A is an oxygen atom or a sulfur atom, and B is one of the following formulas:

[0031] }.

[0032] [7] The photosensitive resin composition according to [6] above, wherein the above Y1 is as shown in the following chemical formula:

[0033]

[0034] or

[0035]

[0036] or

[0037]

[0038] [8] The photosensitive resin composition according to any one of [1] to [7] above, wherein X1 in the above general formula (1) is as shown in the following chemical formula:

[0039]

[0040] {In the formula, each Ry is independently a monovalent organic group having 1 to 10 carbon atoms optionally containing a halogen atom, a is an integer of 0 to 4, C is an oxygen atom or a sulfur atom, and D is one of the following chemical formulas:

[0041] }.

[0042] [9] The photosensitive resin composition according to [8] above, wherein the above X1 is as shown in the following chemical formula:

[0043]

[0044] or

[0045]

[0046]

[10] The photosensitive resin composition according to any one of [1] to [9] above, wherein the photosensitive resin composition is a negative type and contains (A) a polyimide precursor: 50 to 85 parts by mass, (B) a photosensitizer: 0.5 to 10 parts by mass, and (D) a solvent: 100 to 300 parts by mass, and contains 15% to 50% by mass of the polyimide precursor, and the polyimide precursor is the polyimide precursor represented by the following general formula (11) having a structure shown in the following general formula (1) in the molecule,

[0047]

[0048] {In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and m is an integer of 2 to 150.}.

[0049]

[11] The photosensitive resin composition according to any one of [1] to [9] above, wherein the photosensitive resin composition is a negative type and contains (A) a polyimide precursor: 50 to 85 parts by mass, (B) a photosensitizer: 0.5 to 10 parts by mass, and (D) a solvent: 100 to 300 parts by mass, and contains 15% to 50% by mass of the polyimide precursor, and the polyimide precursor is a blend of the polyimide precursor represented by the above general formula (1) and a polyimide having a structure shown in the following general formula (11),

[0050]

[0051] {In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and m is an integer of 2 to 150.}.

[0052]

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

[11] above, which further contains (C) at least one organic compound selected from the group consisting of an organic titanium compound and an organic zirconium compound: 0.01 to 5 parts by mass.

[0053]

[13] The photosensitive resin composition according to

[12] above, wherein the (C) organic compound is an organic titanium compound.

[0054]

[14] The photosensitive resin composition according to

[12] or

[13] above, wherein the organic titanium compound is at least one compound selected from the group consisting of a tetraalkoxy titanium compound, a titanium chelate compound, a titanate compound, and a titanocene compound.

[0055]

[15] The photosensitive resin composition according to

[14] above, wherein the organic titanium compound is a titanium chelate having two or more alkoxy groups or tetraalkoxy titanium.

[0056]

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

[15] is used for forming an interlayer insulating film for a rewiring layer.

[0057]

[17] The photosensitive resin composition according to any one of the above [1] to

[16] further comprises (E) monomer: 0.5 to 15 parts by mass.

[0058]

[18] In the photosensitive resin composition according to the above

[17] , the (E) monomer contains at least one group selected from the group consisting of a hydroxyl group and an amino group.

[0059]

[19] A method for manufacturing the photosensitive resin composition according to any one of the above [1] to

[18] , comprising the following steps:

[0060] A step of mixing the above (A) polyimide precursor, the above (B) photosensitizer, and the above (D) solvent; and

[0061] A step of curing the obtained mixture at 23°C to 50°C for 24 hours to 360 hours to adjust the imidization rate to 15% to 50%.

[0062]

[20] A method for manufacturing a polyimide cured film, comprising the following steps (1) to (5):

[0063] (1) A step of coating the photosensitive resin composition according to any one of the above [1] to

[17] on a substrate to form a photosensitive resin layer on the substrate;

[0064] (2) A step of heating and drying the obtained photosensitive resin layer;

[0065] (3) A step of exposing the heated and dried photosensitive resin layer;

[0066] (4) A step of developing the exposed photosensitive resin layer; and

[0067] (5) A step of heat-treating the developed photosensitive resin layer to form a polyimide cured film.

[0068]

[21] In the method for manufacturing a polyimide cured film according to the above

[20] , the dielectric loss tangent of the polyimide cured film measured at 10 GHz by the perturbed split cylinder resonator method is 0.0021 to 0.007.

[0069]

[22] The manufacturing method of the polyimide cured film according to

[20] or

[21] above, wherein the tangent of the dielectric loss angle of the above polyimide cured film measured at 28 GHz by the perturbed split cylinder resonator method is 0.0021 to 0.008.

[0070]

[23] The manufacturing method of the polyimide cured film according to any one of

[20] to

[22] above, wherein the tangent of the dielectric loss angle of the above polyimide cured film measured at 40 GHz by the perturbed split cylinder resonator method is 0.0021 to 0.008.

[0071]

[24] The manufacturing method of the polyimide cured film according to any one of

[20] to

[23] above, wherein the tangent of the dielectric loss angle of the above polyimide cured film measured at 60 GHz by the perturbed split cylinder resonator method is 0.0021 to 0.009.

[0072]

[25] A manufacturing method of a polyimide cured film, wherein the polyimide cured film uses a photosensitive resin composition containing the following components:

[0073] (A) A polyimide precursor represented by the following general formula (1): 100 parts by mass,

[0074]

[0075] {In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. Among them, at least one of R1 and R2 is a group represented by the following general formula (2),

[0076]

[0077] (In the formula, R3, R4 and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.);

[0078] (B) A photosensitizer: 0.5 to 10 parts by mass; and

[0079] (D) A solvent: 100 to 300 parts by mass,

[0080] The manufacturing method includes the following steps (1) to (5):

[0081] (1) A step of coating the above photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate;

[0082] (2) A step of heating and drying the obtained photosensitive resin layer to remove the solvent;

[0083] (3) A step of exposing the photosensitive resin layer after removing the solvent;

[0084] (4) A step of developing the photosensitive resin layer after exposure; and

[0085] (5) A step of heat-treating the developed photosensitive resin layer to form a polyimide cured film,

[0086] The imidization rate of the photosensitive resin layer before exposure obtained by removing the solvent after heating and drying in this step (2) is 15 to 50%.

[0087] Effects of the Invention

[0088] By using the photosensitive resin composition of the present invention, a cured resin film excellent in dielectric loss tangent can be manufactured while maintaining the resolution of the relief pattern under a thick film. In one embodiment, by increasing the imidization rate of the photosensitive resin layer obtained from the photosensitive resin composition to a specified range, it becomes easy to remove the polar compounds from the side chains of the polyimide precursor through the heating step, and the dielectric loss tangent of the obtained cured film can be reduced and the frequency dependence can be decreased. In addition, by adjusting the absorbance of the photosensitive resin layer obtained from the photosensitive resin composition to a specified range, the resolution of the relief pattern under a thick film can be maintained. Detailed Embodiments

[0089] Hereinafter, the mode for implementing the present invention (hereinafter simply referred to as "embodiment") will be described in detail. It should be noted that the present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of its gist. Throughout this specification, when there are multiple structures represented by the same symbol in the general formula in the molecule, they are independently selected respectively as long as there is no other specification, and they can be the same or different from each other. In addition, regarding the structures represented by the same symbol in different general formulas, they are also independently selected respectively as long as there is no other specification, and they can be the same or different from each other.

[0090] [Photosensitive Resin Composition]

[0091] The photosensitive resin composition of this embodiment contains (A) a polyimide precursor, (B) a photosensitizer (photoinitiator), and (D) a solvent, and may further contain, as desired: (C) an organic compound, such as a titanium or zirconium compound; (E) a monomer; and other components.

[0092] Each component will be described in turn below.

[0093] From the viewpoint of the physical properties of the (A) polyimide precursor described later, the photosensitive resin composition is preferably negative type.

[0094] Preferably used as the photosensitive resin composition in the present invention is a photosensitive resin composition having an absorbance at 365 nm (i-line) of 0.02 to 0.09 per 1 μm.

[0095] The i-line absorbance of a 1-μm-thick film can be measured as follows: The photosensitive polyimide precursor is formed alone on a quartz glass, and after pre-baking the resulting coating film, it is measured using a usual spectrophotometer. When the thickness of the formed film is not 1 μm, the absorbance obtained for the film is converted to a 1-μm thickness according to the Lambert-Beer law, whereby the i-line absorbance of a 1-μm thickness can be obtained.

[0096] The i-line absorbance is more preferably 0.04 or more, and further preferably 0.05 or more from the viewpoint of suppressing reflected light. Reflected light is light that travels through the film without being absorbed, reaches the bottom of the film, and is reflected at the substrate, which can cause pattern defects. If the i-line absorbance is 0.09 or less, light can reach the bottom of the photosensitive resin layer, and the solubility difference between the soluble part and the insoluble part can be maintained.

[0097] [(A) Polyimide precursor]

[0098] In the present embodiment, the (A) polyimide precursor is a resin component contained in the photosensitive resin composition, and is a polyamide having a structural unit represented by the following general formula (1).

[0099]

[0100] {In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. Among them, at least one of R1 and R2 is a group represented by the following general formula (2):

[0101]

[0102] (In the formula, R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.).}. It should be noted that R1 and R2 in the general formula (1) are also referred to as side chains or side chain structures of the polyimide precursor.

[0103] From the viewpoints of the photosensitive characteristics and mechanical characteristics of the photosensitive resin composition, n1 in the above general formula (1) is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

[0104] In the above general formula (1), from the viewpoints of heat resistance and photosensitive properties, the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, more preferably an aromatic group or an alicyclic aliphatic group in which -COOR1 group, -COOR2 group and -CONH- group are adjacent to each other. As the tetravalent organic group represented by X1, specifically, an organic group having 6 to 40 carbon atoms with an aromatic ring can be cited. For example, a group having a structure represented by the following general formula (20):

[0105]

[0106] {In formula (20), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group and a C1-C10 fluorinated hydrocarbon group, l is an integer of 0 to 2, m is an integer of 0 to 3, and n is an integer of 0 to 4.}, but not limited to these. In addition, the structure of X1 can be one kind or a combination of two or more kinds. From the viewpoints of heat resistance and photosensitive properties, the X1 group having the structure represented by the above formula (20) is particularly preferred.

[0107] In the above general formula (1), from the viewpoints of heat resistance and photosensitive properties, the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, and examples thereof include structures represented by the following general formula (21):

[0108]

[0109]

[0110] {In formula (21), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group and a C1-C10 fluorinated hydrocarbon group, m is an integer of 0 to 3, and n is an integer of 0 to 4.}, but not limited to these. In addition, the structure of Y1 can be one kind or a combination of two or more kinds. From the viewpoints of heat resistance and photosensitive properties, the Y1 group having the structure represented by the above formula (21) is particularly preferred.

[0111] As the Y1 group, in the structure represented by the above formula (21), the structure represented by the following formula is particularly preferred from the viewpoints of low dielectric loss tangent, low dielectric constant and lithography:

[0112]

[0113] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group and a C1-C10 fluorinated hydrocarbon group, m is an integer of 0 to 3, and n is an integer of 0 to 4.}.

[0114] In the general formula (2) above, R3 is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitive properties. In addition, m1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitive properties.

[0115] In this specification, the term "imide group concentration" means the proportion of imide groups in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition of the present embodiment, relative to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic acid and diamine.

[0116] It should be noted that in this specification, the term "polyimide precursor" includes a partially imidized polyimide precursor.

[0117] In the present embodiment, the imide group concentration of the obtained polyimide cured film is 12 wt% to 30 wt%, preferably 12 wt% to 24 wt%. When the imide group concentration is 12 wt% or more, the mold resin and the cured relief pattern tend to have good adhesion. The imide group concentration is preferably 12.5 wt% or more, more preferably 13.5 wt% or more. On the other hand, by making the imide group concentration 30 wt% or less, the obtained polyimide cured film tends to have good dielectric loss tangent. The imide group concentration is more preferably 23.0 wt% or less, and further preferably 21.0 wt% or less.

[0118] The imide group concentration of each repeating unit of the polyimide is represented by the following formula (I) using the molecular weights of the tetracarboxylic acid and diamine used in the preparation of the polyimide precursor.

[0119] 70.02×2 / [Mw(A)+Mw(B)]×100 (I)

[0120] {In formula (I), Mw(A) represents the molecular weight of the tetracarboxylic acid, and Mw(B) represents the molecular weight of the diamine.}. It should be noted that when using two or more kinds of tetracarboxylic acids and / or diamines, for example, when using two kinds of tetracarboxylic acids and / or diamines for preparation, it is represented by the following formula (II).

[0121] 70.02×2 / [Mw(A1)×a1+Mw(A2)×a2+Mw(B1)×b1+Mw(B2)×b2]×100 (II)

[0122] In formula (II), Mw(A1) represents the molecular weight of the first tetracarboxylic acid, Mw(A2) represents the molecular weight of the second tetracarboxylic acid, a1 represents the content of the first tetracarboxylic acid, a2 represents the content of the second tetracarboxylic acid, Mw(B1) represents the molecular weight of the first diamine, Mw(B2) represents the molecular weight of the second diamine, b1 represents the content of the first diamine, and b2 represents the content of the second diamine. Among them, a1, a2, b1, and b2 respectively satisfy a1 + a2 = 1 and b1 + b2 = 1.

[0123] The same calculation is performed when using more than 3 types of tetracarboxylic acids and / or diamines. When using tetracarboxylic dianhydride as a raw material, it is converted to tetracarboxylic acid for calculation.

[0124] When measuring the cured film obtained from the photosensitive resin composition by the ATR method, the peak intensity ratio at 1380 cm -1 and 1500 cm -1 (the imidization index of the cured film) represents the ratio of the imide groups (1380 cm -1 ) present in the cured film to the aromatic rings (1500 cm -1 ). In this embodiment, X1 and Y1 in the general formula (1) are preferably selected from the structures with an imidization index of 0.10 - 0.54 of the cured film. From the perspective of reducing the dielectric loss tangent, it is preferably 0.10 - 0.53, and from the perspective of lithography, it is more preferably 0.35 - 0.53.

[0125] (A) Preparation method of polyimide precursor

[0126] The polyimide precursor containing the structure shown in the above general formula (1) in this embodiment can be obtained, for example, by the following method. The method includes: reacting a tetracarboxylic dianhydride containing a tetravalent organic group X1 with 6 - 40 carbon atoms as described above with (a) alcohols having a structure formed by bonding a monovalent organic group shown in the above general formula (2) and a hydroxyl group, and (b) alcohols having a structure other than the group shown in the above general formula (2) used as desired, to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester body); then, subjecting the obtained acid / ester body to polycondensation with diamines containing a divalent organic group Y1 with 6 - 40 carbon atoms as described above.

[0127] (Preparation of acid / ester body)

[0128] In the present embodiment, examples of the tetracarboxylic dianhydride containing the tetravalent organic group X1 having 6 to 40 carbon atoms include, for example, 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, diphenyl methane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, 4,4'-(4,4'-isopropylidenediphenoxy) dianhydride, and the like. In addition, these may be used alone or in combination of two or more.

[0129] Examples of the alcohol (b) having a structure other than the group represented by the above general formula (2) include aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms, such as 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, benzyl alcohol, and the like.

[0130] The content of the organic group of the general formula (2) in the polyimide precursor is preferably 50 mol% or more relative to the total content of R1 and R2 in the general formula (1). When the content of the organic group of the general formula (2) exceeds 50 mol%, the desired photosensitive characteristics can be obtained, and thus it is preferred.

[0131] The content of the organic group of the general formula (2) in the photosensitive resin composition is preferably 75 mol% or more relative to the total content of R1 and R2 in the general formula (1).

[0132] By dissolving and mixing the above tetracarboxylic dianhydride and the alcohol (a) in a reaction solvent in the presence of a basic catalyst such as pyridine, a semi-esterification reaction of the acid dianhydride can be carried out to obtain a desired acid / ester body. The reaction conditions are preferably stirring at a reaction temperature of 20 to 50 °C for 4 to 10 hours.

[0133] As the above reaction solvent, a solvent that can dissolve the acid / ester body and the polyimide precursor which is the polycondensation product of the acid / ester body and diamines is preferably used. Examples of the reaction solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. These can be used alone as needed or in combination of two or more.

[0134] (Preparation of polyimide precursor)

[0135] After mixing a known dehydrating condensing agent with the above acid / ester body (typically a solution in the above reaction solvent) under ice cooling to form a polyanhydride of the acid / ester body, a product obtained by separately dissolving or dispersing a diamine containing a divalent organic group Y1 having 6 to 40 carbon atoms in a solvent is added dropwise thereto to carry out polycondensation, whereby a polyimide precursor can be obtained. Examples of the dehydrating condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc.

[0136] Examples of the diamine compound containing a divalent organic group Y1 having 6 to 40 carbon atoms include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 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, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 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(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, o-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis{3-methyl-4-(4-aminophenoxy)phenyl}propane, bis{4-(4-aminophenoxy)phenyl}ketone; and compounds in which a part of the hydrogen atoms on these benzene rings are substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, 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'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl; and mixtures thereof. However, the diamine compounds are not limited to these.

[0137] In order to improve the adhesion between the photosensitive resin layer formed on the substrate by coating the photosensitive resin composition of the present embodiment on the substrate and various substrates, when preparing the (A) polyimide precursor, diamino siloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane may be copolymerized.

[0138] After the above polycondensation reaction is completed, if necessary, the water-absorbing by-products of the dehydrating condensing agent present in the reaction solution can be filtered out, and then a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof is added to the reaction solution to precipitate the polymer components. Furthermore, by repeating the above re-dissolution and re-precipitation operations, etc., the polymer can be purified. Also, the polymer can be vacuum-dried to separate the polyimide precursor. To improve the purity, the solution of the polymer can be passed through a column filled with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0139] (A) When the molecular weight of the polyimide precursor is measured as the polystyrene-equivalent weight-average molecular weight based on gel permeation chromatography (GPC), it is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000. If the weight-average molecular weight is 8,000 or more, the mechanical properties are good, so it is preferred. On the other hand, if it is 150,000 or less, the dispersibility in the developer and the resolution performance of the relief pattern are good, so it is preferred. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight is determined from a standard curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0140] The photosensitive resin composition using the (A) polyimide precursor undergoes imidization of the compound contained in the photosensitive resin composition and / or a part of the (A) polyimide precursor in the manufacturing process of the photosensitive resin composition in the resin composition.

[0141] In the present embodiment, the imidization rate of the (A) polyimide precursor in the resin composition is 15% to 50%, preferably 15% to 40%, from the viewpoints of low dielectric loss tangent, absorbance, and resolution when measured by the ATR method. The absorbance of the polyimide precursor is related to the imidization rate, and the absorbance increases as the imidization rate increases. It should be noted that in this specification, the term "imidization rate" is calculated in the following form: when the value obtained by dividing the peak intensity at 1380 cm -1 by the peak intensity at 1500 cm -1 is set as the "imidization index of the photosensitive resin layer", the value obtained by dividing the imidization index of the photosensitive resin layer by the "imidization index of the cured film" obtained by curing the photosensitive resin composition at 350°C.

[0142] When the polyimide precursor is imidized, with the ring-closing reaction, the side chains corresponding to R1 and R2 in the general formula (1) are detached and dispersed into the resin composition. In the present embodiment, a part of the polyimide precursor in the photosensitive resin composition is imidized, and the side chains are already dispersed in the resin composition before heat curing. Therefore, the concentration of methacrylate in the resin composition remains unchanged, and the lithography property can be maintained. On the other hand, the methacrylate is easily volatilized by heating in the heat curing process. Therefore, the residual amount of polar compounds in the cured film can be reduced.

[0143] From the viewpoints of low dielectric loss tangent and absorbance, it is preferable that the imide group concentration a and the imidization rate b satisfy the following formula (1).

[0144] 0.10 ≤ a × (1 - b) ≤ 0.17...(1)

[0145] Although not bound by theory, by making a × (1 - b) in the range of 0.1 to 0.17, the residual amount of the polyimide precursor side chain in the polyimide cured film can be reduced, and low dielectric loss tangent can be achieved. Moreover, the absorbance that increases with the progress of imidization can be kept below a certain value.

[0146] [(B) Photosensitizer]

[0147] The photosensitive resin composition of this embodiment contains a photosensitizer. In one embodiment, the photosensitizer can be a photoinitiator. The photoinitiator promotes the curing of the relief pattern based on light irradiation, so it is preferred. As the photoinitiator, a photo radical polymerization initiator is preferred, and examples include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzil derivatives such as benzil, benzil dimethyl ketal, benzil-β-methoxyethyl ketal; benzoin derivatives such as benzoin, 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; N-aryl glycine compounds such as N-phenylglycine; peroxide compounds such as benzoyl perchlorate; aromatic bisimidazole compounds; titanocene compounds; photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyan, but are not limited to these. Among the above photoinitiators, oxime compounds are more preferred from the viewpoint of sensitivity.

[0148] The compounding amount of the photoinitiator is 0.5 parts by mass or more and 10 parts by mass or less, preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. The above compounding amount is preferably 0.5 parts by mass or more from the viewpoint of sensitivity or patterning property. On the other hand, from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition, it is preferably 10 parts by mass or less.

[0149] [(C) Organic compound]

[0150] In this embodiment, the photosensitive resin composition may contain a (C) organic compound. The (C) organic compound preferably contains at least one metal element selected from the group consisting of titanium and zirconium in one molecule. As the organic group, a hydrocarbon group or a hydrocarbon group containing a heteroatom is preferred. By containing the above organic compound, the imidization rate of the polyimide precursor contained in the photosensitive resin composition is increased, and the dielectric loss tangent of the cured film is decreased.

[0151] Examples of usable organotitanium or organozirconium compounds include, for example, compounds in which an organic group is bonded to a titanium atom or a zirconium atom by a covalent bond or an ionic bond.

[0152] Specific examples of the organotitanium or organozirconium compounds are illustrated in the following I) to VII):

[0153] As I) chelate compounds, from the viewpoints of the storage stability of the photosensitive resin composition and obtaining a good pattern, compounds having two or more alkoxy groups are more preferred. Specific examples of chelate compounds include bis(triethanolamine)diisopropoxytitanium, dibutoxybis(2,4-pentanedionato)titanium, diisopropoxybis(2,4-pentanedionato)titanium, diisopropoxybis(tetramethylheptanedionato)titanium, diisopropoxybis(ethyl acetoacetate)titanium, and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but are not limited to these.

[0154] As II) tetraalkoxy compounds, examples include tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexoxy)titanium, tetra(isobutoxy)titanium, tetra(isopropoxy)titanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetra(n-propoxy)titanium, tetrastearoxytitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but are not limited to these.

[0155] As III) titanocene or zirconocene compounds, examples include trimethoxypentamethylcyclopentadienyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but are not limited to these.

[0156] As IV) monoalkoxy compounds, examples include isopropoxytri(dioctylphosphatooxy)titanium, isopropoxytri(dodecylbenzenesulfonyl)titanium, and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but are not limited to these.

[0157] As V) titanium oxide or zirconium oxide compounds, examples include bis(pentanedionato)titanium oxide, bis(tetramethylheptanedionato)titanium oxide, titanyl phthalocyanine, and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but are not limited to these.

[0158] As VI) tetraacetylacetonato titanium or tetraacetylacetonato zirconium compounds, examples include tetraacetylacetonato titanium, and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but are not limited to these.

[0159] As the (VII) titanate coupling agent, examples include isopropyl tris(dodecylbenzenesulfonyl)titanate, etc., but are not limited thereto.

[0160] Among the above (I) to (VII), from the viewpoint of exhibiting a better dielectric loss tangent, the organotitanium compound is preferably at least one compound selected from the group consisting of the above (I) titanium chelate compound, (II) tetraalkoxytitanium compound, and (III) titanocene compound. Diisopropoxybis(ethyl acetoacetate)titanium, tetra(n-butoxy)titanium, and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

[0161] Regarding the compounding amount of the organotitanium or zirconium compound during compounding, it is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the (A) resin. If the compounding amount is 0.01 part by mass or more, the imidization rate of the resin composition and the dielectric loss tangent of the cured film are favorably exhibited. On the other hand, if it is 10 parts by mass or less, the storage stability is excellent, and thus it is preferred.

[0162] The photosensitive resin composition of the present embodiment can increase the imidization rate of the polyimide precursor contained in the resin composition and reduce the dielectric loss tangent of the cured film using the resin composition by containing the above (C) organic compound. Although not bound by theory, it is considered that the reason for increasing the imidization rate of the polyimide precursor is that the metal element contained in the (C) organic compound coordinates with the carbonyl group of the ester group and / or carboxyl group from the polyimide precursor, thereby reducing the electron density of the carbon atom of the carbonyl group and promoting the ring closure reaction. As the reason for the reduction of the dielectric loss tangent, it is considered that since a part of the ring closure reaction is carried out before the heat treatment for curing the resin composition, R1 and / or R2 in the polyimide precursor represented by the following general formula (1) are detached from the polymer structure through the ring closure of the polyimide precursor and become volatile easily in the heat treatment step of the cured film manufacturing process.

[0163]

[0164] {In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms.}. Moreover, when R1 and / or R2 have a polymerizable functional group, they remain in the film in the exposure step of the cured film manufacturing process. Therefore, even if the imidization rate increases, the concentration of the polymerizable functional group in the film remains unchanged, and the resolution is not affected.

[0165] [(D) Solvent]

[0166] The photosensitive resin composition of the present embodiment contains a (D) solvent (also referred to as a solvent). As the solvent, from the viewpoint of solubility in the (A) polyimide precursor, a polar organic solvent is preferably used. Specific examples of the solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, 2-octanone, etc. These can be used alone or in combination of two or more.

[0167] In the present embodiment, depending on the desired coating film thickness and viscosity of the photosensitive resin composition, the above (D) solvent is in the range of 100 to 300 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0168] From the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing an alcohol is preferably included. Typically, the alcohol that can be preferably used is an alcohol having an alcohol hydroxyl group in the molecule but not having an olefinic double bond. Specific examples include: alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol; lactate esters such as ethyl lactate; propylene glycol monoalkyl ethers such as propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-n-propyl ether, propylene glycol-2-n-propyl ether; monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether; 2-hydroxyisobutyrate esters; diols such as ethylene glycol and propylene glycol. Among these, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethanol are preferred, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-n-propyl ether are particularly preferred.

[0169] When the solvent contains an alcohol not having an olefinic double bond, based on the mass of all solvents, the content of the alcohol not having an olefinic double bond in all solvents is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass. If the above content of the alcohol not having an olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition becomes good. On the other hand, if it is 50% by mass or less, the solubility of the (A) polyimide precursor becomes good.

[0170] [(E) Monomer]

[0171] In the present embodiment, in order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain an (E) monomer having a photopolymerizable unsaturated bond. As such a monomer, (meth)acrylic compounds that undergo a radical polymerization reaction based on a photoinitiator are preferred. Although not particularly limited to the following, examples include: mono- or di-acrylates or methacrylates of ethylene glycol or polyethylene glycol, represented by diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; mono- or di-acrylates or methacrylates of propylene glycol or polypropylene glycol; mono-, di- or tri-acrylates or methacrylates of glycerol; cyclohexanediol diacrylate or dimethacrylate; 1,4-butanediol diacrylate or dimethacrylate; 1,6-hexanediol diacrylate or dimethacrylate; neopentyl glycol diacrylate or dimethacrylate; mono- or di-acrylates or methacrylates of bisphenol A; benzenetricrylate; isobornyl acrylate or methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate or methacrylate; di- or tri-acrylates or methacrylates of glycerol; di-, tri- or tetra-acrylates or methacrylates of pentaerythritol; and ethylene oxide or propylene oxide adducts of these compounds. In addition, one of these monomers may be used, or a mixture of two or more thereof may be used.

[0172] When the resin composition is cured and the polyimide precursor contained in the resin composition undergoes a ring closure, the side-chain molecules are detached, but the detached side-chain molecules can exist in the resin composition in the form of monomers. The monomer preferably has at least one group selected from the group consisting of a hydroxyl group and an amino group, and more preferably has a structure represented by the following general formula (3).

[0173]

[0174] {In formula (3), Z is at least one group selected from the group consisting of a hydroxyl group and an amino group, R7, R8 and R9 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m2 is an integer of 2 to 10.}.

[0175] In the present embodiment, the compounding amount of the monomer having a photopolymerizable unsaturated bond is 0.5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0176] [Other Components]

[0177] The photosensitive resin composition of the present embodiment may further contain components other than the above components (A) to (E). Examples of other components include: resin components other than the (A) polyimide precursor; sensitizers; monomers having a photopolymerizable unsaturated bond; adhesion aids; thermal polymerization inhibitors; azole compounds; and hindered phenol compounds.

[0178] In one embodiment, the photosensitive resin composition may further contain a resin component other than the (A) polyimide precursor. Examples of the resin component that can be contained in the photosensitive resin composition include, for example, polyimide, polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, silicone resin, acrylic resin, etc. The compounding amount of these resin components is preferably in the range of 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0179] When a positive photosensitive resin composition is prepared using a polyoxazole precursor together with the (A) polyimide precursor, as the positive photosensitive material, a compound having a quinonediazide group, such as a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure, etc., can be used in combination.

[0180] In one embodiment, the photosensitive resin composition may optionally contain a sensitizer in order to improve the sensitivity. Examples of the sensitizer include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminobenzylidene)biphenyl-benzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)isoindolothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzoyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, etc. These can be used alone or in combination of multiple (for example, 2 to 5 kinds).

[0181] The compounding amount of the sensitizer is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

[0182] In one embodiment, in order to improve the adhesiveness between the film formed using the photosensitive resin composition and the substrate, the photosensitive resin composition may optionally contain an adhesion aid. Examples of the adhesion aid include silane coupling agents such as γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyldimethoxysilane, γ-glycidoxypropyl methyldimethoxysilane, γ-mercaptopropyl methyldimethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropyl methylsilane, N-(3-diethoxymethylsilylpropyl) succinimide, N-[3-(triethoxysilyl)propyl] phthalic acid amide, benzophenone-3,3'-bis(N-[3-triethoxysilyl] propionamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl] propionamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyl trimethoxysilane; and aluminum-based adhesion aids such as tris(ethyl acetoacetate)aluminum, tris(acetylacetone)aluminum, ethyl acetoacetate aluminum diisopropyl ester. In addition, one of these adhesion aids may be used, or a mixture of two or more thereof may be used.

[0183] Among these adhesion aids, from the viewpoint of adhesive force, it is more preferable to use a silane coupling agent. The compounding amount of the adhesion aid is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

[0184] In one embodiment, particularly in order to improve the viscosity and the stability of the photosensitivity of the photosensitive resin composition during storage in a solution state containing a solvent, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-cresol, 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. In addition, one of these thermal polymerization inhibitors may be used, or a mixture of two or more thereof may be used.

[0185] The compounding amount of the heat-resistant polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0186] For example, in order to suppress discoloration of a substrate when using a substrate containing copper or a copper alloy, the photosensitive resin composition may optionally contain an azole compound. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-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, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole are particularly preferred. In addition, one of these azole compounds may be used, or two or more of them may be used as a mixture.

[0187] The compounding amount of the azole compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and more preferably 0.5 part by mass to 5 parts by mass from the viewpoint of the sensitivity characteristics. When the compounding amount of the azole compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 part by mass or more, discoloration of the surface of the copper or copper alloy is suppressed when the photosensitive resin composition is formed on the copper or copper alloy. On the other hand, when it is 20 parts by mass or less, the sensitivity is excellent, and thus it is preferred.

[0188] In the present embodiment, in order to suppress discoloration on copper, the photosensitive resin composition may contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanuric acid ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-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-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-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-trimethylethyl-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-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc., but not limited to these. Among these, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.,

[0189] The compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the (A) polyimide precursor. When the compounding amount of the hindered phenol compound is 0.1 part by mass or more based on 100 parts by mass of the (A) polyimide precursor, for example, when forming a photosensitive resin composition on copper or a copper alloy, discoloration and corrosion of copper or a copper alloy can be prevented. On the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent, so it is preferred.,

[0190] The photosensitive resin composition of the present embodiment can be produced by a production method including the following steps:

[0191] A step of mixing the above (A) polyimide precursor, the above (B) photosensitizer, and the above (D) solvent; and

[0192] A step of curing the obtained mixture at 23°C to 50°C for 24 hours to 360 hours to adjust the imidization rate to 15% to 50%.,

[0193] "Curing" refers to the process of allowing the photosensitive resin composition to stand at a constant temperature for a certain period of time. The curing temperature is 23°C to 50°C, preferably 30 to 50°C. The curing time is 24 hours to 360 hours, preferably 48 hours to 280 hours. Through the above curing, defoaming of the photosensitive resin composition can be carried out, and the imidization rate of the (A) polyimide precursor in the photosensitive resin composition can be adjusted to a specified range.

[0194] [Polyimide]

[0195] The polyimide contained in the cured relief pattern formed from the above polyimide precursor composition preferably has a structure represented by the following general formula (11).

[0196]

[0197] {In the general formula (11), X 1 and Y 1 are the same as X1 and Y1 in the general formula (1), and m is a positive integer.}.

[0198] For the same reason, the preferred X1 and Y1 in the general formula (1) are also preferred in the polyimide of the general formula (11). The number of repeating units m of the general formula (11) is not particularly limited and may be an integer from 2 to 150.

[0199] [Cured Film and Method for Producing the Same]

[0200] Another embodiment of the present invention is a method for producing a polyimide cured film, which includes the step of converting the above photosensitive resin composition into polyimide.

[0201] That is, the method for producing a polyimide cured film of the present embodiment includes the following steps (1) to (5):

[0202] (1) A step of coating the above photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate;

[0203] (2) A step of heating and drying the obtained photosensitive resin layer;

[0204] (3) A step of exposing the heated and dried photosensitive resin layer;

[0205] (4) A step of developing the exposed photosensitive resin layer; and

[0206] (5) A step of heat-treating the developed photosensitive resin layer to form a polyimide cured film.

[0207] In another embodiment of the present invention, there are provided a polyimide cured film obtained from the photosensitive resin composition described above and a method for manufacturing the same. When measured by the perturbed split cylinder resonator method at 10 GHz, the tangent of the dielectric loss angle of the cured film is preferably 0.0021 to 0.007, more preferably 0.0030 to 0.0065. When measured at 28 GHz, the tangent of the dielectric loss angle is preferably 0.0021 to 0.008, and from the viewpoint of frequency dependence, more preferably 0.0030 to 0.0075. When measured at 40 GHz, the tangent of the dielectric loss angle is preferably 0.0021 to 0.008, and from the viewpoint of frequency dependence, more preferably 0.0030 to 0.0075. Further, when measured at 60 GHz, the tangent of the dielectric loss angle is preferably 0.0021 to 0.009, and from the viewpoint of frequency dependence, more preferably 0.0030 to 0.0085. It should be noted that the tangent of the dielectric loss angle can be measured by the perturbed split cylinder resonator method shown in the examples described later.

[0208] The photosensitive resin composition used in the method for manufacturing the cured film preferably contains 100 parts by mass of a polyimide precursor, 0.5 to 10 parts by mass of a photosensitizer, and 100 to 300 parts by mass of a solvent. More preferably, a photo radical polymerization initiator is contained as the photosensitizer, and further preferably, the photosensitive resin composition is negative type.

[0209] The specific steps in the method for manufacturing the cured film can be carried out according to steps (1) to (5) of the method for manufacturing the cured film described above.

[0210] The following describes each step.

[0211] [(1) Step of coating the above photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate]

[0212] In this step, the photosensitive resin composition of the present embodiment is coated on a substrate, and if necessary, dried thereafter to form a photosensitive resin layer. As the coating method, a method conventionally used for coating a photosensitive resin composition can be used, for example, a method of coating with a spin coater, a bar coater, a knife coater, a curtain coater, a screen printer, etc., and a method of spray coating with a sprayer.

[0213] [(2) Step of heating and drying the obtained photosensitive resin layer]

[0214] As needed, the coating film formed from the photosensitive resin composition can be dried, and as the drying method, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying can be used. Additionally, it is desirable to dry the coating film under conditions that do not cause imidization of the (A) polyimide precursor in the photosensitive resin composition. Specifically, in the case of air drying or heat drying, drying can be carried out under the conditions of 20°C to 140°C for 1 minute to 1 hour. By the above operations, a photosensitive resin layer can be formed on the substrate.

[0215] [(3) Step of exposing the heat-dried photosensitive resin layer]

[0216] In this step, for the photosensitive resin layer that has undergone the above step (2), exposure is performed using an exposure apparatus such as a contact aligner, mirror projection, or stepper, through a photomask or reticle with a pattern or directly using an ultraviolet light source, etc.

[0217] Then, for the purpose of improving the sensitivity, etc., post-exposure bake (PEB) and / or pre-development bake can be carried out as needed in any combination of temperature and time. Regarding the range of baking conditions, the temperature is preferably 40°C to 120°C, and the time is preferably 10 seconds to 240 seconds, but as long as the characteristics of the negative photosensitive resin composition are not impaired, it is not limited to this range. The imidization rate of the polyimide precursor remains unchanged before and after baking.

[0218] [(4) Step of developing the exposed photosensitive resin layer]

[0219] In this step, the exposed photosensitive resin layer is developed to form a relief pattern.

[0220] In this step, when the photosensitive resin composition is negative, the unexposed portion in the exposed photosensitive resin layer is developed and removed. As a developing method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist developing methods, such as spin spray method, paddle method, dipping method with ultrasonic treatment, etc. for use. In addition, after development, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking can be carried out at any combination of temperature and time as needed. As the developer used for development, preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water, etc. are preferred. When the good solvent and the poor solvent are used in combination, it is preferred to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more kinds of each solvent, for example, a plurality of kinds, can also be used in combination.

[0221] [(5) Step of forming a polyimide cured film by heat-treating the developed photosensitive resin layer]

[0222] In this step, the relief pattern obtained by the above development is heated to volatilize the photosensitive component and imidize the (A) polyimide precursor, thereby converting it into a cured relief pattern formed of polyimide. As a method for heat curing, for example, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-programmable heating oven can be selected. The heating can be carried out, for example, under the conditions of 150 °C to 400 °C for 30 minutes to 5 hours. As the atmosphere gas during heat curing, air can be used, or an inert gas such as nitrogen or argon can also be used.

[0223] [Semiconductor device]

[0224] The photosensitive resin composition of the present embodiment can also provide a semiconductor device having a cured relief pattern obtained by the above-described method for manufacturing a cured relief pattern. Therefore, a semiconductor device can be provided that has a substrate as a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described method for manufacturing a cured relief pattern. In addition, another embodiment can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern as part of a process. The semiconductor device of the present embodiment can be manufactured as follows: A cured relief pattern formed by the above-described method for manufacturing a cured relief pattern is formed as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and is combined with a known method for manufacturing a semiconductor device for manufacturing.

[0225] [Display device]

[0226] The photosensitive resin composition of the present embodiment can also provide a display device including a display element and a cured film provided on the upper portion of the display element, and the cured film is the above-described cured relief pattern. Here, the cured relief pattern can be laminated in direct contact with the display element, or can be laminated with other layers interposed therebetween. For example, as the cured film, a surface protective film, an insulating film, and a planarizing film for a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition for a cathode of an organic EL element can be cited.

[0227] The photosensitive resin composition of the present embodiment is useful not only in applications in semiconductor devices as described above, but also in applications such as interlayer insulation of multilayer circuits, cover coatings of flexible copper clad laminates, solder resist films, and liquid crystal alignment films.

[0228] Examples

[0229] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

[0230] [Measurement and evaluation methods]

[0231] (1) Weight-average molecular weight

[0232] The weight-average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used in the measurement was the trade name "Shodex 805M / 806M tandem" manufactured by Showa Denko K.K., the standard monodisperse polystyrene was the trade name "Shodex STANDARD SM-105" manufactured by Showa Denko K.K., the developing solvent was N-methyl-2-pyrrolidone, and the detector used was the trade name "Shodex RI-930" manufactured by Showa Denko K.K.

[0233] (2) Measurement of the imidization index of the cured film

[0234] On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625 ± 25 μm), Ti with a thickness of 200 nm and Cu with a thickness of 400 nm were successively sputtered using a sputtering device (type L-440S-FHL, manufactured by Canon Anelva Corporation). Then, a photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a Coater Developer (type D-Spin60A, manufactured by SOKUDO Co., Ltd.) and heated and dried on a hot plate at 110 °C for 3 minutes to form a photosensitive resin layer with a thickness of approximately 15 μm. On this photosensitive resin layer, irradiation was performed at an energy of 200 mJ / cm 2 using a mask with a test pattern and Prisma GHI (manufactured by Ultratech Inc.) equipped with an i-line filter.

[0235] For the wafer on which the relief pattern was formed on Cu, using a temperature-programmed curing furnace (type VF-2000, manufactured by Koyo Lindbergh Co., Ltd.), heat treatment was performed at 350 °C for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern formed of resin with a thickness of approximately 10 μm on Cu.

[0236] For this cured relief pattern, measurement was performed using an ATR-FTIR measurement device (Nicolet Continuum, manufactured by ThermoFisher Scientific Inc.) with a Si prism, and the measurement was performed under the conditions of a measurement range of 4000 - 700 cm -1 and 50 measurement times. By obtaining the peak height near 1380 cm -1 (1350 - 1450 cm -1 ; when there are multiple peaks, the one with the maximum peak intensity) and the peak height near 1500 cm -1 (1460 - 1550 cm -1 ; when there are multiple peaks, the one with the maximum peak intensity), the calculation was performed.

[0237] (3) Measurement of imidization rate of photosensitive resin composition

[0238] On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625 ± 25 μm), the photosensitive resin composition prepared by the method described below was spin-coated using a CoaterDeveloper (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and dried by heating on a hot plate at 110 °C for 3 minutes, thereby forming a photosensitive resin layer with a thickness of approximately 10 μm.

[0239] For the above-mentioned photosensitive resin layer, measurement was carried out using a Si prism with an ATR-FTIR measurement device (Nicolet Continuum, manufactured by ThermoFisher Scientific Inc.) in the measurement range of 4000 to 700 cm -1 and under the condition of 50 measurement times. The peak height of the cured film near 1380 cm -1 (1350 - 1450 cm -1 , when there are multiple peaks, the one with the maximum peak intensity) was divided by the peak height near 1500 cm -1 (1460 - 1550 cm -1 , when there are multiple peaks, the one with the maximum peak intensity) to obtain the imidization index of the photosensitive resin layer. The value obtained by dividing the imidization index of the photosensitive resin layer of the resin composition in each example and comparative example by the imidization index of the cured film obtained by curing the resin composition at 350 °C was used as the imidization rate.

[0240] (4) Resolution of cured relief pattern on Cu

[0241] On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625 ± 25 μm), 200 nm thick Ti and 400 nm thick Cu were sequentially sputtered using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Corporation). Then, the photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a Coater Developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and dried by heating on a hot plate at 110 °C for 3 minutes, thereby forming a photosensitive resin layer with a thickness of approximately 25 μm. On this photosensitive resin layer, irradiation was carried out at 200 mJ / cm 2The energy. Next, for this photosensitive resin layer, cyclopentanone was used as the developer, and spray development was carried out using a Coater Developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and rinsing was carried out with propylene glycol monomethyl ether acetate, whereby a relief pattern located on Cu was obtained.

[0242] For the wafer on which this relief pattern was formed on Cu, a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.) was used, and heat treatment was carried out at 230 °C for 2 hours in a nitrogen atmosphere, whereby a cured relief pattern formed of resin with a thickness of about 20 μm located on Cu was obtained.

[0243] The relief pattern produced was observed under an optical microscope, and the size of the smallest opening pattern was determined. At this time, if the area of the opening of the obtained pattern was 1 / 2 or more of the corresponding pattern mask opening area, it was regarded as resolvable, and the resolution was judged based on the length of the mask opening edge corresponding to the opening with the smallest area among the resolvable openings (the size of the opening pattern) according to the following evaluation criteria.

[0244] (Evaluation criteria)

[0245] "Excellent": The size of the smallest opening pattern is less than 25 μm

[0246] "Good": The size of the smallest opening pattern is 25 μm or more and less than 30 μm

[0247] "Acceptable": The size of the smallest opening pattern is 30 μm or more and less than 35 μm

[0248] "Unacceptable": The size of the smallest opening pattern is 35 μm or more.

[0249] (5) Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df)

[0250] On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625 ± 25 μm), aluminum (Al) with a thickness of 100 nm was sputtered using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Corporation), whereby a wafer substrate sputtered with Al was prepared.

[0251] The negative photosensitive resin composition was spin-coated on the above-mentioned wafer substrate sputtered with Al using a spin coater (D-spin60A type, manufactured by SOKUDO Co., Ltd.), and heat-dried at 110 °C for 180 seconds, whereby a spin-coated film was produced. Then, using a locator (PLA-501F, manufactured by Canon Inc.), with an exposure amount of 600 mJ / cm 2The entire surface is exposed to the ghi line, and a heat curing treatment is carried out at 230 °C for 2 hours in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindbergh Co., Ltd., model name VF-2000B), thereby producing a cured film. The film thickness of the cured film is measured by the method described below. The cured film is cut into a length of 80 mm and a width of 60 mm or a length of 40 mm and a width of 30 mm using a cutting machine (manufactured by DISCO, model name DAD-2H / 6T), and is immersed in a 10% hydrochloric acid aqueous solution to be peeled off from the silicon wafer, serving as a thin film sample.

[0252] For the thin film sample, the relative dielectric constant (Dk) and the dielectric loss tangent (Df) at 10, 28, 40, and 60 GHz are measured respectively by the resonator perturbation method. The details of the measurement method are described below.

[0253] (Measurement method)

[0254] Perturbation type split cylinder resonator method

[0255] (Device configuration)

[0256] Network analyzer: PNA Network analyzer E5224B (manufactured by Agilent technologies)

[0257] Split cylinder resonator: CR-710 (manufactured by Kanto Electronic Application Development Co., Ltd., measurement frequency: about 10 GHz), CR-728 (manufactured by Kanto Electronic Application Development Co., Ltd., measurement frequency: about 28 GHz), CR-740 (manufactured by Kanto Electronic Application Development Co., Ltd., measurement frequency: about 40 GHz), CR-760 (manufactured by Kanto Electronic Application Development Co., Ltd., measurement frequency: about 60 GHz)

[0258] (6) Absorbance

[0259] The negative photosensitive resin composition is spin-coated onto a quartz glass (length 50 mm, width 50 mm, thickness 1 mm) using a manual spin coater (ELS306MA, manufactured by SEBACS), and is heated and dried at 110 °C for 180 seconds, thereby producing a spin-coated film. The rotation speed of the manual spin coater is set such that the spin-coated film reaches 10 μm.

[0260] The obtained spin-coated film is measured using a UV-visible (UV-VIS) spectrophotometer (UV-1800, manufactured by Shimadzu Corporation). The absorbance at 365 nm is measured and converted to 1 μm according to the Lambert-Beer law, thereby obtaining the absorbance.

[0261] [(A) Manufacture of polyimide precursor]

[0262] <Manufacturing Example 1> (Synthesis of ((A) Polyimide Precursor (Polymer A-1)))

[0263] 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) was added to a 2-liter detachable flask, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 79.1 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the exothermic reaction ended, it was naturally cooled to room temperature and then allowed to stand for 16 hours.

[0264] Then, while stirring under ice cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes, and then a suspension prepared by suspending 93.0 g of 4,4'-oxydianiline (ODA) in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0265] The obtained reaction solution was added to 3 liters of ethanol to form a precipitate containing the crude polymer. The formed crude polymer was filtered out and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was purified with an anion exchange resin ("Amberlyst TM 15") manufactured by ORGANO CORPORATION to obtain a polymer solution. The obtained polymer solution was added to 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered out and then dried under vacuum to obtain powdery Polymer A-1.

[0266] The weight-average molecular weight (Mw) of this Polymer A-1 was measured, and the result was 22,000. The imide group concentration per repeating unit of the polyimide obtained from Polymer A-1 was 27.4 wt%.

[0267] <Manufacturing Example 2> (Synthesis of Polyimide Precursor (Polymer A-2))

[0268] In the above Manufacturing Example 1, 175.9 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane (BAPP) was used instead of 93.0 g of ODA, and the reaction was carried out in the same manner as described in Manufacturing Example 1 to obtain Polymer A-2.

[0269] The weight-average molecular weight (Mw) of this Polymer A-2 was measured, and the result was 24,000. The imide group concentration per repeating unit of the polyimide obtained from Polymer A-2 was 19.4 wt%.

[0270] <Manufacturing Example 3> (Synthesis of Polyimide Precursor (Polymer A-3))

[0271] In the above Manufacturing Example 1, 169.9 g of bis{4-(4-aminophenoxy)phenyl}ketone (BAPK) was used instead of 93.0 g of ODA, and the reaction was carried out in the same manner as described in Manufacturing Example 1. Thus, Polymer A-3 was obtained.

[0272] The weight-average molecular weight (Mw) of this Polymer A-3 was measured, and the result was 21,000. The imide group concentration per repeating unit of the polyimide obtained from Polymer A-3 was 21.5 wt%.

[0273] <Manufacturing Example 4> (Synthesis of Polyimide Precursor (Polymer A-4))

[0274] In the above Manufacturing Example 1, 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) dianhydride (BPADA) was used instead of 155.1 g of ODPA, and 175.9 g of BAPP was used instead of 93.0 g of ODA. The reaction was carried out in the same manner as described in Manufacturing Example 1. Thus, Polymer A-4 was obtained.

[0275] The weight-average molecular weight (Mw) of this Polymer A-4 was measured, and the result was 29,000. The imide group concentration per repeating unit of the polyimide obtained from Polymer A-4 was 15.0 wt%.

[0276] <Manufacturing Example 5> (Synthesis of Polyimide Precursor (Polymer A-5))

[0277] In the above Manufacturing Example 2, 260.2 g of BPADA was used instead of 155.1 g of ODPA, and 169.9 g of BAPK was used instead of 93.0 g of ODA. The reaction was carried out in the same manner as described in Manufacturing Example 1. Thus, Polymer A-5 was obtained.

[0278] The weight-average molecular weight (Mw) of this Polymer A-5 was measured, and the result was 28,000. The imide group concentration per repeating unit of the polyimide obtained from Polymer A-5 was 16.3 wt%.

[0279] <Manufacturing Example 6> (Synthesis of Polyimide Precursor (Polymer A-6))

[0280] In the above Manufacturing Example 1, 77.6 g of ODPA and 130.1 g of BPADA were used instead of 155.1 g of ODPA, and 175.9 g of BAPP was used instead of 93.0 g of ODA. The reaction was carried out in the same manner as described in Manufacturing Example 1. Thus, Polymer A-6 was obtained.

[0281] The weight-average molecular weight (Mw) of the polymer A-6 was measured and found to be 24,000. The imide group concentration per repeating unit of the polyimide obtained from the polymer A-6 was 17.0 wt%.

[0282] <Manufacturing Example 7> (Synthesis of Polyimide Precursor (Polymer A-7))

[0283] In the above Manufacturing Example 1, 73.6 g of diphenyl 3,3',4,4'-tetracarboxylic dianhydride (BPDA) and 130.1 g of BPADA were used instead of 155.1 g of ODPA, and 175.9 g of BAPP was used instead of 93.0 g of ODA. Otherwise, the reaction was carried out in the same manner as described in Manufacturing Example 1, whereby polymer A-7 was obtained.

[0284] The weight-average molecular weight (Mw) of the polymer A-7 was measured and found to be 24,000. The imide group concentration per repeating unit of the polyimide obtained from the polymer A-7 was 17.1 wt%.

[0285] <Manufacturing Example 8> (Synthesis of Polyimide Precursor (Polymer A-8))

[0286] In the above Manufacturing Example 1, 219.3 g of 2,2-bis{3-methyl-4-(4-aminophenoxy)phenyl}propane (MBAPP) was used instead of 93.0 g of ODA. Otherwise, the reaction was carried out in the same manner as described in Manufacturing Example 1, whereby polymer A-8 was obtained.

[0287] The weight-average molecular weight (Mw) of the polymer A-8 was measured and found to be 25,000. The imide group concentration per repeating unit of the polyimide obtained from the polymer A-8 was 18.7 wt%.

[0288] <Manufacturing Example 9> (Synthesis of Polyimide Precursor (Polymer A-9))

[0289] In the above Manufacturing Example 1, 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of ODA. Otherwise, the reaction was carried out in the same manner as described in Manufacturing Example 1, whereby polymer A-9 was obtained.

[0290] The weight-average molecular weight (Mw) of the polymer A-9 was measured and found to be 24,000. The imide group concentration per repeating unit of the polyimide obtained from the polymer A-9 was 26.8 wt%.

[0291] <Manufacturing Example 10> (Synthesis of Polyimide Precursor (Polymer A-10))

[0292] In the above Production Example 1, 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) dianhydride (BPADAN) was used instead of 155.1 g of ODPA, and 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 175.9 g of BAPP. Otherwise, the reaction was carried out in the same manner as described in Production Example 1, whereby Polymer A-10 was obtained.

[0293] The weight-average molecular weight (Mw) of this Polymer A-10 was measured, and the result was 23,000. The imide group concentration per repeating unit of the polyimide obtained from Polymer A-10 was 19.1 wt%.

[0294] <Production Example 11> (Synthesis of polyimide precursor (Polymer A-11))

[0295] 260.2 g of BPADA was added to a 2-liter detachable flask, 400 ml of γ-butyrolactone was added under a nitrogen atmosphere, and m-TB was added while stirring at room temperature to obtain a polyamic acid solution.

[0296] Subsequently, the mixture was stirred at 185 °C for 4 hours. After confirming that the theoretical amount of water had been removed, it was cooled to room temperature to obtain Polymer A-11.

[0297] The weight-average molecular weight (Mw) of this Polymer A-11 was measured, and the result was 22,000. The imide group concentration per repeating unit of the polyimide obtained from Polymer A-11 was 19.1 wt%.

[0298] <Production Example 12> (Synthesis of polyimide precursor (Polymer A-12))

[0299] 155.1 g of ODPA was added to a 2-liter detachable flask, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 79.1 g of pyridine was added while stirring at room temperature to obtain a reaction mixture.

[0300] Next, the reaction mixture was cooled to -10°C, and 124.4 g of SOCl2 was added over 60 minutes while maintaining the temperature at -10°C. Next, a suspension prepared by suspending 93.0 g of 4,4'-oxydianiline (ODA) in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The resulting reaction solution was added to 3 liters of ethanol to form a precipitate containing the crude polymer. The resulting crude polymer was dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was purified by using a mixed anion exchange resin ("Amberlyst TM15" manufactured by ORGANO CORPORATION) and a cation exchange resin ("IRA96SB" manufactured by ORGANOCORPORATION) to obtain a polymer solution. The obtained polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered and then vacuum dried to obtain powdery polymer A-12.

[0301] The weight-average molecular weight (Mw) of this polymer A-12 was measured, and the result was 9,000. The imide group concentration per repeating unit of the polyimide obtained from polymer A-12 was 27.4 wt%.

[0302] <Manufacturing Example 13> (Synthesis of polyimide precursor (polymer A-13))

[0303] In the above Manufacturing Example 12, 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of ODA, and the reaction was carried out in the same manner as described in Manufacturing Example 1 except for this, thereby obtaining polymer A-13.

[0304] The weight-average molecular weight (Mw) of this polymer A-13 was measured, and the result was 8,000. The imide group concentration per repeating unit of the polyimide obtained from polymer A-13 was 26.8 wt%.

[0305] [Manufacture of photosensitive resin composition]

[0306] The following compounds were used in the examples and comparative examples.

[0307] Photoinitiator B-1: TR-PBG-304 (manufactured by Changzhou Qiangli Electronic Co., Ltd.)

[0308] Photoinitiator B-2: TR-PBG-305 (manufactured by Changzhou Qiangli Electronic Co., Ltd.)

[0309] Photoinitiator B-3: TR-PBG-3057 (manufactured by Changzhou Qiangli Electronic Co., Ltd.)

[0310] Organic compound C-1: Titanium bis(2,4-pentanedionate) dibutoxide

[0311] Organic compound C-2: Titanium bis(ethyl acetoacetate) diisopropoxide

[0312] Solvent D-1: γ-Butyrolactone (GBL)

[0313] Solvent D-2: Dimethyl sulfoxide (DMSO)

[0314] <Example 1>

[0315] Using polyimide precursor A-2, a negative photosensitive resin composition was prepared according to the following method, and the prepared composition was evaluated. 100 g of A-2 as (A) polyimide precursor and 5 g of B-1 as (B) photoinitiator were dissolved in 100 g of (D) GBL. For the viscosity of the obtained solution, a small amount of GBL was further added to adjust it to about 40 poise. Furthermore, the composition was allowed to stand in a thermostat IN601 (manufactured by Yamato Scientific co., ltd.) at 40 °C for 48 hours for curing to prepare a negative photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 1-1 below.

[0316] <Example 2>

[0317] The curing conditions were set to 144 hours at 40 °C, and a negative photosensitive resin composition was prepared in the same manner as in Example 1 except for this, and the same evaluation as in Example 1 was carried out. The results are shown in Table 1-1 below.

[0318] <Example 3>

[0319] 1 g of C-1 as (C) organic compound was added, the curing conditions were set to 48 hours at 23 °C, and a negative photosensitive resin composition was prepared in the same manner as in Example 1 except for this, and the same evaluation as in Example 1 was carried out. The results are shown in Table 1-1 below.

[0320] <Examples 4 to 21, Comparative Examples 1 to 12>

[0321] Preparation and curing were carried out according to the compounding ratios shown in Tables 1 and 2 below, and a negative photosensitive resin composition was prepared in the same manner as in Examples 1 to 3 except for this, and the same evaluation as in Example 1 was carried out. It should be noted that in the tables, when the curing temperature and curing time are recorded as "-", it means that curing was not carried out. The results are shown in Tables 1 and 2 below.

[0322] [Table 1]

[0323]

[0324] [Table 2]

[0325]

[0326] As shown in Table 1 and Table 2, the imidization rates of the photosensitive resin compositions of Examples 1 to 21 showed high values compared with those of Comparative Examples 1 to 7, 11, and 12. High absorbance values were shown in Comparative Examples 8 and 9, and the resolution was "not possible". In Comparative Example 8, the imidization rate was 52.6%, which was a value exceeding 50%. In Comparative Example 10, the resin composition was gelled and evaluation could not be carried out.

[0327] Industrial Applicability

[0328] By using the photosensitive resin composition of the present invention, a cured film having high resolution under a thick film and showing a low dielectric loss tangent can be obtained. Therefore, the photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for, for example, manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. A photosensitive resin composition, comprising: (A) A polyimide precursor represented by the following general formula (1): 100 parts by mass, In formula (1), X1 is a tetravalent organic group having 6 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 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, where, At least one of R1 and R2 is a group represented by the following general formula (2), In formula (2), R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10; (B) A photosensitizer: 0.5 to 10 parts by mass; and (D) A solvent: 100 to 300 parts by mass, The imidization ratio b of the photosensitive resin composition is 15% to 50%. The imidization ratio b is the value obtained by dividing the peak intensity near 1380 cm -1 in the infrared absorption spectrum of the photosensitive resin layer before exposure obtained by desolvation of the photosensitive resin composition by the ATR (attenuated total reflection) method by the peak intensity near 1500 cm -1 and then dividing the imidization index of the photosensitive resin layer by the imidization index of the cured film obtained by heating and curing the photosensitive resin composition at 350 °C. Moreover, in the polyimide of the cured film, the proportion of imide groups, that is, the imide group concentration a, relative to the molecular weight of the repeating unit containing the structure derived from the tetracarboxylic acid and the diamine is 12 wt% to 30 wt%. The photosensitive resin composition further contains (C) at least one organic compound selected from organic titanium compounds or organic zirconium compounds: 0.01 to 5 parts by mass.

2. The photosensitive resin composition according to claim 1, wherein, The n1 is an integer of 3 to 100.

3. The photosensitive resin composition according to claim 1, wherein, The n1 is an integer of 5 to 70.

4. The photosensitive resin composition according to claim 1, wherein The R3 is a hydrogen atom or a methyl group, the R4 and R5 are hydrogen atoms, and m1 is an integer of 2 to 4.

5. The photosensitive resin composition according to claim 1, wherein, The imidization rate b is 15% to 40%.

6. The photosensitive resin composition according to claim 1, wherein The (B) photosensitizer is a photo radical polymerization initiator.

7. The photosensitive resin composition according to claim 6, wherein, The photo radical polymerization initiator is an oxime-based photo radical polymerization initiator.

8. The photosensitive resin composition according to claim 1, wherein, The (B) photosensitizer is 1 part by mass or more and 8 parts by mass or less relative to 100 parts by mass of the (A) polyimide precursor.

9. The photosensitive resin composition according to claim 1, wherein The imide group concentration a and the imidization rate b satisfy the following formula (1), 0.10 ≤ a × (1 - b) ≤ 0.17...(1).

10. The photosensitive resin composition according to any one of claims 1 to 9, wherein In the polyimide of the polyimide cured film, the proportion of the imide group, that is, the imide group concentration a, is 12 wt% to 24 wt% relative to the molecular weight of the repeating unit containing the structure derived from the tetracarboxylic acid and the diamine.

11. The photosensitive resin composition according to claim 10, wherein, The imide group concentration a is 12.5 wt% to 23.0 wt%.

12. The photosensitive resin composition according to claim 10, wherein, The imide group concentration a is 13.5 wt% to 21.0 wt%.

13. The photosensitive resin composition according to any one of claims 1 to 9, wherein, The imidization index of the polyimide cured film obtained by heating and curing at 350 °C is 0.10 to 0.

54.

14. The photosensitive resin composition according to claim 13, wherein, The imidization index of the polyimide cured film obtained by heating and curing at 350 °C is 0.35 to 0.

53.

15. The photosensitive resin composition according to any one of claims 1 to 9, wherein, The absorbance at 365 nm per 1 μm of the photosensitive resin layer obtained by coating the photosensitive resin composition on quartz glass and heating at 110 °C for 3 minutes is 0.02 to 0.

09.

16. The photosensitive resin composition according to claim 15, wherein The absorbance at 365 nm per 1 μm of the photosensitive resin layer obtained by coating the photosensitive resin composition on quartz glass and heating at 110 °C for 3 minutes is 0.04 to 0.

09.

17. The photosensitive resin composition according to claim 15, wherein, The absorbance at 365 nm per 1 μm of the photosensitive resin layer obtained by coating the photosensitive resin composition on quartz glass and heating at 110 °C for 3 minutes is 0.05 to 0.

09.

18. The photosensitive resin composition according to any one of claims 1 to 9, wherein, Y1 in the general formula (1) is as shown in the following formula (Y1), In formula (Y1), Rz are each independently a monovalent organic group having 1 to 10 carbon atoms optionally containing a halogen atom, a is an integer of 0 to 4, A is an oxygen atom or a sulfur atom, and B is one of the following formulas:

19. The photosensitive resin composition according to claim 18, wherein, The Y1 is as shown in the following chemical formula:

20. The photosensitive resin composition according to any one of claims 1 to 9, wherein, X1 in the general formula (1) is as shown in the following chemical formula: In formula (X1), each Ry is independently a monovalent organic group having 1 to 10 carbon atoms optionally containing a halogen atom, a is an integer of 0 to 4, C is an oxygen atom or a sulfur atom, and D is one of the following chemical formulas:

21. The photosensitive resin composition according to claim 20, wherein, The X1 is as shown in the following chemical formula:

22. The photosensitive resin composition according to any one of claims 1 to 9, wherein, The photosensitive resin composition is negative and contains (A) a polyimide precursor: 50 to 85 parts by mass, (B) a photosensitizer: 0.5 to 10 parts by mass, and (D) a solvent: 100 to 300 parts by mass, and contains 15% to 50% by mass of the polyimide precursor, and the polyimide precursor is the polyimide precursor represented by the following general formula (1) having a structure represented by the following general formula (11) in the molecule, In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and m is an integer of 2 to 150.

23. The photosensitive resin composition according to any one of claims 1 to 9, wherein, The photosensitive resin composition is negative and contains (A) a polyimide precursor: 50 to 85 parts by mass, (B) a photosensitizer: 0.5 to 10 parts by mass, and (D) a solvent: 100 to 300 parts by mass, and contains 15% to 50% by mass of the polyimide precursor, and the polyimide precursor is a blend of the polyimide precursor represented by the general formula (1) and a polyimide having a structure represented by the following general formula (11), In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and m is an integer of 2 to 150.

24. The photosensitive resin composition according to any one of claims 1 to 9, which contains (C) at least one organic compound selected from an organic titanium compound or an organic zirconium compound: 0.1 to 3 parts by mass.

25. The photosensitive resin composition according to any one of claims 1 to 9, wherein, The (C) organic compound is an organic titanium compound.

26. The photosensitive resin composition according to claim 25, wherein, The organic titanium compound is at least one compound selected from the group consisting of a tetraalkoxy titanium compound, a titanium chelate compound, a titanate compound, and a titanocene compound.

27. The photosensitive resin composition according to claim 26, wherein, The organic titanium compound is a titanium chelate having two or more alkoxy groups or tetraalkoxy titanium.

28. The photosensitive resin composition according to any one of claims 1 to 9, which is used for forming an interlayer insulating film for a rewiring layer.

29. The photosensitive resin composition according to any one of claims 1 to 9, which further contains (E) a monomer: 0.5 to 15 parts by mass.

30. The photosensitive resin composition according to claim 29, wherein, The (E) monomer contains at least one group selected from the group consisting of a hydroxyl group and an amino group.

31. A method for manufacturing a photosensitive resin composition according to any one of claims 1 to 30, which includes the following steps: A step of mixing the (A) polyimide precursor, the (B) photosensitizer, and the (D) solvent; and A step of curing the obtained mixture at 23°C to 50°C for 24 hours to 360 hours to adjust the imidization rate b to 15% to 50%.

32. A method for manufacturing a photosensitive resin composition according to any one of claims 1 to 30, which includes the following steps: A step of mixing the (A) polyimide precursor, the (B) photosensitizer, and the (D) solvent; and A step of curing the obtained mixture at 30°C to 50°C for 48 hours to 280 hours to adjust the imidization rate b to 15% to 50%.

33. A method for manufacturing a polyimide cured film, comprising the following steps (1) to (5): (1) A step of coating the photosensitive resin composition according to any one of claims 1 to 29 on a substrate to form a photosensitive resin layer on the substrate; (2) A step of heating and drying the obtained photosensitive resin layer; (3) A step of exposing the heated and dried photosensitive resin layer; (4) A step of developing the exposed photosensitive resin layer; and (5) A step of heat-treating the developed photosensitive resin layer to form a polyimide cured film.

34. The method for manufacturing a polyimide cured film according to claim 33, wherein, The polyimide cured film has a dielectric loss tangent of 0.0021 to 0.007 when measured at 10 GHz by the perturbed split-cylinder resonator method.

35. The manufacturing method of the polyimide cured film according to claim 34, wherein, The polyimide cured film has a dielectric loss tangent of 0.0030 to 0.0065 when measured at 10 GHz by the perturbed split-cylinder resonator method.

36. The method for manufacturing a polyimide cured film according to claim 33 or 34, wherein, The polyimide cured film has a dielectric loss tangent of 0.0021 to 0.008 when measured at 28 GHz by the perturbed split-cylinder resonator method.

37. The method for manufacturing a polyimide cured film according to claim 36, wherein, The polyimide cured film has a dielectric loss tangent of 0.0030 to 0.0075 when measured at 28 GHz by the perturbed split-cylinder resonator method.

38. The method for manufacturing a polyimide cured film according to claim 33 or 34, wherein, The polyimide cured film has a dielectric loss tangent of 0.0021 to 0.008 when measured at 40 GHz by the perturbed split-cylinder resonator method.

39. The manufacturing method of the polyimide cured film according to claim 38, wherein, The polyimide cured film has a dielectric loss tangent of 0.0030 to 0.0075 when measured at 40 GHz by the perturbed split-cylinder resonator method.

40. The method for manufacturing a polyimide cured film according to claim 33 or 34, wherein, The polyimide cured film has a dielectric loss tangent of 0.0021 to 0.009 when measured at 60 GHz by the perturbed split-cylinder resonator method.

41. The method for manufacturing a polyimide cured film according to claim 40, wherein, The polyimide cured film has a dielectric loss tangent of 0.0030 to 0.0085 when measured at 60 GHz by the perturbed split-cylinder resonator method.

42. A method for manufacturing a polyimide cured film, wherein the polyimide cured film uses a photosensitive resin composition containing the following components: (A) A polyimide precursor represented by the following general formula (1): 100 parts by mass, In formula (1), X1 is a tetravalent organic group having 6 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 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, wherein, At least one of R1 and R2 is a group represented by the following general formula (2), In formula (2), R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10; (B) A photosensitizer: 0.5 to 10 parts by mass; and (D) A solvent: 100 to 300 parts by mass, The manufacturing method includes the following steps (1) to (5): (1) A step of coating the photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate; (2) A step of heating and drying the obtained photosensitive resin layer to remove the solvent; (3) A step of exposing the photosensitive resin layer after removing the solvent; (4) A step of developing the exposed photosensitive resin layer; and (5) A step of heat-treating the developed photosensitive resin layer to form a polyimide cured film, The imidization ratio b of the photosensitive resin layer before exposure obtained by removing the solvent after heating and drying in the step (2) is 15 to 50%, and the imidization ratio b is the value obtained by dividing the peak intensity near 1380 cm -1 in the infrared absorption spectrum of the photosensitive resin layer before exposure obtained by removing the solvent from the photosensitive resin composition by the ATR (attenuated total reflection) method by the peak intensity near 1500 cm -1 and then dividing the imidization index of the photosensitive resin layer thus obtained by the imidization index of the cured film obtained by heating and curing the photosensitive resin composition at 350 °C.

43. The manufacturing method of the polyimide cured film according to claim 42, wherein, wherein n1 is an integer of 3 to 100.

44. The manufacturing method of the polyimide cured film according to claim 42, wherein, wherein n1 is an integer of 5 to 70.

45. The method for manufacturing a polyimide cured film according to claim 42, wherein, R3 is a hydrogen atom or a methyl group, and R4 and R5 are hydrogen atoms.

46. The method for manufacturing a polyimide cured film according to claim 42, wherein, The imidization rate b is 15% to 40%.

47. The method for manufacturing a polyimide cured film according to claim 42, wherein, The photosensitizer (B) is a photo radical polymerization initiator.

48. The manufacturing method of the polyimide cured film according to claim 47, wherein, The photo radical polymerization initiator is an oxime-based photo radical polymerization initiator.

49. The method for manufacturing a polyimide cured film according to claim 42, wherein, The photosensitizer (B) is 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the polyimide precursor (A).

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