Photosensitive resin composition, cured film, production method for cured film, and semiconductor device

Abstract

A photosensitive resin composition according to the present invention includes (A) at least one type of resin selected from the group that consists of polyimide precursors and polyimides, (B) a photopolymerization initiator, and (C) a compound that has an alkyl group. The refractive index Nave of a dried film formed by applying the photosensitive resin composition and then drying for 360 seconds at 110°C is no more than 1.5800, and the water permeability WVTR (g / m2·24 hr) of a cured film formed by curing the dried film for 2 hours at 230°C is no more than 300.

Description

Photosensitive resin composition, cured film, method for producing cured film, and semiconductor device

[0001] The present disclosure relates to a photosensitive resin composition, a cured film obtained using the composition, a method for producing the cured film, and a semiconductor device.

[0002] Polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which combine excellent heat resistance, electrical properties, and mechanical properties, have traditionally been used as insulating materials for electronic components, and passivation films, surface protective films, and interlayer insulating films for semiconductor devices. Among these resins, those provided in the form of photosensitive resin compositions are easily able to form relief pattern films with excellent heat resistance by undergoing ring-closing treatment (imidization or benzoxazole formation) by coating, exposure, development, and curing of the composition, as well as thermal crosslinking. Such photosensitive resin compositions facilitate significant shortening of the manufacturing process compared to conventional non-photosensitive materials, and are therefore suitable for use in the fabrication of semiconductor devices.

[0003] Semiconductor devices (hereinafter referred to as "elements") are mounted on printed circuit boards using various methods depending on the purpose. Conventional elements were generally fabricated using the "wire bonding method," which connects the element's external terminals (pads) to the lead frame with thin wires. However, as elements have become faster and their operating frequencies have reached the GHz range, differences in the wiring length of each terminal during mounting have come to affect the operation of the element. Therefore, when mounting elements for high-end applications, it has become necessary to precisely control the length of the mounting wiring, and wire bonding has become difficult to meet this requirement.

[0004] To address this issue, a "flip-chip mounting" technique has been proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped over and directly mounted on a printed circuit board. Because flip-chip mounting allows for precise control of the wiring distance, it is well-suited for use in high-end applications that handle high-speed signals, and because of its small mounting size, it is suitable for use in devices such as mobile phones. Consequently, demand for this technology is rapidly expanding. Recently, a semiconductor chip mounting technology called "fan-out wafer-level packaging (FOWLP)" has been proposed, in which a pre-processed wafer is diced to produce individual chips, the individual chips are then reassembled on a support, encapsulated with molding resin, and a redistribution layer is formed after the support is peeled off (see, for example, Patent Document 1). In fan-out wafer-level packaging, the redistribution layer is formed with a thin film thickness, which facilitates the reduction of the package height and facilitates the realization of high-speed transmission and low cost.

[0005] In recent years, with the significant increase in the volume of information and communications, there has been a growing need to achieve faster communication speeds than conventional standards. Against this backdrop, a transition to fifth-generation communications (5G) using frequencies above 3 GHz or to communications in ultra-high frequency bands from the quasi-millimeter wave band (20 GHz to 30 GHz) to the millimeter wave band (30 GHz or higher), where wider frequency bandwidths are more easily secured, is unavoidable. Therefore, not only printed circuit boards but also the semiconductor chips on which the boards are mounted are required to be compatible with high frequencies. To reduce transmission loss, "antenna-in-package (AiP)" has been developed, in which a front-end module (FEM) that transmits and receives radio waves is integrated with an antenna (see, for example, Patent Document 2). AiPs have short wiring lengths, making it possible to suppress transmission loss, which increases in proportion to wiring length. However, there is also a demand for rewiring materials that can reduce transmission loss.

[0006] In order to reduce transmission loss in the high frequency band, the thickness of the insulating film (i.e., the cured film) can be increased, and the dielectric loss tangent of the cured film itself can be reduced. For this reason, photosensitive resin compositions used in high frequency band devices are required to be able to form good pattern shapes even when the film is thick, and to be able to achieve high resolution and a low dielectric loss tangent.

[0007] In this technical field, for example, Patent Documents 3 and 4 disclose photosensitive resin compositions each containing a specific additive or a specific crosslinking agent as an essential component. Also, Patent Document 5 (see particularly the Examples section) focuses on the dielectric loss tangent at 1 GHz and discloses a photosensitive resin composition for providing a cured film capable of reducing it.

[0008] JP 2005-167191 A U.S. Patent Application Publication No. 2016 / 0104940 Specification WO 2021 / 157306 JP 2021-152634 A WO 2019 / 044874

[0009] Polyimides tend to have high material reliability due to their excellent insulating properties and thermomechanical properties. On the other hand, when the dried film (e.g., a film obtained by drying a coating of a polyimide precursor) has a thickness of 30 μm or more, the development time becomes long and the light absorption of the film itself becomes large, making it difficult to form a good pattern shape and achieve high resolution compared to when the film is thinner. In addition, the dielectric loss tangent of the cured film tends to be high due to the influence of polar functional groups derived from the imide group, polar functional groups added for photosensitization, and additives, etc., which is a problem.

[0010] In the photosensitive resin composition described in Patent Document 3, the additive, which is an essential component, contains a highly polar functional group, which may result in a deterioration in dielectric loss tangent. Also, in the photosensitive resin composition described in Patent Document 4, there is a concern that the dielectric properties may be deteriorated in the high frequency band due to the influence of the crosslinking agent (polyfunctional (meth)acrylate), which is an essential component.

[0011] The photosensitive resin composition described in Patent Document 5 is discussed only for a low frequency of 1 GHz, and therefore its performance may be insufficient as a rewiring layer for AiP, which is used for high frequency applications.

[0012] An object of the present disclosure is to provide a photosensitive resin composition that can achieve both high resolution and a low dielectric loss tangent even when the film is thick, and that is advantageous for realizing a device that can suppress transmission loss in the high frequency band. Another object of the present disclosure is to provide a cured film obtained using the photosensitive resin composition, a method for producing the cured film, and a semiconductor device.

[0013] One aspect of the present disclosure is as follows: [1] A photosensitive resin composition comprising the following components: (A) at least one resin selected from a polyimide precursor and a polyimide, (B) a photopolymerization initiator, and (C) a compound having an alkyl group, wherein the photosensitive resin composition is applied and then dried at 110°C for 360 seconds to form a dried film having a refractive index Nave of 1.5800 or less, and the dried film is cured at 230°C for 2 hours to form a cured film having a water permeability WVTR (g / m ２ 24 hr) is 300 or less. [2] The photosensitive resin composition according to item 1, wherein the component (C) has an alkyl group having 4 or more carbon atoms. [3] The photosensitive resin composition according to item 1, wherein the component (C) is a compound represented by the following general formula (1): (wherein X is an alkyl group, Y is an organic group having 1 to 30 carbon atoms and containing at least one selected from an ester group, an isocyanurate group, an amide group, and a urea group, and m １ is an integer from 1 to 4, where m １ [4] The photosensitive resin composition according to item 1 or 2, wherein, in general formula (1), m １ The photosensitive resin composition according to any one of items 1 to 3, wherein the total number of carbon atoms of the X's is 10 to 20. [5] In the general formula (1), m １ When m is 1, X is a linear alkyl group; １[6] The photosensitive resin composition according to any one of items 1 to 4, wherein when is 2 or more, at least one of X is a linear alkyl group. [7] The photosensitive resin composition according to any one of items 1 to 5, wherein the content of the component (C) is 0.5 to 50 parts by mass per 100 parts by mass of the component (A). [8] The photosensitive resin composition according to any one of items 1 to 5, wherein the content of the component (C) is 0.5 to 50 parts by mass per 100 parts by mass of the component (A): (wherein X is an organic group having 1 to 30 carbon atoms, a plurality of X may be the same or different, and at least one of the plurality of X is an alkyl group). [8] The photosensitive resin composition according to any one of items 1 to 6, wherein the component (C) has at least one selected from the structures represented by general formulas (4) to (6). [9] The photosensitive resin composition according to item 7, wherein the component (A) has at least one selected from the structures represented by the following general formula (8): (In the formula, A １ is a tetravalent organic group having 6 to 40 carbon atoms, and B １ is a divalent organic group having 6 to 40 carbon atoms, and n １ is an integer from 2 to 100, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms), and / or a group represented by the following general formula (9): (In the formula, A ２ is a tetravalent organic group having 6 to 40 carbon atoms, and B ２ is a divalent organic group having 6 to 40 carbon atoms, and n ２

[10] The photosensitive resin composition according to any one of items 1 to 8, having at least one structure selected from the following general formula (8): １ , and R ２ At least one of the following general formula (10): (In the formula, R ３ , R ４ , and R ５ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １

[11] The photosensitive resin composition according to item 9, containing a group represented by the formula (8): １ and / or B in the general formula (9) ２ is represented by the following general formula (11): (In the formula, R ６ , and R ７ are each independently an organic group having 1 to 5 carbon atoms, and m ２ , and m ３ are each independently an integer of 1 to 4, and * is a bonding portion to the main chain of the resin.

[12] The photosensitive resin composition according to item 9 or 10, wherein the component (B) is a compound represented by the following general formula (12): (In the formula, R ８ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and R ９ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and R １０ is -H, -OH, -COOH, -O(CH ２ )OH, —O(CH ２ )2OH, -COO(CH ２ )OH or —COO(CH ２ ) ２OH).

[13] The photosensitive resin composition according to any one of items 1 to 12, wherein a cured film of the photosensitive resin composition has a dielectric loss tangent of 0.015 or less, measured at 10 GHz using a perturbation split cylinder resonator method.

[14] The photosensitive resin composition according to any one of items 1 to 13, which is used to form an interlayer insulating film.

[15] A method for producing a cured film, the method comprising: applying the photosensitive resin composition according to any one of items 1 to 10 onto a substrate, and forming a photosensitive resin layer on the substrate; exposing the photosensitive resin layer; developing the photosensitive resin layer after exposure; and heating the photosensitive resin layer after development to form a cured film.

[16] A cured film of the photosensitive resin composition according to any one of items 1 to 14, wherein the cured film has a thickness of 25 μm or more.

[17] A cured film of the photosensitive resin composition according to any one of items 1 to 14, wherein the cured film has a dielectric loss tangent of 0.015 or less as measured at 10 GHz using a perturbation split cylinder resonator method.

[18] The cured film according to item 17, wherein the cured film has a thickness of 25 μm or more.

[19] A semiconductor device comprising the cured film according to any one of items 16 to 18.

[0014] According to the present disclosure, it is possible to provide a photosensitive resin composition capable of forming a cured film (in one embodiment, a cured relief pattern) that can achieve both high resolution and a low dielectric loss tangent even under conditions of a thick film thickness. Such a photosensitive resin composition is advantageous for realizing a device that can suppress transmission loss in the high frequency band. Furthermore, according to the present disclosure, it is possible to provide a cured film obtained using such a photosensitive resin composition, a method for producing the cured film, and a semiconductor device.

[0015] Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, when a structure represented by the same symbol in a general formula is present in a molecule, each structure is independently selected unless otherwise specified, and may be the same or different from each other. In the present specification, in numerical ranges described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. Furthermore, the term "step" includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as the function of the step is achieved.

[0016] <Photosensitive Resin Composition> The photosensitive resin composition of the present disclosure contains the following components: (A) at least one resin selected from a polyimide precursor and a polyimide, (B) a photopolymerization initiator, and (C) a compound having an alkyl group. The photosensitive resin composition may further contain components other than (A) to (C) (other components) as desired. When components (A) to (C) and their raw materials, as well as solvents required for producing components (A) to (C), and other components are included, such other components may be used alone or in combination, in cases where a mixture of two or more types is possible.

[0017] Here, the photosensitive resin composition of the present disclosure has a refractive index N of 100 μm when the photosensitive resin composition is applied and then dried at 110° C. for 360 seconds. ａｖｅ The dry film has a water permeability WVTR (g / m) of 1.5800 or less, and when the dry film is cured at 230°C for 2 hours, the cured film has a water permeability WVTR (g / m ２ 24 hr) is 300 or less. This makes it possible to provide a photosensitive resin composition capable of forming a cured film (in one embodiment, a cured relief pattern) that can achieve both high resolution and a low dielectric loss tangent even when the film thickness is large.

[0018] The refractive index is an index of the propagation speed of light in a substance. The present inventors have found that when the refractive index of a dried film of a photosensitive resin composition (a dried film at 110°C for 360 seconds) is in the range of 1.5800 or less, good resolution is achieved even when the dried film thickness is 30 μm or more. The mechanism by which this is achieved is unclear, but the inventors speculate as follows.

[0019] In a dried film of a photosensitive resin composition, when the polymer chains are weakly oriented and have an amorphous structure, the refractive index tends to be low. It is believed that weakly oriented polymer chains have higher solubility in a developer and lower absorbance than strongly oriented polymer chains. By using a photosensitive resin composition whose dried film (dried at 110°C for 360 seconds) has a refractive index within the above range, the solubility of the unexposed areas is high, thereby suppressing development residues. Furthermore, since a sufficient amount of light reaches the bottom of the film, the crosslinking reaction easily proceeds, thereby suppressing dissolution of the bottom of the film in the exposed areas. In other words, the contrast between the unexposed and exposed areas is ensured, allowing for a good pattern shape to be obtained with high resolution. In particular, when the film thickness of the dried film is 30 μm or more, the required development time tends to be longer and the absorbance tends to be higher compared to when the film thickness is thinner than that, which is presumably a significant effect.

[0020] Methods for lowering the refractive index of a dried film of a photosensitive resin composition include making the polymer skeleton bend and flexible, and adding a bulky component (e.g., a component that hinders the orientation of the polymer chain) as an additive. The refractive index N of the dried film of the photosensitive resin composition of the present disclosure when dried at 110°C for 360 seconds is ａｖｅ As described above, the refractive index N ａｖｅ From the viewpoint of reliability, the lower limit of may be, for example, 1.0000 or more, preferably 1.5000 or more, and may be 1.5500 or more.

[0021] On the other hand, water permeability is an index of the ease with which water vapor passes through a substance. When a cured film absorbs moisture, polarization in the cured film increases, which is thought to worsen the dielectric loss tangent. Therefore, there is a correlation between low water permeability and low dielectric loss tangent. The higher the density of the cured film and the more hydrophobic it is, the lower the water permeability tends to be. For the photosensitive resin composition of the present disclosure, the water permeability WVTR (g / m) of the cured film when the above-mentioned dried film is cured at 230°C for 2 hours is ２ 24 hr) is 300 or less, preferably less than 280. The lower limit of the water permeability WVTR, which can be arbitrarily combined with these upper limits, is not particularly limited, but may be, for example, more than 0, 100 or more, 150 or more, or 200 or more.

[0022] As described above, in a photosensitive resin composition, reducing the refractive index of a dried film and reducing the water permeability of a cured film are contradictory designs. However, according to the present disclosure, it has been discovered that the problem can be solved by combining components (A), (B), and (C).

[0023] <Component (A)> The component (A) is at least one resin selected from a polyimide precursor and a polyimide. The component (A) is represented by the following general formula (8): (In the formula, A １ is a tetravalent organic group having 6 to 40 carbon atoms, and B １ is a divalent organic group having 6 to 40 carbon atoms, and n １ is an integer from 2 to 100, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms), and / or a group represented by the following general formula (9): (In the formula, A ２ is a tetravalent organic group having 6 to 40 carbon atoms, and B ２ is a divalent organic group having 6 to 40 carbon atoms, and n ２is an integer of 2 to 100), it is preferable that the photosensitive resin composition has at least one structure selected from the following:

[0024] In formula (8), R １ , and R ２ At least one of the groups preferably contains a reactive substituent that initiates or advances a reaction by heat and / or light, and from the viewpoint of easily achieving the effects of the present disclosure and easily realizing a cured film excellent in various properties, it is particularly preferable that the group be a group represented by the following general formula (10): (In the formula, R ３ , R ４ , and R ５ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ is an integer of 2 to 10).

[0025] In formula (10), examples of the monovalent organic group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is preferred. ３ is preferably a hydrogen atom or a methyl group, and R ４ , and R ５ are preferably each independently a hydrogen atom or a methyl group, and more preferably, R ４ , and R ５ Both are hydrogen atoms. １ is preferably an integer of 2 to 5, more preferably an integer of 2 to 3.

[0026] In formula (8) and / or (9), n １ , and n ２ is preferably an integer of 1 to 100, more preferably an integer of 3 to 70, from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition.

[0027] In formula (8) and / or (9), A １ , and A ２ From the viewpoint of achieving both heat resistance and photosensitive properties, the tetravalent organic group represented by the formula (I) is preferably an organic group having 6 to 40 carbon atoms, more preferably -COOR ２ group, and -COOR ３ A group (particularly, an aromatic group or an alicyclic aliphatic group) in which the —CONH— group and the —CONH— group are in the ortho position relative to each other. １ , and A ２ Specific examples of the tetravalent organic group represented by the formula (13) include an organic group having 6 to 40 carbon atoms and containing an aromatic ring, such as a tetravalent organic group represented by the formula (13) below: (In the formula, R １１ are each independently a monovalent group selected from a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms; m ４ is an integer from 1 to 2, and m ５ is an integer from 1 to 3, and m ６ is an integer of 1 to 4). １ , and A ２ The tetravalent organic group represented by the formula (13) may be one type or a combination of two or more types. １ , and A ２ The group is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0028] In formula (8) and / or (9), B １ , and B ２ From the viewpoint of achieving both heat resistance and photosensitive properties, the divalent organic group represented by the following general formula (14): (In the formula, R １１ are each independently a monovalent group selected from a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms; m ５ is an integer from 1 to 3, and m ６ is an integer of 1 to 4). １ , and B ２The divalent organic group represented by the formula (14) may be one type or a combination of two or more types. １ , and B ２ The group is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0029] In formula (8) and / or (9), B １ , and B ２ The divalent organic group represented by the following general formula (11): (In the formula, R ６ , and R ７ are each independently an organic group having 1 to 5 carbon atoms, and m ２ , and m ３ are each independently an integer of 1 to 4, and * is a bonding portion to the main chain of the resin. １ , and / or B ２ However, by including the structure represented by formula (11), the structure represented by formula (11) can be introduced into component (A).

[0030] B １ , and / or B ２ By including the structure of formula (11), it is easy to obtain a cured film having high resolution and a low dielectric loss tangent even under conditions where the film thickness is thick. ６ , and R ７ By introducing an organic group of the formula (11), the solubility in a developer is improved even under conditions of a thick film thickness, and therefore, a good pattern shape and high resolution can be easily realized. Furthermore, since the structure of formula (11) has a biphenyl skeleton, the mobility of the polymer chain is likely to decrease, and therefore the low dielectric tangent is likely to decrease. Furthermore, when the biphenyl skeleton is ６ , and R ７ The introduction of β-glucan causes a twist in the biphenyl skeleton due to steric hindrance, which tends to reduce the absorbance of the polymer. In this case, the amount of light reaching the bottom of the film is ensured even under conditions of thick film thickness, making it easier to achieve good pattern shapes with high resolution.

[0031] In formula (11), R ６ , and R ７ is more preferably an alkyl group having 1 to 5 carbon atoms. ６, and R ７ However, by using an alkyl group having 1 to 5 carbon atoms, a structure with low molar polarizability can be achieved, and such a structure can be introduced into component (A). In this case, the low polarity reduces water permeability, making it easier to achieve a cured film with a lower dielectric dissipation factor.

[0032] The above formula (11) is represented by the following general formula (15): (wherein * is a bonding site to the main chain of the resin)

[0033] Component (A) may have other reactive unsaturated bonds at the ends of the main chain that initiate polymerization by heat and / or light. Such reactive unsaturated bonds refer to bonds that react with heat and / or light and can crosslink with each other. An example of the structure of the main chain end modified with such a reactive substituent is represented by the following formula: Examples include:

[0034] <<Method for Producing Component (A)>> (Tetracarboxylic Acid Dianhydride) Tetracarboxylic acid dianhydrides are preferably used to prepare polyimide precursors and / or polyimides. In particular, tetracarboxylic acid dianhydrides containing A, a tetravalent organic group having 6 to 40 carbon atoms, are preferred. １ , and A ２ {A in formula (8) and formula (9) １ , and A ２) In addition to the tetracarboxylic dianhydrides derived from the structures listed above, examples of the tetracarboxylic dianhydrides having the above structure include 4,4'-oxydiphthalic dianhydride, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, diphenylsulfone-3,3',4,4 Examples of the tetracarboxylic dianhydride include 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)diphthalic anhydride, and 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride. The tetracarboxylic dianhydrides may be used alone or in combination of two or more.

[0035] (Diamine Compound) A diamine compound is preferably used to prepare a polyimide precursor and / or a polyimide. In particular, a divalent organic group B having 6 to 40 carbon atoms is preferably used. １ , and B ２ {B in formula (8) and formula (9) １ , and B ２) In addition to the diamines derived from the structures listed above, examples of the diamine compounds having the structure include p-phenylenediamine, m-phenylenediamine, 2,2'-dimethylbiphenyl-4,4'-diamine, 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, 3,3',5,5'-tetramethylbenzidine, 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 l) Benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl) propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and bis{4-(4-aminophenoxy)phenyl}ketone, as well as compounds in which part of the hydrogen atoms on the benzene rings of these compounds have been substituted with alkyl chains such as methyl groups and ethyl groups, for example, 2,Examples of the diamine compound include 2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. The diamine compounds may be used alone or in combination of two or more.

[0036] (Terminal reactive substituent-introducing compound) For the polyimide precursor and / or polyimide, examples of compounds for introducing reactive substituents into the main chain terminals thereof (terminal reactive substituent-introducing compound) include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, allylamine, methacrylic acid chloride, and mixtures thereof. The terminal reactive substituent-introducing compound may be used alone or in combination of two or more.

[0037] (Reaction Solvent) The reaction solvent used in the synthesis of the polyimide precursor and / or polyimide is preferably one that can suitably dissolve the raw materials, i.e., the tetracarboxylic dianhydride, the first substituent-introducing compound described below, and the product, i.e., the acid / ester compound. More preferably, the reaction solvent is one that can also suitably dissolve the polyimide precursor, which is the amide polycondensation product of the acid / ester compound and a diamine.

[0038] Examples of solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), and tetramethylurea. Furthermore, examples of solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate. Examples of lactones include γ-butyrolactone. Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran. Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene. Examples of hydrocarbons include hexane, heptane, benzene, toluene, xylene, etc. The reaction solvent may be used alone or in combination of two or more.

[0039] In order to improve the adhesion between the photosensitive resin layer obtained using the photosensitive resin composition and various substrates, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can be used as copolymerization components when preparing component (A).

[0040] (Synthesis of Polyimide Precursor) The polyimide precursor (polyamic acid ester) of the present disclosure can be prepared, for example, by the following (step i): １ with an alcohol having a photopolymerizable unsaturated double bond (at this time, a saturated aliphatic alcohol having 1 to 4 carbon atoms may be optionally used in the reaction) to prepare a partially esterified tetracarboxylic acid (acid / ester form); and the following (step ii): １and a diamine containing the compound (II) and (III) are subjected to amide polycondensation.

[0041] (Step i) Preparation of Acid / Ester Form In this step, a tetravalent organic group A having 6 to 40 carbon atoms is prepared. １ and a compound having a reactive substituent that reacts with heat and / or light (also referred to as a "substituent-introduced compound" in the present disclosure), an esterified tetracarboxylic acid (acid / ester form) can be obtained.

[0042] Substituent-introducing compounds (also referred to as "first substituent-introducing compounds" in the present disclosure) suitable for use in synthesizing esterified tetracarboxylic acids include alcohols having reactive substituents that react with heat and / or light. Examples of alcohols having such reactive substituents include 2-hydroxyethyl methacrylate (HEMA), 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0043] As the saturated aliphatic alcohols that can be optionally used together with the alcohols having a reactive substituent, saturated aliphatic alcohols having 1 to 4 carbon atoms are preferred, and specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

[0044] The tetracarboxylic dianhydride and the first substituent-introducing compound are mixed and stirred preferably in the presence of a basic catalyst such as pyridine, preferably in an appropriate reaction solvent, at a temperature of 20 to 50°C for 4 to 10 hours, whereby the esterification reaction of the acid anhydride proceeds, and the desired acid / ester form can be obtained.

[0045] (Step ii): Amide polycondensation reaction of acid / ester and diamine In this step, the acid / ester prepared above is subjected to a condensation reaction with a diamine to synthesize a polyamic acid ester. The acid / ester is typically in the form of a solution dissolved in the reaction solvent after the acid / ester is prepared by the above method. A suitable dehydration condensing agent is added and mixed, preferably under ice cooling, to convert the acid / ester into a polyacid anhydride. Next, a solvent in which a diamine is dissolved or dispersed is added dropwise, and the two are subjected to amide polycondensation to obtain a polyamic acid ester. At this time, the divalent organic group B １ Diaminosiloxanes may be used in combination with diamines having the formula (I). Examples of the dehydration condensation agent include dicyclohexylcarbodiimide (DCC), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. In this manner, a polyanhydride intermediate is obtained.

[0046] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution is filtered off, if necessary. Then, a suitable poor solvent, such as water, a lower aliphatic alcohol, or a mixture thereof, is added to the solution containing the polymer component. This precipitates the polymer component, and the polymer is purified by repeated redissolution and reprecipitation procedures, if necessary. The target polyimide precursor is then isolated by vacuum drying. To improve the degree of purification, ionic impurities may be removed by passing the polymer solution through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent.

[0047] From the viewpoint of the heat resistance and mechanical properties of the film obtained after heat treatment, the weight-average molecular weight of the polyimide precursor, as measured by gel permeation chromatography (GPC) in terms of polystyrene equivalent, is preferably 3,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 15,000 to 30,000. A weight-average molecular weight of 3,000 or more is preferred because of good mechanical properties, while a weight-average molecular weight of 150,000 or less is preferred because of good dispersibility in the developer and resolution performance of the relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0048] (Synthesis of Polyimide) The polyimide of the present disclosure is a polyimide having the above-mentioned tetravalent organic group A ２ or an acid / ester thereof, and the divalent organic group B ２ and a diamine containing the same, followed by imidization.

[0049] The tetracarboxylic acid dianhydride used in the synthesis of polyimide is preferably in the form of an acid dianhydride rather than in the form of an acid / ester, from the viewpoint of increasing the imide ring closure rate.２ and a divalent organic group B having 6 to 40 carbon atoms. ２ The imidization can be carried out by condensation reaction with an excess amount of a diamine compound containing the compound, followed by thermal ring closure. The imidization can be carried out, for example, by heating at a temperature of 160 to 300°C for 1 to 10 hours. The higher the imide ring closure rate, the better, and for example, 90% or more, preferably 95% or more, and more preferably 99% or more or 100%.

[0050] After the imidization reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off, if necessary, and then a suitable poor solvent, such as water, a lower aliphatic alcohol, or a mixture thereof, is added to the solution containing the polymer component. This precipitates the polymer component, and the polymer is purified by repeated procedures such as redissolution and reprecipitation, if necessary. The target polyimide is then isolated by vacuum drying. To improve the degree of purification, ionic impurities may be removed by passing the polymer solution through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent.

[0051] From the viewpoint of the heat resistance and mechanical properties of the film obtained after heat treatment, the weight-average molecular weight of the polyimide, as measured by gel permeation chromatography (GPC) in terms of polystyrene equivalent, is preferably 3,000 to 150,000, more preferably 5,000 to 40,000, and particularly preferably 15,000 to 30,000. A weight-average molecular weight of 3,000 or more is preferred because it provides good mechanical properties, while a weight-average molecular weight of 150,000 or less is preferred because it provides good solubility in solvents, dispersibility in developers, and resolution performance of relief patterns. The conditions for gel permeation chromatography are the same as those described above.

[0052] <Component (B)> The component (B) is a photopolymerization initiator. Such a photopolymerization initiator generates radicals when exposed to actinic rays, and can polymerize an ethylenically unsaturated group-containing compound or the like. Examples of initiators that generate radicals when exposed to actinic rays include compounds containing structures such as benzophenone, N-alkylaminoacetophenone, oxime ester, acridine, and phosphine oxide.

[0053] Examples of component (B) include aromatic ketones such as benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, acrylated benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; 1,2-Octanedione, 1-[4-(phenylthio)-phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (manufactured by BASF Japan, Irgacure Oxime ester compounds such as 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (Changzhou Powerful Electronic New Materials Co., Ltd., PBG-305), 1-[4-(phenylthio)phenyl]-3-propane-1,2-dione-2-(O-acetyloxime) (Changzhou Powerful Electronic New Materials Co., Ltd., PBG-3057), and 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (Nikko Chemtech Co., Ltd., TR-PBG-326); benzyl derivatives such as benzyl dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide;

[0054] From the viewpoint of resolution, the component (B) is preferably an oxime ester compound, more preferably an oxime ester compound represented by the following general formula (12): (In the formula, R ８ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and R ９ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and R １０ is -H, -OH, -COOH, -O(CH ２ )OH, —O(CH ２ )2OH, -COO(CH ２ )OH or —COO(CH ２ ) ２ From the same viewpoint as above, it is preferable that the component (B) contains a structure represented by the following general formula (16): (In the formula, R １３ is an alkyl group having 1 to 6 carbon atoms, and R １４ No ２ or ArCO (Ar is an aryl group), and R １５ , and R １６ are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group), and (In the formula, R １７ is an alkyl group having 1 to 6 carbon atoms, and R １８ is an organic group having an acetal bond, and R １９ , and R ２０ are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group).

[0055] Component (B) more preferably contains a structure represented by general formula (12). This structure can suppress absorption at 365 nm originating from the photopolymerization initiator and exhibit a photobleaching effect, thereby ensuring that the amount of light reaching the bottom of the film even when the film is thick, making it easier to achieve a good pattern shape with high resolution.

[0056] In formula (12), from the viewpoint of reaction efficiency, R ９is preferably an alkyl group having 1 to 12 carbon atoms, more preferably a methyl group. ９ By having the above structure, even if the amount of light reaching the bottom of the film is small under conditions where the film is thick, the crosslinking reaction can be easily carried out, and therefore, a good pattern shape can be easily realized with high resolution.

[0057] The content of the (B) component is preferably 0.5 to 30 parts by mass, more preferably 2 to 15 parts by mass, per 100 parts by mass of the (A) component. From the viewpoint of photosensitivity or patterning ability, the content is preferably 0.5 parts by mass or more. On the other hand, from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition, the content is preferably 30 parts by mass or less. The (B) component may be used alone or in combination of two or more. When multiple types of (B) components are used, the content of the (B) component refers to the total content of the multiple types of (B) components.

[0058] <<Component (C)>> Component (C) is a compound having an alkyl group. By including component (C), the photosensitive resin composition of the present disclosure is likely to reduce the refractive index of a dried film (for example, a film obtained by drying a coating film of the photosensitive resin composition) and to suppress an increase in the water permeability of a cured film. By easily reducing the refractive index of the dried film, it is easy to achieve a good pattern shape with high resolution even under conditions where the film is thick. From the viewpoints of resolution and dielectric loss tangent, component (C) preferably has a linear alkyl group that does not contain a branched structure. In component (C), from the viewpoints of reducing the refractive index and ensuring water permeability, it is preferable that the alkyl group has 4 or more carbon atoms. The alkyl group may have 10 or less carbon atoms.

[0059] The component (C) is represented by the following general formula (1): (wherein X is an alkyl group, Y is an organic group having 1 to 30 carbon atoms and containing at least one selected from an ester group, an isocyanurate group, an amide group, and a urea group, and m １ is an integer from 1 to 4, where m １is 2 or more, the multiple Xs may be the same or different. When X is an alkyl group, it is easy to realize a dry film with a low refractive index and a cured film with low water permeability. From the viewpoint of compatibility with component (A) and other components, Y in formula (1) is preferably an organic group having at least one group selected from an ester group, an isocyanurate group, an amide group, and a urea group, and more preferably an organic group having 1 to 30 carbon atoms.

[0060] In formula (1), Y may contain at least one group selected from an ester group, an isocyanurate group, an amide group, and a urea group, and may also contain other groups (e.g., other organic groups having 1 to 30 carbon atoms) in addition to these groups. Examples of the organic group include an alkyl group, an aromatic group, and a heterocyclic group. Y may contain a heteroatom such as nitrogen, oxygen, phosphorus, or sulfur. An amide group is represented by -NR ２ -CO-(R ２ are each independently a hydrogen atom or an organic group), and the urea group can be —NR ２ -CO-NR ２ - (R ２ may each independently be a hydrogen atom or an organic group, provided that all R ２ is not a hydrogen atom).

[0061] In formula (1), m １ The total number of carbon atoms of the X's is preferably 10 to 20. From the viewpoint of decreasing the refractive index and decreasing the water permeability, the total number of carbon atoms is preferably 10 or more, and from the viewpoint of compatibility, the total number of carbon atoms is preferably 20 or less.

[0062] m in formula (1) １ When m is 1, from the viewpoint of resolution and dielectric loss tangent, it is preferable that X is a linear alkyl group, and m １ When X is 2 or more, at least one of the plurality of X's is preferably a linear alkyl group, and more preferably all of X's are linear alkyl groups.

[0063] The component (C) is a compound represented by the following general formulas (2) to (7): (wherein X is an organic group having 1 to 30 carbon atoms, and the multiple Xs in the formula may be the same or different, provided that at least one of the multiple Xs is an alkyl group). This makes it easier to achieve the effects of the present disclosure. From the viewpoint of reducing the refractive index and reducing the water permeability, X is preferably a hydrocarbon group, more preferably an alkyl group, and particularly preferably a straight-chain alkyl group. It is sufficient that at least one of the multiple Xs is an alkyl group, and all of the Xs may be alkyl groups. In particular, when the component (C) has a structure represented by any of formulas (2) to (6), compatibility with the component (A) and other components is easily ensured. Therefore, more preferably, the component (C) contains at least one selected from the structures represented by formulas (2) to (6). These structures are similar to the m in formula (1). １ is 2 to 4, so that m １ Compared to when Y is 1, it is possible to introduce an X with a larger carbon number while maintaining compatibility. Furthermore, when Y in formula (1) has a highly polar functional group such as an ester group, an isocyanurate group, an amide group, or a urea group, compatibility with component (A) and other components is more likely to be ensured. In particular, photosensitive resin compositions containing structures of formulas (4) to (6) tend to have high glass transition temperatures (Tg). Therefore, from the viewpoints of compatibility and heat resistance, component (C) preferably contains at least one selected from the structures represented by formulas (4) to (6), and more preferably contains the structure of formula (5).

[0064] Specific examples of such component (C) are as follows: I) to IV), however, component (C) is not limited to these specific examples.

[0065] I) Examples of alkyl group-containing compounds containing an ester group include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, di-n-pentyl phthalate, di-n-hexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate, di-n-undecyl phthalate, di-n-dodecyl phthalate, di-n-tridecyl phthalate, and phthalates. Butyl isopropyl phthalate, butyl isobutyl phthalate, di(2-ethylhexyl) phthalate, benzyl butyl phthalate, benzyl octyl phthalate, benzyl isononyl phthalate, bis(2-ethylhexyl) isophthalate, trimethyl trimellitate, triethyl trimellitate, tri-n-butyl trimellitate, tri-n-pentyl trimellitate, tri-n-hexyl trimellitate, tri-n- heptyl trimellitate, tri-n-octyl trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, tri-n-undecyl trimellitate, tri-n-dodecyl trimellitate, tri-n-tridecyl trimellitate, tri(2-ethylhexyl) trimellitate, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, tri-n-pentyl phosphate, tris(2-ethylhexyl) phosphate, tris(2-butoxyethyl) phosphate, 2-ethylhexyldiphenyl phosphate, dibutyl maleate, bis(2-ethylhexyl)azelate, bis(2-ethylhexyl)sebacate, 2,2-dimethyl-1,3-propanediyl bis(2-ethylhexanoate), bis(2-ethylhexyl) maleate, bis(2-ethylhexyl) dodecanedioate, and diisononyl cyclohexanedicarboxylate.

[0066] II) Examples of alkyl group-containing compounds containing an isocyanurate group include tri-n-butyl isocyanurate and L-DAIC (manufactured by Shikoku Chemicals Corporation).

[0067] III) Examples of alkyl group-containing compounds containing an amide group include butanamide, pentanamide, hexanamide, heptanamide, octanamide, nonanamide, decanamide, undecaneamide, dodecaneamide, N-methyldodecanamide, N,N'-dimethyloctanamide, N,N'-dimethyldodecanamide, N,N'-diethyldodecanamide, and 1-n-octyl-pyrrolidone.

[0068] IV) Examples of alkyl group-containing compounds containing a urea group include 1,3-di-n-butylurea, 1,3-di-n-pentylurea, 1,3-di-n-hexylurea, 1,3-di-n-heptylurea, 1,3-di-n-octylurea, 1,3-di-n-nonylurea, 1,3-di-n-decylurea, 1,1,3,3-tetra-n-propylurea, 1,1,3,3-tetra-n-pentylurea, and N-dodecyl acylamido.

[0069] The content of the (C) component is preferably 0.5 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of the (A) component. From the viewpoint of forming a high-resolution pattern and more effectively realizing a low dielectric tangent under conditions of a thick film thickness, the content is more preferably 5 parts by mass or more. On the other hand, from the viewpoint of compatibility with the solvent and the (A) component, the content is more preferably 30 parts by mass or less. The (C) component may be used alone or in combination of two or more. When multiple types of (C) components are used, the content of the (C) component refers to the total content of the multiple types of (C) components.

[0070] <<Component (D)>> The component (D) is a component (other component) other than the above components (A) to (C). The photosensitive resin composition may further contain the component (D) as another component. Examples of the other component include a solvent, a resin component other than the component (A), a chelating agent containing a metal element other than a transition metal of Group 4 elements, a silane coupling agent, a radical polymerizable compound, a thermal crosslinking agent, a filler, a sensitizer, a thermal polymerization inhibitor, an azole compound, and a hindered phenol compound.

[0071] (Solvent) The photosensitive resin composition may optionally contain a solvent. The solvent may be any solvent capable of uniformly dissolving or suspending component (A) and component (B). Examples of such solvents include γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, N,N-dimethylacetoacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide.

[0072] The solvent can be used in an amount of, for example, 30 to 1,500 parts by mass, preferably 100 to 1,000 parts by mass, per 100 parts by mass of component (A), depending on the thickness and viscosity of the coating film of the photosensitive resin composition. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is likely to be good, and when it is 50% by mass or less, the solubility of component (A) is likely to be good.

[0073] (Resin Components Other Than Component (A)) The photosensitive resin composition can optionally contain a resin component other than component (A). Examples of resin components other than (A) include polyamic acid, polybenzoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The blending amount of these resin components is preferably 0.01 to 20 parts by mass per 100 parts by mass of component (A).

[0074] (Chelating Agent Containing a Group 4 Transition Metal) The photosensitive resin composition may optionally contain a chelating agent containing a Group 4 transition metal. The chelating agent containing a Group 4 transition metal may be added as desired to achieve a low dielectric loss tangent and high heat resistance. Without being bound by theory, it is believed that the inclusion of the chelating agent allows the metal element contained in the organic compound containing the metal element to be coordinated to the ester group and / or carbonyl group derived from the carboxyl group of the polyimide precursor, thereby suppressing molecular motion of the polymer chain, and as a result, a low dielectric loss tangent is preferably achieved.

[0075] The chelating agent containing a transition metal of Group 4 preferably contains at least one metal element selected from titanium and zirconium, and an organic group in one molecule. The organic group preferably contains a hydrocarbon group or a hydrocarbon group containing a heteroatom. The inclusion of an organic group increases the imidization rate of the polyimide precursor contained in the photosensitive resin composition, and therefore the dielectric loss tangent of the cured film is likely to decrease. Usable chelating agents containing a transition metal of Group 4 include, for example, those in which an organic group is bonded to a titanium atom or a zirconium atom via a covalent bond or an ionic bond, i.e., organic titanium compounds or zirconium compounds.

[0076] Specific examples of the organic titanium compound or organic zirconium compound are as follows I) to VII).

[0077] I) Examples of chelate compounds having two or more alkoxy groups as organic groups include titanium bis(acetylacetonate)diisopropoxide, titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0078] II) Examples of tetraalkoxy compounds include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0079] III) Examples of titanocene or zirconocene compounds include pentamethylcyclopentadienyltitanium trimethoxide, bis(η ５ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η ５ and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0080] IV) Examples of monoalkoxy compounds include titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0081] V) Examples of titanium oxide or zirconium oxide compounds include titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0082] VI) Titanium tetraacetylacetonate or zirconium tetraacetylacetonate compounds include, for example, titanium tetraacetylacetonate and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0083] VII) Examples of titanate coupling agents include isopropyl tridodecylbenzenesulfonyl titanate.

[0084] Among the above I) to VII), it is preferable that the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better dielectric properties. In particular, titanium bis(acetylacetonate)diisopropoxide, titanium tetraacetylacetonate, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η ５ In terms of compatibility with solvents, titanium bis(acetylacetonate)diisopropoxide and titanium tetraacetylacetonate are more preferred.

[0085] When an organic titanium compound or zirconium compound is blended, the content of the organic titanium compound or zirconium compound is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to component (A). When the content is 0.01 part by mass or more, a good imidization rate of the resin composition and dielectric properties of the cured film are likely to be exhibited, while when the content is 5 parts by mass or less, excellent storage stability is likely to be achieved.

[0086] (Silane Coupling Agent) The photosensitive resin composition may optionally contain a silane coupling agent to improve the adhesion of the relief pattern. Examples of such compounds include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrialkoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0087] The content of the silane coupling agent in the resin composition is preferably 0.2 to 10% by mass, and from the viewpoint of copper adhesion, more preferably 1 to 8% by mass, and even more preferably 2 to 6% by mass, relative to 100 parts by mass of component (A).

[0088] (Radical Polymerizable Compound) The photosensitive resin composition may optionally contain a radical polymerizable compound in order to improve the resolution of the relief pattern and the residual film rate after curing by heat curing. As such a compound, a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator is preferred. Specific examples include, but are not limited to, di(meth)acrylates of ethylene glycol or polyethylene glycol, including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, di(meth)acrylates of propylene glycol or polypropylene glycol, di(meth)acrylate or tri(meth)acrylate of glycerol, cyclohexane di(meth)acrylate, di(meth)acrylate of 1,4-butanediol, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of neopentyl glycol, di(meth)acrylate of bisphenol A, (meth)acrylamide, derivatives thereof, trimethylolpropane tri(meth)acrylate, di(meth)acrylate or tri(meth)acrylate of glycerol, di(meth)acrylate, tri(meth)acrylate or tetra(meth)acrylate of pentaerythritol, and compounds such as ethylene oxide or propylene oxide adducts of these compounds. Among these radical polymerizable compounds, those having three or more radical polymerizable groups are preferred from the viewpoint of improving the residual film rate after curing.

[0089] The content of the radical polymerizable compound in the resin composition is preferably 0.5 to 50 mass % relative to 100 parts by mass of the component (A). From the viewpoint of improving the resolution and the residual film rate after curing, the content is more preferably 5 to 40 mass %, and even more preferably 10 to 30 mass %.

[0090] (Thermal Crosslinking Agent) The photosensitive resin composition may optionally contain a thermal crosslinking agent to improve the residual film rate after curing. A thermal crosslinking agent refers to a compound that undergoes an addition reaction or a condensation polymerization reaction due to heat. These reactions occur, for example, in a combination of component (A) and a thermal crosslinking agent, a combination of two thermal crosslinking agents, or a combination of a thermal crosslinking agent and another component, and the reaction temperature is preferably 150°C or higher.

[0091] Examples of the thermal crosslinking agent include an alkoxymethyl compound, an epoxy compound, an oxetane compound, a bismaleimide compound, an allyl compound, and a blocked isocyanate compound. From the viewpoint of improving the residual film rate after curing, the thermal crosslinking agent preferably contains a nitrogen atom.

[0092] Examples of the alkoxymethyl compound include the following compounds:

[0093] Examples of the epoxy compound include an epoxy compound containing a bisphenol A group, and hydrogenated bisphenol A diglycidyl ether (for example, Epolight 4000 manufactured by Kyoeisha Chemical Co., Ltd.).

[0094] Examples of the oxetane compound include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, and bis(3-ethyl-3-oxetanylmethyl)diphenyl. phenolate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicate, phenol novolac-type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei Co., Ltd., trade name), and OXT221 (manufactured by Toagosei Co., Ltd., trade name).

[0095] Examples of the bismaleimide compound include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

[0096] Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0097] Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882N manufactured by Mitsui Chemicals, Inc., and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), and tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc.). , 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Inc., and Coronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N manufactured by Mitsui Chemicals, Inc., and Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (e.g., 7950, 7951, and 7990 manufactured by Baxenden).

[0098] Of the above, the thermal crosslinking agent is preferably a blocked isocyanate or a bismaleimide compound from the viewpoint of storage stability.

[0099] The content of the thermal crosslinking agent in the resin composition is preferably 0.2 to 40 parts by mass relative to 100 parts by mass of the component (A). From the viewpoint of achieving a low dielectric loss tangent and improving the residual film rate after curing, the content is more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass.

[0100] (Filler) The photosensitive resin composition may optionally contain a filler to improve the residual film rate after curing. The filler may be any inert substance added to improve the strength and various properties of the cured film.

[0101] The filler is preferably particulate from the viewpoint of suppressing an increase in viscosity when the resin composition is prepared. Examples of particulate shapes include needle-like, plate-like, and spherical shapes, but spherical shapes are preferred from the viewpoint of suppressing an increase in viscosity when the resin composition is prepared.

[0102] Examples of acicular fillers include wollastonite, potassium titanate, xonotlite, aluminum borate, and acicular calcium carbonate. Examples of plate-like fillers include talc, mica, sericite, glass flakes, montmorillonite, boron nitride, and plate-like calcium carbonate. Examples of spherical fillers include calcium carbonate, silica, alumina, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, and barium titanate. Among these, silica, alumina, titanium oxide, and barium titanate are preferred, with silica and alumina being more preferred, from the viewpoints of electrical properties and storage stability when formed into a resin composition.

[0103] The size of the filler, when defined as the primary particle diameter in the case of a spherical shape or the length of the long side in the case of a plate-like or needle-like shape, is preferably 5 to 1,000 nm, more preferably 10 to 1,000 nm. If the size is 10 nm or more, the filler tends to be sufficiently uniformly dispersed when the resin composition is prepared, and if the size is 1,000 nm or less, it is easy to impart photosensitivity. From the viewpoint of imparting photosensitivity, the size is preferably 800 nm or less, more preferably 600 nm or less, and particularly preferably 300 nm or less. Furthermore, from the viewpoints of adhesion and resin composition uniformity, the size is preferably 15 nm or more, more preferably 30 nm or more, and particularly preferably 50 nm or more.

[0104] The content of the filler in the resin composition is preferably 1 to 20 vol % relative to the total volume of the resin composition, and from the viewpoint of dielectric properties, preferably 5 to 20 vol %, and from the viewpoint of resolution, more preferably 5 to 10 vol %.

[0105] (Sensitizer) The photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene indanone. , p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl

[0039] Examples of the methylaminobenzoate include methylaminobenzoate, ... These can be used alone or in combination of two or more (for example, two to five types). The content of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of the component (A).

[0106] Some compounds contained in component (B) can function as a sensitizer. In one embodiment, a compound containing a structure selected from benzophenone, N-alkylaminoacetophenone, oxime ester, acridine, and phosphine oxide can be understood as component (B), and compounds having a structure other than these and added to improve photosensitivity can also be understood as sensitizers.

[0107] (Thermal Polymerization Inhibitor) The photosensitive resin composition may optionally contain a thermal polymerization inhibitor, particularly from the viewpoint of improving the viscosity and photosensitivity stability of the photosensitive resin composition during storage in the form of a solvent-containing solution. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0108] The content of the thermal polymerization inhibitor is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the component (A) from the viewpoint of photosensitivity characteristics and patterning properties.

[0109] (Azole Compound) When a substrate made of copper or a copper alloy is used, the photosensitive resin composition may optionally contain an azole compound to suppress discoloration of the substrate. 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-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and the like. Examples of benzotriazole include 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-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, and 1-methyl-1H-tetrazole. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole.

[0110] The content of the azole compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), and from the viewpoint of photosensitivity characteristics, more preferably 0.5 to 5 parts by mass. When the content of the azole compound is 0.1 part by mass or more relative to 100 parts by mass of component (A), discoloration of the copper or copper alloy surface is likely to be suppressed when the photosensitive resin composition is formed on copper or a copper alloy, while when the content is 20 parts by mass or less, photosensitivity is likely to be excellent.

[0111] (Hindered Phenol Compound) When a substrate made of copper or a copper alloy is used, the photosensitive resin composition may contain a hindered phenol compound to suppress discoloration and corrosion of the substrate. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butylphenol). N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene- Bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4- isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] ... 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2 ,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxybenzyl) Examples of the hydroxybenzoates include 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and the like. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0112] The content of the hindered phenol compound is preferably 0.1 to 20 parts by mass, and from the viewpoint of photosensitivity characteristics, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A). If the content of the hindered phenol compound is 0.1 part by mass or more, when the photosensitive resin composition is formed on copper or a copper alloy, for example, discoloration and corrosion of the copper or copper alloy are easily prevented, while if the content is 20 parts by mass or less, excellent photosensitivity is easily achieved.

[0113] <Method for producing photosensitive resin composition> Another aspect of the present disclosure is a method for producing the photosensitive resin composition of the present disclosure. Such a method can include, for example, the following steps: a step of producing component (A); and a step of obtaining a photosensitive resin composition by mixing component (A), component (B), and component (C), and optionally mixing component (D) as another component. Note that an example of the method for producing component (A) is as described above.

[0114] <Cured film and manufacturing method thereof> A further aspect of the present disclosure is a method for manufacturing a cured film, comprising the following steps: (1) applying the photosensitive resin composition onto a substrate and forming a photosensitive resin layer on the substrate; (2) optionally, additionally drying the formed photosensitive resin layer; (3) exposing the photosensitive resin layer to light; (4) developing the photosensitive resin layer after exposure; and (5) heating the photosensitive resin layer after development to form a cured film.

[0115] The photosensitive resin composition used in the method for producing a cured film preferably contains 100 parts by mass of component (A), 0.5 to 30 parts by mass of component (B), 0.5 to 50 parts by mass of component (C), and 100 to 1,000 parts by mass of a solvent. As described above, the photosensitive resin composition used in the method for producing a cured film may optionally contain component (D) as another component. The photosensitive resin composition of the present disclosure is preferably negative.

[0116] The specific steps in the method for producing a cured film can be carried out in accordance with the steps in the production method described above. Typical aspects of each step will be described below.

[0117] <<Step (1): Photosensitive Resin Layer Forming Step>> In this step, the photosensitive resin composition of the present disclosure is applied onto a substrate, and a photosensitive resin layer is formed on the substrate. In this step, by applying the photosensitive resin composition of the present disclosure onto the substrate, a coating film can be formed on the substrate. Then, by drying the coating film as necessary, the coating film can be obtained as a photosensitive resin layer. As the coating method, methods conventionally used for applying photosensitive resin compositions can be used, such as a method of applying using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or a method of spray coating using a spray coater, etc.

[0118] <<Step (2): Drying Step>> This step is optionally performed. In this step, the photosensitive resin layer formed above can be optionally further dried. Drying methods include air drying, heat drying using an oven or hot plate, and vacuum drying. It is desirable to dry the coating film under conditions that do not cause imidization of the polyimide precursor portion (polyamic acid ester) of component (A) in the photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be performed under conditions of 20°C to 140°C for 1 minute to 1 hour. Note that "drying" of the photosensitive resin layer may also be "heating."

[0119] <<Step (3): Drying Step>> In this step, the photosensitive resin layer is exposed to light. Examples of the exposure device that can be used include a contact aligner, a mirror projection device, and a stepper. The exposure can be performed directly or via a photomask or reticle having a pattern. The light used for exposure is, for example, an ultraviolet light source.

[0120] After exposure, post-exposure baking (PEB) and / or pre-development baking may be performed as necessary using any combination of temperature and time for the purpose of improving photosensitivity, etc. The baking conditions are preferably in the range of a temperature of 40 to 120°C and a time of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition of the present disclosure.

[0121] <<Step (4): Development Step>> In this step, the photosensitive resin layer after exposure is developed. A relief pattern can be formed through this step. When the photosensitive resin composition is a negative type, in this step, the unexposed portions of the photosensitive resin layer after exposure are removed by development. As a development method for developing the photosensitive resin layer after exposure (irradiation), conventionally known photoresist development methods, such as a rotary spray method, a paddle method, or an immersion method accompanied by ultrasonic treatment, can be used. After development, post-development baking may be performed at any temperature and time combination, as necessary, for the purpose of adjusting the shape of the relief pattern, etc. The developer used for development is preferably, for example, a good solvent for the negative type photosensitive resin composition or a combination of the good solvent and a poor solvent.

[0122] Preferred examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition.

[0123] Here, it is preferable to carry out the above coating to development steps so as to obtain a relief pattern having a film thickness of 5 to 40 μm. The thickness of the obtained relief pattern can be adjusted by controlling various conditions in the above coating to development steps.

[0124] <<Step (5): Cured Film Forming Step>> In this step, the photosensitive resin layer after development is heated to form a cured film. For example, in this step, the relief pattern obtained by development is heated to dissolve the photosensitive component and imidize component (A), thereby converting it into a cured relief pattern made of polyimide. Curing (heat curing) methods include those using a hot plate, an oven, and a temperature-programmable heating oven. Heating can be performed, for example, at 160 to 400°C for 30 minutes to 5 hours. The ambient gas used during curing may be air or an inert gas such as nitrogen or argon.

[0125] A further aspect of the present disclosure is a cured film obtained from the photosensitive resin composition described above. From the viewpoint of suppressing dielectric-induced transmission loss, the cured film preferably has a dielectric loss tangent of 0.015 or less, measured at 10 GHz using a perturbation split cylinder resonator method. The lower the measured dielectric loss tangent value, the more preferable. The measured dielectric loss tangent value may be greater than 0. The cured film preferably has a dielectric constant of 1.5 to 3.5, measured at 10 GHz using a perturbation split cylinder resonator method.

[0126] In the present disclosure, the cured film obtained from the photosensitive resin composition preferably has a thickness of 25 μm or more from the viewpoint of suppressing transmission loss in devices used for high-speed communication. The thickness of the cured film may be 100 μm or less.

[0127] <Semiconductor Device> Another aspect of the present disclosure is a semiconductor device having the cured relief pattern (cured film) of the present disclosure. The semiconductor device of the present disclosure includes a cured film of the photosensitive resin composition. Thus, the present disclosure provides a semiconductor device having a substrate that is a semiconductor element and a cured film of polyimide.

[0128] A further aspect of the present disclosure is a method for manufacturing a semiconductor device, which uses a semiconductor element as a substrate and includes the above-described manufacturing method as part of its steps. The cured relief pattern can be formed as a surface protective film, an interlayer insulating film, a redistribution insulating film, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and can be combined with a known method for manufacturing a semiconductor device to manufacture a desired semiconductor device.

[0129] The polyimide contained in the cured relief pattern (cured film) formed from the photosensitive resin composition of the present disclosure is represented by the following general formula (18): (In the formula, A １ is a tetravalent organic group having 6 to 40 carbon atoms, and B １ is a divalent organic group having 6 to 40 carbon atoms, and n １ is an integer of 2 to 100), and / or the following general formula (9): (In the formula, A ２ is a tetravalent organic group having 6 to 40 carbon atoms, and B ２ is a divalent organic group having 6 to 40 carbon atoms, and n ３ is an integer of 2 to 100. The structure represented by formula (18) may be understood as an imidized version of the structure represented by formula (8).

[0130] In addition to being applied to the semiconductor devices described above, the photosensitive resin composition of the present disclosure is also useful for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[0131] Hereinafter, embodiments of the present disclosure will be described with reference to examples and comparative examples. However, the embodiments of the present disclosure are not limited to the following examples. Regarding the examples and comparative examples, various productions, measurements, evaluations, etc. were performed by the following methods.

[0132] [Measurement and Evaluation] (1) Weight-average molecular weight The weight-average molecular weight (Mw) of the diamine oligomer and copolymer resin was measured by gel permeation chromatography (standard polystyrene equivalent). For the measurement, a series of Shodex 805M / 806M columns manufactured by Resonaq Co., Ltd. was used as the column, Shodex STANDARD SM-105 columns manufactured by Resonaq Co., Ltd. was used as the standard monodisperse polystyrene, N-methyl-2-pyrrolidone was used as the developing solvent, and Shodex RI-930 columns manufactured by Resonaq Co., Ltd. was used as the detector.

[0133] (2) Refractive index (N ａｖｅ A photosensitive resin composition prepared by the method described below was spin-coated onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a spin coater (D-spin 60A model, manufactured by SOKUDO Corporation) to form a coating film. The coating film was then dried on a hot plate at 110°C for 360 seconds to form a photosensitive resin layer (dried film) with a thickness of 30±1 μm.

[0134] The refractive index of this dry film was measured using a laser refractometer (Prism Coupler, manufactured by Metricon). The wavelength was 1312.5 nm, and the refractive index was calculated from the measured values ​​in TE mode (TE) and TM mode (TM) using the following calculation formula (Formula Y): ａｖｅ = {(TE × 2) + (TM)} / 3 ... (Equation Y) Based on this, the refractive index N ａｖｅ asked for.

[0135] (3) Water permeability (WVTR) A 100 nm thick aluminum (Al) was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a sputtering apparatus (SME-200E, manufactured by ULVAC) to prepare a sputtered Al wafer substrate. A photosensitive resin composition prepared by the method described below was spin-coated using a spin coater (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) to form a coating film. The coating film was then dried on a hot plate at 110°C for 360 seconds to form a photosensitive resin layer (dried film).

[0136] Thereafter, a stepper (FPA-3030iWa, manufactured by Canon Inc.) was used to expose the film to light at an exposure dose of 1000 mJ / cm. ２ The photosensitive resin layer was entirely exposed to i-rays. The exposed film was further cured in a vertical curing furnace (Koyo Lindberg, model VF-2000B) at 230°C for 2 hours under a nitrogen atmosphere to produce a cured film 25±1 μm thick on the Al wafer. This cured film was then cut into a length of 80 mm and a width of 62 mm using a dicing saw (Disco, model DAD-2H / 6T). The film was then immersed in a 10% aqueous hydrochloric acid solution and peeled off from the silicon wafer, and the resulting film was used as a sample for measurement. Water permeability was measured in accordance with the cup method of JIS Z0208. The amount of calcium chloride used was 40 g, and the water permeability was measured under conditions of a temperature of 65°C and a humidity of 90% RH. After the water permeability measurement test was performed for 24 hours, the sample was removed from the thermo-hygrostat and left at room temperature for 30 minutes, after which its mass was measured. The following calculation formula (Formula X) is used: WVTR = {(Weight after test) - (Weight before test)} / (0.03 ２ ×π) ... (Equation X) {where 0.03 represents the radius of the cup (m)} Based on this, the water permeability WVTR (g / m ２ The WVTR (Watts per minute, 24 hours) was determined. The WVTR here is a value based on a film thickness of 25 μm and is a value that depends on the film thickness. For example, the WVTR for a film thickness of 50 μm is calculated as half the WVTR value obtained for a film thickness of 25 μm. The lower the WVTR value, the lower the water vapor transmission rate of the film.

[0137] (4) Resolution A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick titanium (Ti) and a 400 nm thick copper (Cu) in that order using a sputtering apparatus (SME-200E, manufactured by ULVAC). A photosensitive resin composition prepared by the method described below was spin-coated onto this wafer using a spin coater (D-Spin 60A, manufactured by SOKUDO Corporation), thereby forming a coating film. The coating film was then dried on a hot plate at 110°C for 360 seconds to form a photosensitive resin layer (dried film).

[0138] This photosensitive resin layer was exposed to i-line radiation using a stepper (FPA-3030iWa, manufactured by Canon Inc.) with a test pattern mask. The exposed film was then spray-developed using a developer (D-SPIN636, manufactured by Dainippon Screen Mfg. Co., Ltd.) with cyclopentanone as the developer. The film was then washed with propylene glycol methyl ether acetate and then dried by spin drying. The developed film was then cured in a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) at 230°C for 2 hours under a nitrogen atmosphere, producing a cured film (cured relief pattern) on the Cu wafer that was 25±1 μm thick and may have via openings (openings penetrating in the thickness direction).

[0139] The prepared cured relief pattern was observed under an optical microscope, and the area of ​​the via opening (the area occupied by the penetrating opening portion when the cured relief pattern was observed in the thickness direction) was determined. If the area of ​​the obtained via opening was at least half the mask opening area of ​​the corresponding pattern, it was evaluated as "resolved." Then, based on the diameter of the mask opening corresponding to the resolved via with the smallest via opening area (the size of the smallest opening pattern), the resolution was evaluated according to the following evaluation criteria.

[0140] (Evaluation Criteria) E (◎): The minimum opening pattern size is 25 μm or less. G (◯): The minimum opening pattern size is greater than 25 μm and less than 35 μm. P (×): The minimum opening pattern size is greater than 35 μm or development is not possible.

[0141] (5) Dielectric tangent (tan δ １０) A 100 nm thick aluminum (Al) was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a sputtering apparatus (SME-200E, manufactured by ULVAC). This prepared a sputtered Al wafer substrate. A photosensitive resin composition prepared by the method described below was spin-coated onto the sputtered Al wafer substrate using a spin coater (D-spin 60A, manufactured by SOKUDO Corporation), thereby forming a coating film. The coating film was then dried on a hot plate at 110°C for 360 seconds to form a photosensitive resin layer (dried film).

[0142] This photosensitive resin layer was exposed to light at a dose of 1000 mJ / cm using a stepper (FPA-3030iWa, manufactured by Canon Inc.). ２ The entire surface was exposed to i-rays. Thereafter, a vertical curing furnace (Koyo Lindberg, model name VF-2000B) was used to cure (heat cure) the film in a nitrogen atmosphere at 230°C for 2 hours, producing a cured film with a film thickness of 25±1 μm on the Al wafer. This cured film was cut into a length of 80 mm and a width of 62 mm using a dicing saw (Disco, model name DAD-2H / 6T). The film was then immersed in a 10% aqueous hydrochloric acid solution to peel it off from the silicon wafer, and the resulting film was used as a sample for measurement. The dielectric loss tangent (tanδ) of the sample was measured at 10 GHz using a resonator perturbation method. １０ ) was measured, and the dielectric loss tangent was determined according to the following evaluation criteria.

[0143] (Evaluation Criteria) E (◎): tan δ １０ is 0.01 or less G (◯): tan δ １０ is greater than 0.01 and less than 0.015 P(×): tan δ １０ is greater than 0.015

[0144] Details of the method for measuring the dielectric loss tangent are as follows: (Measurement method) Resonator perturbation method (perturbation type split cylinder resonator method) (Measurement sample humidity control) 23°C / 50%RH, left to stand for 24 hours (Measurement conditions) 23°C / 50%RH (Apparatus configuration) Network analyzer: PNA Network analyzer N5224B (manufactured by KEYSIGHT) Split cylinder resonator: CR-710 (manufactured by Kanto Electronics Application Development Co., Ltd., measurement frequency: approximately 10 GHz)

[0145] (6) Glass transition temperature (Tg) A 100 nm thick aluminum (Al) was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a sputtering apparatus (SME-200E, manufactured by ULVAC). This prepared a sputtered Al wafer substrate. A photosensitive resin composition prepared by the method described below was spin-coated onto the sputtered Al wafer substrate using a spin coater (D-Spin 60A, manufactured by SOKUDO Corporation), thereby forming a coating film. The coating film was then dried on a hot plate at 110°C for 360 seconds to form a photosensitive resin layer (dried film).

[0146] This photosensitive resin layer was exposed to light at a dose of 1000 mJ / cm using a stepper (FPA-3030iWa, manufactured by Canon Inc.). ２The entire surface was exposed to i-rays. Subsequently, a vertical curing furnace (Koyo Lindberg, model name VF-2000B) was used to cure (heat cure) the film at 230°C for 2 hours under a nitrogen atmosphere, producing a cured film with a film thickness of 25±1 μm on the Al wafer. This cured film was then cut into 3 mm-wide strips using a dicing saw (Disco, model name DAD-2H / 6T). It was then immersed in a 10% aqueous hydrochloric acid solution and peeled off from the silicon wafer, and the resulting film was used as a sample for measurement. The resulting polyimide tape was then left to stand for 24 hours or more in an atmosphere at a temperature of 23°C and a humidity of 50%, after which the elongation of the test specimen was measured in the range of 50 to 450°C using a thermomechanical analyzer (Shimadzu Corporation, TMA) under the following conditions, and the inflection point was determined as the glass transition temperature (Tg). The glass transition temperature was then determined according to the following evaluation criteria.

[0147] (Evaluation criteria) E (◎): Tg is 200°C or higher G (◯): Tg is greater than 180°C and less than 200°C P (×): Tg is less than 180°C

[0148] The details of the method for measuring the glass transition temperature (Tg) are as follows: (Load) 15 g (Measurement atmosphere) Nitrogen (flow rate 20 ml / min) (Temperature rise rate) 10°C / min (Measurement temperature) 50 to 450°C

[0149] [Synthesis] <Component (A)> <Polymer A1 (Polyimide Precursor (Polyamic Acid Ester))> 104 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA) as the acid component, 54 g of 2-hydroxyethyl methacrylate (HEMA), and 190 g of GBL were mixed in a 1-liter separable flask. 32 g of pyridine was further added with stirring at room temperature, and the mixture was then heated at 50°C for 4 hours to allow the reaction to proceed. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and then allowed to stand for a further 16 hours, yielding a reaction mixture.

[0150] Next, under ice cooling, a solution of 81 g of dicyclohexylcarbodiimide (DCC) dissolved in 81 g of GBL was added to the reaction mixture while stirring for 30 minutes, and then 30 g of GBL was added. Subsequently, a solution of 35 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) as the diamine component mixed with 106 g of GBL was added while stirring for 30 minutes. After further stirring at room temperature for 4 hours, 18 g of ethyl alcohol and 140 g of GBL were added and stirred for 30 minutes. The precipitate that formed in the reaction mixture was removed by filtration, and a reaction solution was obtained.

[0151] The resulting reaction solution was mixed with 2250 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer thus produced was collected by filtration and dissolved in 1000 g of GBL to obtain a crude polymer solution. The resulting crude polymer solution was then passed through an anion exchange resin ("Amberlyst" manufactured by Organo Corporation) to obtain a crude polymer solution. ＴＭ The resulting polymer solution was purified using a filtration membrane ("15JWET") to obtain a polymer solution. The resulting polymer solution was added dropwise to 9,200 g of water to precipitate the polymer, and the resulting precipitate was collected by filtration and dried in vacuum to obtain a powdery polymer A1. The weight average molecular weight (Mw) of polymer A1 was 23,000.

[0152] <Polymer A2 (Polyimide)> In a 0.5-liter separable flask equipped with a Dean-Stark tube and a condenser, 104 g of BPADA as an acid component, 64 g of m-TB as a diamine component, and 670 g of NMP as a solvent were mixed and dissolved with stirring. 42.3 g of toluene was then mixed and stirred, and the mixture was heated to 185°C under a nitrogen stream. After stirring at 185°C for 2.5 hours, the toluene in the system and the water produced by imidization were removed over 1.5 hours. The mixture was then cooled to room temperature, thereby obtaining a polymer A4 solution. The weight-average molecular weight (Mw) of polymer A4 was 7,000. Regarding polymer A4 １ The imide ring closure rate was confirmed by H-NMR measurement and comparing the peaks derived from amide bonds with the peaks derived from aromatic rings of the polyimide. The imide ring closure rate was 99% or more.

[0153] <Polymer A3 (Polyimide Precursor (Polyamic Acid Ester))> Powdery polymer A3 was obtained by carrying out a reaction in the same manner as in the synthesis method of polymer A1, except that 62 g of 4,4'-oxydiphthalic dianhydride (ODPA) was used instead of 104 g of BPADA. The weight average molecular weight (Mw) of polymer A3 was 18,000.

[0154] <Polymer A4 (Polyimide Precursor (Polyamic Acid Ester))> Powdery Polymer A4 was obtained by carrying out a reaction in the same manner as in the synthesis method for Polymer A1, except that 40 g of 3,3',5,5'-tetramethylbenzidine (TMB) was used instead of 35 g of m-TB. The weight average molecular weight (Mw) of Polymer A4 was 22,000.

[0155] Polymer A5 (Polyimide Precursor (Polyamic Acid Ester)) Powdery polymer A5 was obtained by carrying out a reaction in the same manner as in the synthesis method for polymer A1, except that 59 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 104 g of BPADA. The weight average molecular weight (Mw) of polymer A5 was 24,000.

[0156] <Polymer A6 (Polyimide Precursor (Polyamic Acid Ester))> Powdered polymer A6 was obtained by carrying out a reaction in the same manner as in the synthesis method for polymer A1, except that 62 g of ODPA was used instead of 104 g of BPADA and 31 g of 4,4'-diaminodiphenyl ether (DADPE) was used instead of 35 g of m-TB. The weight average molecular weight (Mw) of polymer A6 was 22,000.

[0157] <Components (B), (C), and (D)> Component (B) B1: 1-[4-(phenylthio)phenyl]-3-propane-1,2-dione-2-(O-acetyloxime) (trade name: PBG-3057, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.)

[0158] Component (C) C1: di-n-octyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) C2: tri-n-butyl trimellitate (manufactured by Tokyo Chemical Industry Co., Ltd.) C3: 1,3,5-tributyl-1,3,5-triazinane-2,4,6-trione (manufactured by Sigma-Aldrich Chemical Industry Co., Ltd.) C4: tri-n-butyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) C5: N,N'-diethyldodecanamide (manufactured by Tokyo Chemical Industry Co., Ltd.) C6: bis(2-ethylhexyl) phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) C7: triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.) C8: polyethylene glycol dimethacrylate (EO=9) (trade name: NK Ester 9G, manufactured by Shin-Nakamura Kogyo Co., Ltd.) C9: tetradecane (manufactured by Tokyo Chemical Industry Co., Ltd.) C10: dipropyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) C11: Diundecyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) Note that C9 and C11 have an alkyl group with 11 or more carbon atoms.

[0159] Example 1 As shown in the table below, 100 g of the above "Polymer A1" as component (A), 3 g of the above "B1" as component (B), 10 g of the above "C1" as component (C), and a mixed solvent of GBL and DMSO (mass ratio of GBL:DMSO = 127:23) as solvent were mixed to obtain a photosensitive resin composition (solution). This composition was evaluated by the above-mentioned method.

[0160] Examples 2 to 10 and Comparative Examples 1 to 10 Photosensitive resin compositions (solutions) were prepared and evaluated in the same manner as in Example 1, except that the types and amounts of components were changed as shown in the table below.

[0161]

[0162] As shown in the table, it was confirmed that the cured relief patterns of the Examples could achieve both high resolution and low dielectric loss tangent when the dried film (the dried film obtained by applying the photosensitive resin composition and then drying it at 110°C for 360 seconds) had a thickness of 30 μm or more. Therefore, it was confirmed that the Examples can provide a photosensitive resin composition capable of forming a cured relief pattern having such properties. Specifically, the Examples show that under thick film conditions, the evaluation result of "resolution" is "E" or "G" and the "dielectric loss tangent (tanδ)" is "E" or "G". １０ It was confirmed that the evaluation result of "E" or "G" in the "Test for Optical Fiber Resonance Imaging Test" (Test No. 10 ...

[0163] On the other hand, in the comparative examples, the evaluation results of "resolution" and / or "dielectric loss tangent" were poor compared to the examples. ａｖｅ In Comparative Examples 1 to 3, 5 to 6, and 9, in which the water permeability WVTR of the cured film was greater than 1.5800, the evaluation result of "resolution" was "P." In Comparative Examples 5 and 7, in which the water permeability WVTR of the cured film was greater than 300, the evaluation result of "dielectric loss tangent (tanδ １０ The evaluation result of "P" was obtained. Note that cloudiness was observed in the dried film obtained in Comparative Example 4, and therefore, the "refractive index N ａｖｅ It was difficult to properly conduct the "test."

[0164] Furthermore, the present disclosure focuses on an embodiment in which a thick dry film is required, and an embodiment in which a thick dry film is required, and for example, it is required that the above-mentioned thick film can be realized for various compositions in a photosensitive resin composition. In this regard, it was observed that in the photosensitive resin compositions (solutions) of Comparative Examples 8 and 10, some components were not completely dissolved in the solvent, that is, the components were not compatible with the solvent. Therefore, for Comparative Examples 8 and 10, the "refractive index Nａｖｅ It was difficult to properly carry out the tests for "Water Permeability WVTR" and "Water Vapour Retention Ratio", and therefore it was not possible to properly carry out the tests for "Resolution" and "Dielectric Loss Tangent".

[0165] The photosensitive resin composition of the present disclosure can be suitably used in the field of photosensitive materials useful for producing electrical and electronic materials such as semiconductor devices, multilayer wiring boards, etc. In one aspect, the photosensitive resin composition can be suitably used in the field of photosensitive materials useful for producing thick dried films and thick insulating films (cured films).

Claims

1. A photosensitive resin composition comprising the following components: (A) at least one resin selected from a polyimide precursor and a polyimide; (B) a photopolymerization initiator; and (C) a compound having an alkyl group, wherein the photosensitive resin composition is applied and then dried at 110°C for 360 seconds, and the refractive index N of the dried film is ａｖｅ The water permeability WVTR (g / m) of the cured film when the dried film is cured at 230°C for 2 hours is 1.5800 or less. ２ 24 hr) is 300 or less.

2. The photosensitive resin composition according to claim 1, wherein component (C) has an alkyl group having 4 or more carbon atoms.

3. The component (C) is represented by the following general formula (1): (wherein X is an alkyl group, Y is an organic group having 1 to 30 carbon atoms and containing at least one selected from an ester group, an isocyanurate group, an amide group, and a urea group, and m １ is an integer from 1 to 4, where m １ The photosensitive resin composition according to claim 1 or 2, wherein when X is 2 or more, the multiple Xs may be the same or different.

4. In the general formula (1), m １ The photosensitive resin composition according to claim 3, wherein the total number of carbon atoms in the X's is 10 to 20.

5. In the general formula (1), m １ When m is 1, X is a linear alkyl group; １ The photosensitive resin composition according to claim 3, wherein when X is 2 or more, at least one of X is a linear alkyl group.

6. The photosensitive resin composition according to claim 1 or 2, wherein the content of the component (C) is 0.5 to 50 parts by mass per 100 parts by mass of the component (A).

7. The component (C) is represented by the following general formulas (2) to (6): (wherein X represents an organic group having 1 to 30 carbon atoms, and multiple Xs may be the same or different, and at least one of the multiple Xs is an alkyl group).

8. The photosensitive resin composition according to claim 7, wherein the component (C) has at least one structure selected from the structures represented by the general formulas (4) to (6).

9. The component (A) is represented by the following general formula (8): (In the formula, A １ is a tetravalent organic group having 6 to 40 carbon atoms, and B １ is a divalent organic group having 6 to 40 carbon atoms, and n １ is an integer from 2 to 100, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms), and / or a group represented by the following general formula (9): (In the formula, A ２ is a tetravalent organic group having 6 to 40 carbon atoms, and B ２ is a divalent organic group having 6 to 40 carbon atoms, and n ２ The photosensitive resin composition according to claim 1 or 2, having at least one structure selected from the following:

10. In the general formula (8), R １ , and R ２ At least one of the following general formula (10): (In the formula, R ３ , R ４ , and R ５ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ The photosensitive resin composition according to claim 9, comprising a group represented by the following formula:

11. B in the general formula (8) １ and / or B in the general formula (9) ２ is represented by the following general formula (11): (In the formula, R ６ , and R ７ are each independently an organic group having 1 to 5 carbon atoms, and m ２ , and m ３ are each independently an integer of 1 to 4, and * is a bonding moiety to a main chain of the resin.

12. The component (B) is represented by the following general formula (12): (In the formula, R ８ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and R ９ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and R １０ is -H, -OH, -COOH, -O(CH ２ )OH, —O(CH ２ )2OH, -COO(CH ２ )OH or —COO(CH ２ ) ２ The photosensitive resin composition according to claim 1 or 2, comprising a structure represented by the formula:

13. The photosensitive resin composition according to claim 1 or 2, wherein a cured film of the photosensitive resin composition has a dielectric loss tangent of 0.015 or less when measured at 10 GHz using a perturbation split cylinder resonator method.

14. The photosensitive resin composition according to claim 1 or 2, which is used to form an interlayer insulating film.

15. A method for producing a cured film, the method comprising: applying the photosensitive resin composition according to claim 1 or 2 onto a substrate and forming a photosensitive resin layer on the substrate; exposing the photosensitive resin layer; developing the photosensitive resin layer after exposure; and heating the photosensitive resin layer after development to form a cured film.

16. A cured film of the photosensitive resin composition according to claim 1 or 2, having a thickness of 25 μm or more.

17. A cured film of the photosensitive resin composition according to claim 1 or 2, which has a dielectric loss tangent of 0.015 or less when measured at 10 GHz using a perturbation split cylinder resonator method.

18. The cured film according to claim 17, wherein the cured film has a thickness of 25 μm or more.

19. A semiconductor device comprising the cured film according to claim 16.

Images