Negative photosensitive resin composition, cured film using same, cured relief pattern production method, and semiconductor device

Abstract

Provided is a negative photosensitive resin composition comprising the following (A)-(C) components: (A) a polyimide precursor and / or a polyimide; (B) a photoinitiator; and (C) a radical-polymerizable compound. The (C) component includes (C1) a compound having a fluorene backbone. With respect to the total solid content mass, the mass proportion of compounds having a molecular weight of not less than 370 to less than 3000 excluding (C1) the compound having a fluorene backbone is not more than 2.4 mass%.

Description

Negative photosensitive resin composition, cured film using the same, method for producing cured relief pattern, and semiconductor device

[0001] The present invention relates to a negative photosensitive resin composition, a cured film using the same, a method for producing a cured relief pattern, and a semiconductor device.

[0002] Polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components, and as passivation films, surface protective films, and interlayer insulating films for semiconductor devices. Among polyimide resins, those provided in the form of photosensitive polyamic acid esters (polyimide precursors) can easily form heat-resistant relief pattern coatings by applying, exposing, developing, and curing the precursor to thermal imidization.

[0003] On the other hand, there are various semiconductor packaging methods for semiconductor devices. In recent years, a semiconductor packaging method called fan-out has become mainstream as a semiconductor packaging method. In a fan-out type semiconductor package, a semiconductor chip is covered with an encapsulant to form a chip encapsulation body larger than the chip size of the semiconductor chip. Furthermore, a rewiring layer is formed that extends to the semiconductor chip and the encapsulant area. The rewiring layer is formed with a thin film thickness. Furthermore, since the rewiring layer can be formed up to the encapsulant area, the number of external connection terminals can be increased. Here, for example, a device described in Patent Document 1 below is known as a fan-out type semiconductor device.

[0004] JP 2011-129767 A

[0005] In particular, in recent years, the method of mounting semiconductor devices on printed wiring boards has changed in light of improvements in integration density and computing functionality, as well as the need for smaller chip sizes. In structures such as SiP (System in Package), which enable higher-density mounting, polyimide coatings come into direct contact with solder bumps. If a material with low heat resistance is used to form such bump structures, a hardened film with low heat resistance will be formed when the bump structures are mounted on a substrate together with the semiconductor chip through a solder reflow process. In this case, temperature changes are likely to cause degassing and shrinkage, which in turn can lead to cracking and peeling. Therefore, the polyimide coating must have high heat resistance.

[0006] Furthermore, there has been a growing demand recently for thermosetting materials that can be cured at low temperatures (hereinafter, sometimes referred to as "low-temperature curing materials"). Phenolic resins have been widely developed as low-temperature curing materials for insulating film applications. On the other hand, from the viewpoints of chemical resistance and heat resistance, it is desirable to use polyimide resins. To cure polyimide resins, which are usually processed at 300 to 400°C, at low temperatures, common methods include using soluble polyimides and chemical imidization, in which an imidization accelerator is added to polyamic acid ester to perform imidization.

[0007] However, since soluble polyimides have a rigid structure before photocuring, there is a problem in that defects are likely to occur during the patterning steps of photocuring and development.

[0008] On the other hand, when polyamic acid esters are heat-treated at low temperatures, many low-molecular-weight compounds, including side chain components eliminated during the cyclization reaction to polyimide, remain, and the interaction between the resins is weakened, making it difficult to maintain the film properties. In particular, during heating processes such as solder reflow in semiconductor device processing, cracking and peeling are likely to occur due to decomposition and volatilization of low-molecular-weight components and shrinkage of the resin. Furthermore, during reliability tests under high-temperature, high-humidity, and high-pressure environments, known as HAST (High Accelerated Stress Test), the decomposition of the remaining low-molecular-weight components generates polar functional groups, which facilitate the penetration of water molecules and weaken the film properties.

[0009] Therefore, an object of the present invention is to provide a photosensitive resin composition (negative photosensitive resin composition) that can achieve the following (1) and (2): (1) produce a resin film having good patterning properties, and (2) produce a resin film having high thermal stability (i.e., no defects occur in a heating step such as reflow, and no defects occur in a reliability test such as HAST). Another object of the present invention is to provide a cured film and a method for producing a cured relief pattern using the photosensitive resin composition, and a semiconductor device.

[0010]

[0022] Examples of embodiments of the present invention are listed below. [1] A negative-type photosensitive resin composition comprising the following components (A) to (C): (A) a polyimide precursor and / or polyimide, (B) a photopolymerization initiator, and (C) a radically polymerizable compound, wherein the component (C) contains a compound (C1) having a fluorene skeleton, and the mass ratio of compounds having a molecular weight of 370 or more and less than 3,000, excluding the compound (C1) having a fluorene skeleton, to the total solid mass is 2.4 mass% or less. [2] The component (A) is a compound represented by the following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R１ , and R ２ and R are not simultaneously hydrogen atoms. １ , and R ２ At least one of the following general formula (2): (In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ , and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. [4] The negative photosensitive resin composition according to any one of items 1 to 3, wherein the compound having a fluorene skeleton (C1) has at least two radically polymerizable groups. [5] The negative photosensitive resin composition according to any one of items 1 to 3, wherein the compound having a fluorene skeleton (C1) is a group represented by the following general formula (3): (In the formula, R ａ ~R ｄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, an amino group, or an aryl group, and R ｅ is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ｆ[6] The negative photosensitive resin composition according to any one of items 1 to 4, having a structure represented by the following formula: wherein n1 and n2 are each independently an integer of 0 to 4, m1 and m2 are each independently an integer of 0 to 5, p1 and p2 are each independently an integer of 0 or greater, and k1+n1≦5 and k2+n2≦5. [7] The negative photosensitive resin composition according to any one of items 2 to 6, having a fluorine atom content per molecular weight of the structural unit represented by general formula (1), expressed as (the number of fluorine atoms contained in the structural unit represented by general formula (1) × the atomic weight of the fluorine atoms) / (the molecular weight of the structural unit represented by general formula (1)), of 13% or less. [8] Y in the general formula (1) １ In the formula (5): (In the formula, RF １ , and RF ２ each independently represent a fluorine atom or a trifluoromethyl group.) is less than 1 mmol%. [9] The negative photosensitive resin composition according to any one of items 1 to 8, wherein the mass ratio of compounds having a molecular weight of 370 or more and less than 3,000, excluding the compound (C1) having a fluorene skeleton, is 1.8 mass% or less, based on the total solid mass.

[10] The negative photosensitive resin composition according to any one of items 1 to 8, wherein the mass ratio of the compounds having a molecular weight of 370 or more and less than 3,000, excluding the compound (C1) having a fluorene skeleton, is 1.8 mass% or less, based on the total solid mass. １ and R ２The negative photosensitive resin composition according to any one of items 3 to 9, wherein the proportion of groups represented by the general formula (2) is 70 mol % or more.

[11] The negative photosensitive resin composition according to any one of items 1 to 10, further comprising at least one radical polymerizable compound (C2) that does not have a fluorene skeleton.

[12] The negative photosensitive resin composition according to item 11, wherein the radical polymerizable compound (C2) that does not have a fluorene skeleton has an isocyanuric skeleton.

[13] The negative photosensitive resin composition according to item 12, comprising 1 to 30 parts by mass of the radical polymerizable compound (C2) that has an isocyanuric skeleton and does not have a fluorene skeleton, per 100 parts by mass of the component (A).

[14] The negative photosensitive resin composition according to any one of items 1 to 13, further comprising (D) an acidic compound.

[15] In the general formula (1), X １ is represented by the following general formulas (6) to (9): (In the formula, R ６ , R ７ , and R ８ are each independently an oxygen atom, a sulfur atom, or a divalent organic group, and R ９ , and R １０ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R ９ , and R １０

[16] The negative photosensitive resin composition according to any one of items 2 to 14, wherein Y is at least one group selected from the following general formula (1): １ is represented by the following general formulas (10) to (13): (In the formula, R １４ , R １５ , R １６ , and R １７ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R １４ , R １５ , R １６ , and R １７ may be the same or different from each other.) (In the formula, R １８ ~R ２５ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R １８ ~R ２５ may be the same or different from each other, and R ２６ is a divalent group. (In the formula, R ２７ , and R ２８ are each independently a divalent group, and R ２９ , and R ３０ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R ２９ , and R ３０

[17] The photosensitive resin composition according to any one of items 2 to 15, wherein the component (B) is at least one group selected from the following general formula (14) or (15): {In the formula, R ９ is a phenyl group, a tolyl group, or an alkyl group having 1 to 12 carbon atoms, and R １０ is a phenyl group, a tolyl group, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 1 to 5 carbon atoms, and R １１ is a hydrogen atom or a carboxyl group (—COOH). (In the formula, R １２

[18] The negative photosensitive resin composition according to any one of items 1 to 16, having a structure represented by the following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２and (C) a radical polymerizable compound, wherein the negative photosensitive resin composition is spin-coated onto a wafer to a thickness of 10 μm, heated at 110° C. for 240 seconds, and then subjected to irradiation with 500 mJ / cm 2 ２

[19] A negative photosensitive resin composition, wherein when a cured film is exposed to i-rays of 100 nm or less and cured at 230°C for 4 hours, the cured film is cut into 5 mm square pieces and subjected to thermal evolved gas mass spectrometry at a heating rate of 10°C / min, and in each mass spectrum obtained by scan mode analysis, the total fragment count (TIC) obtained by adding up all m / z signals is detected at an abundance of 200,000 or more at a temperature of 300°C or more. (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ and (C) a radical polymerizable compound, wherein the negative photosensitive resin composition is spin-coated onto a wafer to a thickness of 10 μm, and heated at 110° C. for 240 seconds, and then subjected to irradiation with 500 mJ / cm 2 ２

[20] A negative photosensitive resin composition, wherein when a cured film is exposed to i-rays of 100 nm or less and cured at 230°C for 4 hours, cut into 5 mm square pieces, and subjected to thermal evolved gas mass spectrometry at a temperature increase rate of 10°C / min, the temperature at which a fragment having m / z of 41 or 69 is detected with an abundance of 5000 or more is 300°C or higher. (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R２ and (C) a radical-polymerizable compound, wherein the component (C) contains (C1) a compound having a fluorene skeleton, and the negative-type photosensitive resin composition is spin-coated onto a wafer to a thickness of 10 μm, heated at 110° C. for 240 seconds, and then subjected to irradiation with 500 mJ / cm 2 of fluorene. ２

[21] A negative-type photosensitive resin composition, wherein the 5% thermal weight loss temperature of the cured film obtained by exposure to i-rays of 1000 nm or more and curing at 230°C for 4 hours is 360°C or higher. (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ and (C1) a radical polymerizable compound having a fluorene skeleton, and the cured film has a 5% thermal weight loss temperature of 360°C or higher.

[22] A method for producing a cured relief pattern, the method comprising: forming a photosensitive resin layer on a substrate by applying the negative photosensitive resin composition according to any one of items 1 to 20 onto the substrate; exposing the photosensitive resin layer; developing the exposed photosensitive resin layer to form a relief pattern; and heat-treating the relief pattern to form a cured relief pattern.

[23] A semiconductor device comprising a cured relief pattern formed using the negative photosensitive resin composition according to any one of items 1 to 20.

[0011] According to the present invention, it is possible to provide a photosensitive resin composition (negative photosensitive resin composition) that is capable of achieving the following (1) and (2): (1) producing a resin film having good patterning properties, and (2) producing a resin film having high thermal stability (i.e., no defects occur in a heating step such as reflow, and no defects occur in a reliability test such as HAST). Another object of the present invention is to provide a cured film, a method for producing a cured relief pattern, and a semiconductor device using the photosensitive resin composition. Furthermore, according to the present invention, it is possible to provide a cured film, a method for producing a cured relief pattern, and a semiconductor device using the photosensitive resin composition.

[0012] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In this specification, with respect to stepwise numerical ranges, the upper or lower limit of a certain numerical range can be replaced with the upper or lower limit of another stepwise numerical range, and can also be replaced with the corresponding value in the examples. In this specification, the term "step" does not only mean an independent step; therefore, even if a step cannot be clearly distinguished from other steps, the term "step" includes the mode in which the function of the step is achieved. In addition, in the contents shown in the drawings, the scale, shape, and length may be exaggerated for clarity. In this specification, various measurements are performed based on the methods described in the examples, unless otherwise specified.

[0013] [Embodiment 1] [Photosensitive Resin Composition] This embodiment is a negative-type photosensitive resin composition comprising the following components (A) to (C): (A) a polyimide precursor and / or polyimide, (B) a photopolymerization initiator, and (C) a radical-polymerizable compound, wherein the component (C) comprises (C1) a compound having a fluorene skeleton (hereinafter referred to as (C1) compound), and the mass ratio of compounds having a molecular weight of 370 or more and less than 3,000, excluding the (C1) compound, is 2.4 mass% or less, based on the total mass of the solid content of the negative-type photosensitive resin composition. This photosensitive resin composition enables the following (1) and (2): (1) a resin film having good patterning properties can be produced, and (2) a resin film having high thermal stability (i.e., no defects occur in a heating process such as reflow, and no defects occur in a reliability test such as HAST) can be produced.

[0014] The present inventors discovered that a resin composition containing a radically polymerizable compound having a specific fluorene skeleton and containing a specific compound group at a controlled ratio can exhibit the desired effects, leading to the completion of the present embodiment. In this embodiment, a polymer is produced by a radical reaction between the radically polymerizable compound and a polymer side chain, etc., during the exposure process and subsequent thermal curing process. Here, since the radically polymerizable compound contains a fluorene skeleton, the polymer produced by the radical reaction has high thermal stability. When the photosensitive resin composition of this embodiment is cured by thermal curing (curing) to form a cured film, the polymer remaining in the film is unlikely to decompose during the reflow process and reliability test. Therefore, it is presumed that defects caused by decomposition of the polymer remaining in the film can be suppressed. Furthermore, compounds with a molecular weight (in one embodiment, a weight-average molecular weight) of less than 370 are likely to volatilize during the thermal curing process, for example, at 230°C, and therefore are unlikely to remain in the film after thermal curing. On the other hand, compounds with a molecular weight of 370 or more but less than 3000, excluding the (C1) compound, are less likely to volatilize during the thermal curing process than compounds with a molecular weight less than 370. In this embodiment, by setting the mass ratio of compounds with a molecular weight of 370 or more but less than 3000, excluding the (C1) compound, to 2.4 mass% or less of the total solid mass of the photosensitive resin composition, it is possible to reduce the amount of low-molecular-weight components remaining in a film obtained by curing the photosensitive resin composition (film after the thermal curing process). This is presumably effective in suppressing defects caused by decomposition of low-molecular-weight components during the reflow process and reliability test. Here, the (C1) compound and structural units derived therefrom can remain in the film after thermal curing in a thermally stabilized state, for example, by undergoing a crosslinking reaction in the exposure process. In other words, in this embodiment, the exclusion of the (C1) compound from the "compounds with a molecular weight of 370 or more but less than 3000" is intended to focus on factors that may adversely affect film thickness change after thermal curing.

[0015] In this embodiment, the "total solids mass" of the photosensitive resin composition refers to the mass of the photosensitive resin composition excluding any solvent components optionally contained therein. Therefore, the "total solids mass" can be determined by removing any solvent components optionally contained therein from the photosensitive resin composition, and the sum of the raw material components excluding the solvent for producing the photosensitive resin composition corresponds to the "total solids mass."

[0016] In this embodiment, "compounds having a molecular weight of 370 or more and less than 3000, excluding compound (C1)" refers to compounds having a molecular weight of 370 or more and less than 3000, and other than compounds included as compound (C1) in this embodiment. In the photosensitive resin composition of this embodiment, various components other than compound (C1) may be included in this "compounds having a molecular weight of 370 or more and less than 3000." However, since component (A) is a polymer and is basically assumed to have a weight-average molecular weight of 3000 or more, component (A) is not included in this "compounds having a molecular weight of 370 or more and less than 3000."

[0017] The total amount of "compounds having a molecular weight of 370 or more and less than 3000, excluding compound (C1)" corresponds to the total amount of compounds having a weight average molecular weight of 370 or more and less than 3000, among the raw material components other than compound (C1), used to prepare the photosensitive resin composition of this embodiment. When the photosensitive resin composition of this embodiment contains components (A) to (C), optionally contains component (D), and optionally contains other components other than components (A) to (D), the total amount of "compounds having a molecular weight of 370 or more and less than 3000, excluding compound (C1)" corresponds to the total amount of "compounds having a molecular weight of 370 or more and less than 3000, which are component (A), component (B), component (C) other than compound (C1), component (D), and further other components, and which have a molecular weight of 370 or more and less than 3000."

[0018] As described above, the photosensitive resin composition of this embodiment has a mass ratio of compounds having a molecular weight of 370 or more but less than 3,000, excluding the (C1) compound, of 2.4 mass% or less relative to the total solid mass. If the mass ratio exceeds 2.4 mass%, a large amount of components remain in the film after thermal curing at, for example, 230°C. Therefore, defects are likely to occur when heat treatment such as reflow is performed at a temperature higher than this, or when reliability tests such as HAST tests are performed. The mass ratio is preferably 2.0 mass% or less, and more preferably 1.8 mass% or less. The mass ratio may be 0 mass% or more (e.g., 0.0 mass% or more).

[0019] The components (A) to (C) and raw materials thereof contained in the photosensitive resin composition, the component (D) optionally contained in the photosensitive resin composition, and other components optionally contained in the photosensitive resin composition (components other than the components (A) to (D)) may be used alone or in combination of two or more. The combination of two or more may be, for example, a combination of two to five types, but is not limited to this. Each component will be described below.

[0020] Component (A) The photosensitive resin composition of this embodiment contains (A1) a polyimide precursor and / or (A2) a polyimide.

[0021] From the viewpoint of patterning ability of the (A1) polyimide precursor and chemical resistance after curing, the (A) component preferably contains or is the (A1) polyimide precursor. The polyimide precursor is also called a polyamic acid ester and is represented by the following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ and (C) are not simultaneously hydrogen atoms. The polyimide precursor is converted to a polyimide by a cyclization treatment involving heating (for example, at 200° C. or higher).

[0022] In general formula (1), R １ , and R ２ At least one of the following general formula (2): (In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ , and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. ３ , R ４ or R ５ When R is an organic group having 1 to 3 carbon atoms, it is preferably a linear organic group having 1 to 3 carbon atoms from the viewpoint of reactivity with the radical polymerizable compound. １ , and R ２ Only one of the groups may be a group represented by the general formula (2), and R １ , and R ２ may both be groups represented by the above general formula (2).

[0023] In general formula (2), R ３ Examples of R include a hydrogen atom, a methyl group, an ethyl group, and a propyl group, and a methyl group is preferred. ４ , and R ５ In general formula (2), m is more preferably an integer of 2 to 5, and even more preferably an integer of 2 or 3.

[0024] R in general formula (1) １ , and R ２ The proportion of hydrogen atoms in R １ , and R ２ Based on the total number of moles, it is more preferably 20 mol % or less, more preferably 15 mol % or less, and even more preferably 5 mol % or less. １ , and R ２ is a monovalent group represented by general formula (2), R １ , and R２ Based on the total number of moles, it is preferably 70 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more. １ , and R ２ The proportion of hydrogen atoms in R １ , and R ２ It is preferable that the proportion of the group represented by formula (2) is within the above range from the viewpoints of both photosensitive characteristics and storage stability.

[0025] In general formula (1), n ​​is preferably an integer of 3 to 100, more preferably an integer of 5 to 70, from the viewpoint of the photosensitivity and mechanical properties of the photosensitive resin composition.

[0026] The content of fluorine atoms per molecular weight of the structural unit represented by general formula (1) (hereinafter referred to as fluorine atom content) is preferably small, and specifically, the fluorine atom content represented by (number of fluorine atoms contained in the structural unit represented by general formula (1) × atomic weight of fluorine atoms) / (molecular weight of the structural unit represented by general formula (1)) is preferably 13% or less. This makes it easier to achieve the effects of this embodiment. Note that fluorine atoms are contained in X in general formula (1). １ It may be included in Y １ It may be included in some.

[0027] (X in general formula (1) １ In the general formula (1), X １ is, for example, a tetravalent organic group preferably having 6 to 40 carbon atoms, more preferably -COOR １ group, and -COOR ２ In general formula (1), X is 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 The tetravalent organic group represented by the formula (I) is more preferably an organic group having 6 to 30 carbon atoms, and even more preferably an organic group having 6 to 20 carbon atoms. These organic groups can easily achieve both heat resistance and photosensitive properties.

[0028] X １ Examples of the organic group include an aromatic ring-containing organic group having 6 to 40 carbon atoms, specifically, a group represented by the following general formula (I): (In the formula, R ６ is a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.} Examples of X having a structure represented by the above formula (I) include groups having a structure selected from the following. １ The group is particularly preferable from the viewpoint of achieving both heat resistance and photosensitive properties.

[0029] In general formula (1), X １ is particularly represented by the following general formulas (6) to (9): (In the formula, R ６ , R ７ , and R ８ are each independently an oxygen atom, a sulfur atom, or a divalent organic group, and R ９ , and R １０ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R ９ , and R １０ may be the same or different.) When the polyimide precursor has such a structure, film strength and resolution can be easily improved.

[0030] X １ Although one kind or a combination of two or more kinds may be used, a combination of two or more kinds is more preferable from the viewpoint of improving resolution.

[0031] (Y in general formula (1) １ In the general formula (1), Y １ is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (II): {In the formula, R ６represents a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer selected from 0 to 4. １ may be one type or a combination of two or more types. １ is particularly preferable from the viewpoint of achieving both heat resistance and photosensitive properties.

[0032] Here, Y in general formula (1) １ In the formula (5): (In the formula, RF １ , and RF ２ each independently represents a fluorine atom or a trifluoromethyl group.) The content of units represented by the following formula (1) is preferably low, and specifically, is preferably less than 1 mmol%. In this regard, in this embodiment, １ In this case, it is different from the embodiment in which a high content of the unit represented by the above general formula (5) is preferred.

[0033] In the general formula (1), Y １ In particular, the general formulas (10) to (13): (In the formula, R １４ , R １５ , R １６ , and R １７ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R １４ , R １５ , R １６ , and R １７ may be the same or different from each other.) (In the formula, R １８ ~R ２５ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R １８ ~R ２５ may be the same or different from each other, and R ２６ is a divalent group. (In the formula, R ２７ , and R ２８ are each independently a divalent group, and R２９ , and R ３０ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R ２９ , and R ３０ may be the same or different.) When the polyimide precursor (A1) contains a group having such a structure, film strength and resolution can be easily improved.

[0034] (A) Preparation method of polyimide precursor First, １ A tetracarboxylic acid dianhydride containing the compound Y is reacted with an alcohol having a photopolymerizable unsaturated double bond, and optionally, an alcohol having no unsaturated double bond is further reacted therewith. This produces a partially esterified tetracarboxylic acid (hereinafter also referred to as an "acid / ester"), which is then reacted with the tetracarboxylic acid and the aforementioned Y. １ and a diamine containing the same, to obtain a polyimide precursor.

[0035] (Preparation of Acid / Ester Form) X, which is preferably used to prepare a polyimide precursor, １Examples of the tetracarboxylic dianhydride containing the formula (I) include tetracarboxylic dianhydrides having the structure represented by the general formula (I) above, as well as, for example, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. Preferred examples include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, etc. These may be used alone or in combination of two or more.

[0036] Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare a polyimide precursor or a polyamic acid ester resin include 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, 2-hydroxy-3-t ... Examples of the alcohols include hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate. As these alcohols, linear compounds having no branched structure are preferred.

[0037] When using the above-mentioned photopolymerizable alcohols having an unsaturated double bond, they may be mixed with alcohols not having an unsaturated double bond, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

[0038] As the polyimide precursor, a non-photosensitive polyamic acid ester resin prepared only from the above-mentioned alcohols having no unsaturated double bonds may be used by mixing with the polyimide precursor. From the viewpoint of resolution, the amount of the non-photosensitive polyamic acid ester resin is preferably 200 parts by mass or less based on 100 parts by mass of the polyimide precursor (A1).

[0039] The esterification reaction of the acid anhydride can be carried out by dissolving and mixing a tetracarboxylic dianhydride and an alcohol in a solvent as described below in the presence of a basic catalyst such as pyridine, thereby obtaining the desired acid / ester. The dissolving and mixing with stirring is preferably carried out at a temperature of 20 to 50°C for 4 to 24 hours, for example.

[0040] (Preparation of Polyimide Precursor) The acid / ester compound (typically present as a solution in a solvent described below) can be converted into a polyacid anhydride by adding and mixing with an appropriate dehydration condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, under ice cooling. １ A polyimide precursor can be obtained by adding dropwise a solution or dispersion of a diamine containing the compound (I) dissolved or dispersed in a separate solvent and carrying out amide polycondensation. Alternatively, the acid moiety of the acid / ester compound can be converted into an acid chloride using thionyl chloride or the like, and then reacting the acid / ester compound with a diamine compound in the presence of a base such as pyridine to obtain a polyimide precursor.

[0041] As another synthesis method, a polyimide precursor can also be obtained by first reacting a tetracarboxylic dianhydride with a diamine compound to obtain a polyamic acid, and then using an appropriate dehydration condensation agent, for example, trifluoroacetic anhydride, to introduce the above-mentioned alcohol into the carboxylic acid moiety in the side chain of the obtained polyamic acid.

[0042] Y １Examples of diamines containing the formula (10) include diamines represented by the above general formulas (10) to (13), as well as, for example, p-phenylenediamine, m-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3'-diaminodiphenyl ether. ter, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethyl benzene, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] 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 (BAPP), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,Examples of such compounds include 4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, and 9,9-bis(4-aminophenyl)fluorene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diaminooctafluorobiphenyl, and mixtures thereof.

[0043] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off as needed. A poor solvent, such as water, aliphatic lower alcohol, or a mixture thereof, is then added to the resulting polymer component to precipitate the polymer component. The polymer is then purified by repeated redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with anion and / or cation exchange resins swollen with an appropriate organic solvent to remove ionic impurities.

[0044] The molecular weight of the polyimide precursor, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, while when it is 150,000 or less, the dispersibility in the developer is good, and in this case, the resolution of the relief pattern is good. Tetrahydrofuran or N-methyl-2-pyrrolidone is preferred as the developing solvent for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. The standard monodisperse polystyrene is preferably selected from Resonaq's organic solvent-based standard sample, STANDARD SM-105.

[0045] (A2) Polyimide As described above, the component (A) can contain the polyimide precursor (A1). On the other hand, the component (A) can contain the polyimide (A2) regardless of the presence or absence of the polyimide precursor (A1). The polyimide (A2) can be represented by the following general formula (5'): (In the formula, X ２ is a tetravalent organic group, and Y ２ is a divalent organic group, and n is an integer of 2 to 150. The structural unit represented by general formula (5') is particularly preferred from the viewpoint of being suitable for treatment at lower temperatures, since it does not require chemical change in the heat treatment step in order to exhibit sufficient film properties.

[0046] In the general formula (5'), X ２ , and / or Y ２ From the viewpoint of heat resistance, it is preferable that X contains an aromatic ring structure, more preferably has 6 to 40 carbon atoms, and furthermore preferably contains a benzene ring structure. ２ , and / or Y ２ preferably has a structure in which 2 to 6 benzene rings are linked via a single bond or a divalent linking group. Here, examples of the "divalent linking group" include an alkylene group, a fluorinated alkylene group, and an ether group. Both the alkylene group and the fluorinated alkylene group may be linear or branched.

[0047] (A2) Polyimide can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, a tetracarboxylic acid diester dichloride, etc. with a diamine, a corresponding diisocyanate compound, a trimethylsilylated diamine, etc. Polyimide can generally be obtained by dehydrating and ring-closing a polyamic acid, which is one of polyimide precursors obtained by reacting a tetracarboxylic acid dianhydride with a diamine, by heating or chemical treatment with an acid, a base, etc.

[0048] (A2) Examples of tetracarboxylic dianhydrides suitable for synthesizing polyimides include: Pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride aromatic tetracarboxylic acid dianhydrides such as bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic acid dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; or aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride; 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, and the like.

[0049] Among them, suitable tetracarboxylic dianhydrides include, for example, pyromellitic dianhydride (PMDA), diphenylether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA), 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA), and the like. These may be used alone or in combination of two or more. ODPA is also known as 4,4'-oxydiphthalic dianhydride.

[0050] (A2) Examples of diamines suitable for synthesizing polyimides include 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diaminodiphenyl sulfone, 3,3'dimethylbenzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis(p- 2,2'-bis(pentafluoroethoxy)benzidine (TFMOB), 2,2'-trifluoromethyl-4,4'-oxydianiline (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2,2'-bis(2-heptafluoroisopropoxy-tetrafluoroisopropyl)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydianiline (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2,2'-bis(2-heptafluoroisopropoxy-tetrafluoroisopropyl)benzidine (TFMOB), 2,2'-bis(2-heptafluoroisopropoxy-tetrafluoroisopropyl)benzidine (TFEOB), 2,2'-bis(trifluoromethyl-4,4'-oxydianiline) (dichloroethoxy)benzidine (DFPOB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5-diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminobenzotrifluoride (3,5-DABT F), 3,5-diamino-5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethylbenzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)xanthene (6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenylxanthene (3FCDAM), 3,6-diamino-9,9-diphenylxanthene, etc.

[0051] The compounding ratio of the diamine to the acid dianhydride is basically 1:1 in molar ratio. However, to obtain a desired terminal structure, one of them may be used in excess. Specifically, by using an excess of diamine, the terminals (both terminals) of the polyimide (A2) tend to become amino groups. On the other hand, by using an excess of acid dianhydride, the terminals (both terminals) of the polyimide (A2) tend to become acid anhydride groups. In this embodiment, it is preferable that the polyimide (A2) has acid anhydride groups at its terminals. Therefore, in this embodiment, it is preferable to use an excess of acid dianhydride when synthesizing the polyimide (A2).

[0052] The amino group and / or acid anhydride group at the end of the polyimide obtained by condensation polymerization may be reacted with some kind of reagent so that the polyimide end has a desired functional group.

[0053] The molecular weight of the (A2) polyimide, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, and particularly preferably 10,000 to 50,000. A weight average molecular weight of 5,000 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 dispersibility in a developer and good resolution performance of a relief pattern. The above-described details may be referenced for the developing solvent for gel permeation chromatography and the standard monodisperse polystyrene.

[0054] Component (B) The photosensitive resin composition of this embodiment contains a photopolymerization initiator as component (B). As component (B), any compound conventionally used as a photopolymerization initiator for UV curing can be selected.

[0055] Examples of component (B) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone; thioxanthone derivatives such as 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; 2,6-di(4'-diazidobenzal)-4-methylcyclohexanone, and 2, Examples of suitable azides include 6'-di(4'-diazidobenzal)cyclohexanone; oximes such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl peroxide; aromatic biimidazoles; and titanocenes. Of these, the above-mentioned oximes are preferred from the viewpoint of photosensitivity.

[0056] From the viewpoint of improving the thermal stability of the cured film, the component (B) may have a molecular weight (in one embodiment, weight average molecular weight) of 700 or less, preferably 440 or less, and more preferably 370 or less.

[0057] The component (B) is represented by the following general formula (14) or (15): {In the formula, R ９ is a phenyl group, a tolyl group, or an alkyl group having 1 to 12 carbon atoms, and R １０ is a phenyl group, a tolyl group, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 1 to 5 carbon atoms, and R １１is a hydrogen atom or a carboxyl group (—COOH)} (In the formula, R １２ is a hydrogen atom, an alkyl ester, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. This structure makes it easy to generate radicals uniformly throughout the film, and is preferable from the viewpoint of patterning properties.

[0058] The content of component (B) is preferably 0.1 to 20 parts by mass per 100 parts by mass of component (A), and from the viewpoint of photosensitivity characteristics, it is preferably 2 to 15 parts by mass. By containing 0.1 part by mass or more of component (B) per 100 parts by mass of component (A), the photosensitive resin composition is likely to have excellent photosensitivity, while by containing 20 parts by mass or less, the photosensitive resin composition is likely to have excellent thick-film curing properties.

[0059] The photosensitive resin composition of this embodiment includes the component (C). The component (C) is a radically polymerizable compound, and includes a compound (C1) having a fluorene skeleton (hereinafter, referred to as the (C1) compound). That is, the (C1) compound is understood to be a radically polymerizable compound having a fluorene skeleton.

[0060] Compound (C1) The photosensitive resin composition of this embodiment may contain compound (C1) in order to improve the resolution of the relief pattern, to improve stability in a heating step such as reflow, and / or to improve the reliability of a HAST test, etc. From the viewpoint of patterning properties, it is preferable that compound (C1) has at least two radically polymerizable groups.

[0061] Here, the compound (C1) is represented by the following general formula (3): (In the formula, R ａ ~R ｄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, an amino group, or an aryl group, and R ｅ is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ｆis a hydrogen atom or a methyl group, k1 and k2 are each independently an integer of 1 to 5, n1 and n2 are each independently an integer of 0 to 4, m1 and m2 are each independently an integer of 0 to 5, p1 and p2 are each independently an integer of 0 or more, and k1+n1≦5 and k2+n2≦5. (In the formula, R ａ ~R ｄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, an amino group, or an aryl group, and R ｅ is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ｆ is a hydrogen atom or a methyl group, k1 and k2 are each independently an integer of 1 to 5, n1 and n2 are each independently an integer of 0 to 4, m1 and m2 are each independently an integer of 0 to 5, p1 and p2 are each independently an integer of 2 or greater, and k1+n1≦5 and k2+n2≦5.

[0062] In general formula (3), p1 and p2 are each independently an integer of 0 or more, and from the viewpoint of radical polymerizability and adhesion to a copper substrate after a reliability test, preferably, they are each independently an integer of 2 or more.

[0063] From the viewpoint of satisfying patterning properties, film properties, and copper adhesion, the content of compound (C1) is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of component (A). When compound (C1) is contained in an amount of 1 part by mass or more, good patterning performance is easily achieved, and when compound (C1) is contained in an amount of 50 parts by mass or less, film properties and copper adhesion are easily improved.

[0064] Compound (C2) The component (C) may include a radical polymerizable compound that does not have a fluorene skeleton as the compound (C2). That is, in one embodiment, the photosensitive resin composition may further include at least one compound (C2).

[0065] Examples of the (C2) compound include glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cetyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, hydroxyphenyl (meth)acrylate, benzyl (meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, methoxypolypropylene glycol mono(meth)acrylate, lauroxypolyethylene glycol (meth)acrylate, stearoxypolyethylene glycol (meth)acrylate, (2-oxy-1,3-dioxolan-4-yl ) methyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethoxy-o-phenylphenol (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, tricyclodecane dimethanol diacrylate, bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, bis-(2-acryloxyethyl)isocyanurate, tris-(2-acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, polypentaerythritol poly(meth)acrylate, etc. These may be used alone or in combination of two or more.

[0066] As the compound (C2), a compound having an isocyanuric skeleton is preferred from the viewpoint of achieving both patterning properties and thermal stability.

[0067] From the viewpoint of satisfying patterning properties, film properties, and copper adhesion, the content of the (C2) compound is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of the (A) component. By containing 1 part by mass or more of the (C2) compound, good patterning performance is easily achieved, and by containing 50 parts by mass or less, film properties and copper adhesion are easily improved.

[0068] From the viewpoint of improving the patterning properties while improving the stability in heating steps such as reflow, the content of the radical polymerizable compound (C2) that has an isocyanuric skeleton but does not have a fluorene skeleton is preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of the component (A). By containing 1 part by mass or more of the radical polymerizable compound (C2) that has an isocyanuric skeleton but does not have a fluorene skeleton, good thermal stability is easily exhibited, and by containing 30 parts by mass or less, the patterning properties are easily controlled.

[0069] Component (D): Acidic Compound The photosensitive resin composition of this embodiment may contain an acidic compound as component (D). In this specification, "acidic" in component (D) refers to a compound having a pKa of 10 or less. In the present disclosure, the pKa value can be calculated using Advanced Chemistry Software V11.02 (1994-2018 ACD / Labs). Use of component (D) can suppress the generation of foreign matter in the varnish and also suppress gelation of the varnish due to an imidization reaction. As a result, the storage stability of the photosensitive resin composition of this embodiment is likely to be improved. In particular, from the viewpoint of achieving superior thermal stability of the cured film, an organic acidic compound is preferred as the acidic compound (D). Furthermore, from the viewpoint of achieving superior thermal stability of the cured film, the content of the acidic compound (D) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of component (A).

[0070] The component (D) may be any compound having a pKa of 10 or less, preferably containing a sulfonic acid or a carboxylic acid, and more preferably being a sulfonic acid or a carboxylic acid. Examples of such compounds include formic acid, acetic acid, diethylenetriaminepentaacetic acid, propionic acid, butyric acid, oxalic acid, mandelic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, lactic acid, malonic acid, succinic acid, citric acid, glutaric acid, adipic acid, malic acid, ascorbic acid, tartaric acid, valeric acid, benzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-nitrobenzoic acid, carbonic acid, boronic acid, phosphoric acid, phosphonic acid, phosphinic acid, camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like. Examples of suitable sulfonic acids include toluenesulfonic acid, cyclohexanesulfonic acid, octanesulfonic acid, butanesulfonic acid, ethanesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, dodecanesulfonic acid, mesitylenesulfonic acid, 2,4,6-triisopropylbenzenesulfonic acid, β-naphthylsulfonic acid, naphthalene-1,5-disulfonic acid, ethane-1,2-disulfonic acid, 2-hydroxyethanesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, nitric acid, and sulfuric acid. Among these, mandelic acid or p-toluenesulfonic acid is preferred from the viewpoint of storage stability.

[0071] From the viewpoints of heat resistance and adhesion to copper substrates, the content of component (D) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 1 part by mass, per 100 parts by mass of component (A).

[0072] Other Components The photosensitive resin composition of this embodiment may further contain components (other components) other than the above components (A) to (D). Examples of other components include resin components other than component (A); sensitizers; photopolymerization inhibitors; rust inhibitors (e.g., nitrogen-containing heterocyclic compounds); adhesion aids; organometallic complexes; plasticizers; and solvents. When these components are contained, the molecular weight of the components is preferably 700 or less, and more preferably 370 or less, from the viewpoint of improving the thermal stability of the cured film.

[0073] (Resin Components Other Than Component (A)) The photosensitive resin composition of this embodiment may optionally contain a resin component other than component (A). Examples of such a resin component include polyoxazole, polyoxazole precursor, phenolic resin, polyamide, siloxane resin, and acrylic resin. The content of these resin components is preferably 0.01 to 20 parts by mass per 100 parts by mass of component (A).

[0074] (Sensitizer) The photosensitive resin composition of the present embodiment 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-dimethylaminocinnamylideneindano. 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 may be used alone or in combination of two or more. The content of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of the component (A).

[0075] (E): Rust inhibitor: In this embodiment, a rust inhibitor may be optionally contained to suppress copper migration. The rust inhibitor (E) is not limited as long as it can prevent metals from rusting, but examples thereof include nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds include azole compounds, pyrazine derivatives, and purine derivatives.

[0076] Examples of the azole compounds 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, 2- Examples of suitable azole compounds include (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, 1H-tetrazole-5-acetic acid, and 1-methyl-1H-tetrazole. Among these, 1H-tetrazole-5-acetic acid is preferred as the azole compound used as the (E) rust inhibitor.

[0077] Particularly preferred azole compounds include 5-amino-1H-tetrazole and 1H-tetrazole-5-acetic acid. These azole compounds may be used alone or in combination of two or more.

[0078] Purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 2 2-acetamido-9-acetyl-6-oxopurine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 2-acetamido-6-hydroxypurine, 8-azahypoxanthine, and derivatives thereof. Among these, 2-acetamido-6-hydroxypurine is preferred as the purine derivative used as the (E) rust inhibitor.

[0079] Examples of pyrazine derivatives include tetra-2-pyridinylpyrazine, 2,3-bis(2-pyridyl)pyrazine, acetylpyrazine, 2-amino-6-methylpyrazine, 2-amino-5-phenylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 2,5-pyrazinedicarboxylic acid, 3-aminopyrazine-2-carboxylic acid, 2,2'-bipyrazine, tetramethylpyrazine, 2-butyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, and 2,3-diethylpyrazine. Examples of suitable pyrazine derivatives include tetra-2-pyridinylpyrazine, 2,3-diethyl-5-methylpyrazine, 2-ethyl-3-(methylthio)pyrazine, 2-ethyl-3-methylpyrazinecyanopyrazine, 2,3-dicyanopyrazine, 5,6-diamino-2,3-dicyanopyrazine, 2,3-dicyano-5-methylpyrazine, 2-(1-piperazinyl)pyrazine, pyrazinamide, 2-pyrazinecarbohydrazide, 2,3-biphenylpyrido (2,3-B)pyrazine, phenazine, quinoxaline, and derivatives thereof. Among these, tetra-2-pyridinylpyrazine is preferred as the pyrazine derivative used as the (E) rust inhibitor.

[0080] When the photosensitive resin composition of this embodiment contains an azole compound or a purine derivative as the rust inhibitor (E), the content thereof is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (A). When the content of the azole compound or purine derivative per 100 parts by mass of component (A) is 0.05 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the negative photosensitive resin composition of this embodiment is formed on copper or a copper alloy. On the other hand, when the content of the azole compound or purine derivative is 5 parts by mass or less, excellent photosensitivity is achieved.

[0081] Component (F): Photopolymerization Inhibitor The photosensitive resin composition of this embodiment may optionally contain a photopolymerization inhibitor to appropriately control the photoradical crosslinking reaction. Examples of the photopolymerization inhibitor (F) include compounds containing an aromatic hydroxyl group, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, phenothiazine compounds, and hindered phenol compounds.

[0082] Examples of compounds containing an aromatic hydroxyl group include 4-methoxyphenol (p-methoxyphenol), 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6- Diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ester, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, catechol, tert-butyl-catechol, 4,4',4"-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol phenol, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, hydroquinone, methylhydroquinone, t-butylhydroquinone, di-t-butyl-p-cresol, pyrogallol, 4,4-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), phenol resins, and cresol resins.Among these, p-methoxyphenol is preferred as the compound containing an aromatic hydroxyl group used as the photopolymerization inhibitor (F).

[0083] Examples of nitroso compounds include nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitrosodiphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitrosopyrrolidine, N-t-butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperidine, 4-nitrosomorpholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N-nitrosophenylhydroxyamine cerous salt, N-nitrosophenylhydroxyamine aluminum salt, 2,4,6-Tris-t-butyl-nitrosobenzene, and N-nitrosodiphenylamine.

[0084] Examples of the N-oxide compounds include phenyl-t-butylnitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide.

[0085] Examples of quinone compounds include p-benzoquinone, p-xyloquinone, p-toluquinone, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone, 2-tert-butyl-p-benzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-1,4-benzoquinone, thymoquinone, 2,5-di-tert-amylbenzoquinone, and 2-bromo-1,4-benzoquinone. 1,4-benzoquinone, 2,5-dibromo-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, 2-bromo-5-methyl-1,4-benzoquinone, tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone, 2-chloro-5-methyl-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2,5-dihydroxy- 1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, tetrahydroxy-1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-anthraquinone, 2-methyl-1,4-naphthoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 2-hydroxy- Examples of the anthraquinone include 1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 5-hydroxy-2-methyl-1,4-naphthoquinone, 1-nitroanthraquinone, anthraquinone, 1-aminoanthraquinone, 1,2-benzoanthraquinone, 1,4-diaminoanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthraquinone, 2-methylanthraquinone, and 5,12-naphthacenequinone.

[0086] Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and piperidine 1-oxyl free radicals. oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, pyrrolidine 1-oxyl free radical compounds, and 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

[0087] Examples of phenothiazine compounds include phenothiazine, 10-methylphenothiazine, 2-methylthiophenothiazine, 2-chlorophenothiazine, 2-ethylthiophenothiazine, 2-(trifluoromethyl)phenothiazine, and 2-methoxyphenothiazine.

[0088] Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), trimethylolpropane, methylisothiazolinone ... Ethylene 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-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,1,3,5-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(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H ,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6 -ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, Examples include azine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0089] From the viewpoints of patterning properties and the residual film rate after development, the (F) photopolymerization inhibitor is particularly preferably 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-methoxyphenol, or 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0090] The photopolymerization inhibitor (F) may be used alone or in combination of two or more. The content of the photopolymerization inhibitor (F) is preferably 0.005 to 12 parts by mass per 100 parts by mass of the component (A).

[0091] (G): Adhesion Aid The photosensitive resin composition of the present embodiment may optionally contain an adhesion aid to improve adhesion between a film formed using the photosensitive resin composition and a substrate. Examples of the adhesion aid include the following: γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N- [3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and tris[3-(trimethoxysilyl)propyl] isocyanurate; silane coupling agents such as N-phenylaminopropyltrimethoxysilane; and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0092] Among these adhesion aids, from the viewpoint of adhesion, silane coupling agents are preferred, and tris[3-(trimethoxysilyl)propyl]isocyanurate is more preferred. The content of the adhesion aid (G) is preferably 0.1 to 25 parts by mass per 100 parts by mass of the component (A).

[0093] (H): Organometallic Complex The photosensitive resin composition of this embodiment may optionally contain an organometallic complex to improve the storage stability of the varnish. Examples of organometallic complexes include 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), titanium tetraisopropoxide, and titanium tetraisopropoxide diisopropoxybis(acetylacetonate). Of these organometallic complexes, titanium tetraisopropoxide or titanium tetraisopropoxide diisopropoxybis(acetylacetonate) is preferred from the viewpoint of solubility. The content of the (H) organometallic complex is preferably 0.01 to 5 parts by mass per 100 parts by mass of component (A).

[0094] (I): Plasticizer The photosensitive resin composition of this embodiment may optionally contain a plasticizer to obtain a sharp cured pattern during development. Examples of the plasticizer include polycarboxylic acid ester plasticizers, sulfonamide plasticizers, phosphate ester plasticizers, polyester plasticizers, and polyalkylene glycol plasticizers.

[0095] Specific examples of polycarboxylic acid ester plasticizers include benzoate esters such as methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, heptyl benzoate, normal octyl benzoate, nonyl benzoate, isononyl benzoate, isodecyl benzoate, 2-ethylhexyl benzoate, isodecyl benzoate, butylbenzyl benzoate, cyclopropyl benzoate, cyclobutyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, cycloheptyl benzoate, allyl benzoate, butylbenzyl benzoate, and phenyl benzoate; phthalate esters such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, diheptyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, bis(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, dicyclopropyl phthalate, dicyclobutyl phthalate, dicyclopentyl phthalate, dicyclohexyl phthalate, dicycloheptyl phthalate, diallyl phthalate, bisbutyl benzyl phthalate, and diphenyl phthalate; Trimellitic acid esters such as trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, tripentyl trimellitate, triheptyl trimellitate, tri-n-octyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, tris(2-ethylhexyl) trimellitate, triisodecyl trimellitate, trisbutylbenzyl trimellitate, tricyclopropyl trimellitate, tricyclobutyl trimellitate, tricyclopentyl trimellitate, tricyclohexyl trimellitate, tricycloheptyl trimellitate, triallyl trimellitate, trisbutylbenzyl trimellitate, and triphenyl trimellitate;adipic acid esters such as dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dipentyl adipate, diheptyl adipate, di-n-octyl adipate, dinonyl adipate, diisononyl adipate, diisodecyl adipate, bis(2-ethylhexyl) adipate, diisodecyl adipate, butylbenzyl adipate, dicyclopropyl adipate, dicyclobutyl adipate, dicyclopentyl adipate, dicyclohexyl adipate, dicycloheptyl adipate, diallyl adipate, bisbutylbenzyl adipate, and diphenyl adipate; Sebacate esters such as dimethyl sebacate, diethyl sebacate, dipropyl sebacate, dibutyl sebacate, dipentyl sebacate, diheptyl sebacate, di-n-octyl sebacate, dinonyl sebacate, diisononyl sebacate, diisodecyl sebacate, bis(2-ethylhexyl) sebacate, diisodecyl sebacate, butyl benzyl sebacate, dicyclopropyl sebacate, dicyclobutyl sebacate, dicyclopentyl sebacate, dicyclohexyl sebacate, dicycloheptyl sebacate, diallyl sebacate, bisbutyl benzyl sebacate, and diphenyl sebacate; Examples of succinic acid succinates include dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, diheptyl succinate, di-n-octyl succinate, dinonyl succinate, diisononyl succinate, diisodecyl succinate, bis(2-ethylhexyl) succinate, diisodecyl succinate, butylbenzyl succinate, dicyclopropyl succinate, dicyclobutyl succinate, dicyclopentyl succinate, dicyclohexyl succinate, dicycloheptyl succinate, diallyl succinate, bisbutylbenzyl succinate, and diphenyl succinate.

[0096] Specific examples of the sulfonamide plasticizer include aromatic sulfonamide plasticizers, and specific examples include N-butylbenzenesulfonamide, p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-ethyl-o-toluenesulfonamide, N-n-butylbenzenesulfonamide, and N-cyclohexyl-p-toluenesulfonamide.

[0097] Specific examples of the phosphate ester plasticizer include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate.

[0098] Specific examples of polyester-based plasticizers include polyesters composed of an acid component such as adipic acid, terephthalic acid, isophthalic acid, or diphenyldicarboxylic acid and a diol component such as propylene glycol, 1,3-butanediol, 1,4-butanediol, ethylene glycol, or diethylene glycol; and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

[0099] Specific examples of polyalkylene glycol plasticizers include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ethylene oxide addition polymers of bisphenols, and propylene oxide addition polymers of bisphenols; and terminal-blocking compounds such as the above-mentioned terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

[0100] Specific examples of other plasticizers include glycerin fatty acid esters such as glycerin monoacetomonolaurate, glycerin diacetomonolaurate, and glycerin monoacetomonostearate; fatty acid amides such as stearic acid amide; aliphatic carboxylic acid esters such as butyl oleate; oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate; pentaerythritol; and various sorbitols.

[0101] Among these plasticizers, polyethylene glycol dimethyl ether or pentaerythritol tetrabenzoate is preferred from the viewpoint of affinity with the polyimide or polyimide precursor. The content of the plasticizer (I) is preferably 0.1 to 30 parts by mass per 100 parts by mass of the component (A).

[0102] (J): Solvent The photosensitive resin composition of this embodiment may optionally contain a solvent. Examples of the solvent (J) include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, and γ-butyrolactone. Examples of solvents that can be used include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 3-methoxy-N,N-dimethylpropanamide, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, and mesitylene. Among these, from the viewpoints of resin solubility, resin composition stability, and adhesion to substrates, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, 3-methoxy-N,N-dimethylpropanamide, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, and 1,3-dimethyl-2-imidazolidinone are preferred.

[0103] Among these solvents, those which completely dissolve the produced polymer are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, 3-methoxy-N,N-dimethylpropanamide, tetramethylurea, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, etc. One type of solvent may be used, or two or more types of solvents may be mixed and used.

[0104] In the photosensitive resin composition of this embodiment, the amount of solvent used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, relative to 100 parts by mass of component (A).

[0105] [Method for Producing Cured Relief Pattern] One aspect of this embodiment is a method for producing a cured relief pattern, comprising the following steps: a step (step (1)) of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition of this embodiment onto the substrate, a step (step (2)) of exposing the photosensitive resin layer to light, a step (step (3)) of developing the exposed photosensitive resin layer to form a relief pattern, and a step (step (4)) of heat-treating the relief pattern to form a cured relief pattern. Some of steps (1) to (4) may be repeated.

[0106] [Step (1)] In one aspect of this step, a photosensitive resin layer is formed on a substrate by applying the photosensitive resin composition of this embodiment onto the substrate. After applying the photosensitive resin composition to the substrate, it may be dried as needed, and then a photosensitive resin layer may be formed on the substrate. From the viewpoint of the effects of the photosensitive resin composition described above, the substrate is preferably formed from copper or a copper alloy. The photosensitive resin composition is preferably one that has a Young's modulus of 4.0 GPa to 10 GPa when a cured film having a film thickness of approximately 7 μm obtained by heating at 230°C for 2 hours in a nitrogen atmosphere is subjected to a tensile test at a tensile speed of 50 mm / min. Examples of application methods include methods conventionally used for applying photosensitive resin compositions, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printer, etc., and spray application using a spray coater.

[0107] Examples of methods for drying the photosensitive resin composition include air drying, heat drying using an oven or a hot plate, and vacuum drying. Drying of the coating film is desirably carried out under conditions that do not cause imidization of the component (A) in the photosensitive resin composition. Specifically, when air drying or heat drying is carried out, drying can be carried out at a temperature of 20°C to 140°C for 1 minute to 1 hour.

[0108] [Step (2)] In one embodiment of this step, the photosensitive resin layer formed in step (1) is exposed to light. For example, the photosensitive resin layer formed in step (1) is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, a mirror projection, or a stepper, with or without a patterned photomask or reticle.

[0109] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and / or pre-development baking may be performed using any combination of temperature and time, as necessary. The baking conditions are preferably a temperature of 40 to 120°C and a time of 10 to 240 seconds. However, these may be changed as appropriate depending on the properties of the photosensitive resin composition.

[0110] [Step (3)] In one embodiment of this step, the exposed photosensitive resin layer is developed to form a relief pattern. Here, for example, unexposed portions of the exposed photosensitive resin layer are removed by development. Development methods for developing the exposed (irradiated) photosensitive resin layer include conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. Furthermore, after development, post-development baking may be performed at any temperature and time combination, as needed, for the purpose of adjusting the shape of the relief pattern. The developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of such a good solvent and a poor solvent. Examples of suitable 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 good solvent and a poor solvent are used in combination, 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. Two or more types of each solvent, for example, several types, can also be used in combination.

[0111] [Step (4)] In one embodiment of this step, the relief pattern obtained by the development is subjected to a heat treatment to form a cured relief pattern. Here, for example, the relief pattern is heated to dissolve the photosensitive component and imidize component (A), thereby converting the relief pattern into a cured relief pattern made of polyimide. Examples of heat-curing methods include those using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at a temperature of 200 to 400°C for 30 minutes to 5 hours. The atmospheric gas during heat-curing may be air or an inert gas such as nitrogen or argon.

[0112] In this embodiment, it is preferable that the cured film obtained in the heat curing step (step (4)) contains few volatile components. Specifically, the 5% thermal weight loss temperature of the cured film heat cured at 230°C for 4 hours is preferably 360°C or higher, and more preferably 380°C or higher. When the thermal weight loss temperature is 360°C or higher, defects are less likely to occur in the reflow process after the heat curing step.

[0113] Furthermore, when the photosensitive resin composition of this embodiment contains, as component (A), a polyimide precursor having a structural unit represented by general formula (1), examples of components that tend to remain in the film after heat curing include polymethacrylic acid esters and decomposition products derived from polymethacrylic acid esters. Since these components that tend to remain are detected as m / z 41 or 69 when analyzed using a GC-MS device equipped with a heating device, the temperature at which the abundance of the m / z 41 or 69 fragment detected in the film after heat curing at 230°C for 4 hours becomes 5000 or more is preferably 300°C or higher.

[0114] [Cured Film] One aspect of this embodiment is a cured film obtained by curing the photosensitive resin composition of this embodiment, and also a cured film (cured relief pattern) obtained by the above-mentioned production method (production method of cured relief pattern). Such a cured film is a cured relief pattern represented by the general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ and (C1) a radical polymerizable compound having a fluorene skeleton, and (A) a polyamic acid ester represented by the formula (1) ((A1) polyimide precursor) is converted to (A2) a polyimide structure represented by the formula (5') above by imidization.

[0115] [Semiconductor Device] One aspect of the present embodiment is a semiconductor device including a cured relief pattern obtained from the photosensitive resin composition of the present embodiment (in one aspect, a negative photosensitive resin composition). According to one aspect of the present embodiment, there is provided a semiconductor device having a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described method for producing a cured relief pattern. Furthermore, a further aspect of the present embodiment is a method for producing a semiconductor device using a semiconductor element as the substrate and including the above-described method for producing a cured relief pattern as part of the process.

[0116] The cured relief pattern formed by the above-described method for producing a cured relief pattern can be formed as: a surface protective film for electronic components, an interlayer insulating film, an insulating film for rewiring, and a protective film for flip-chip devices; a protective film for a semiconductor device having a bump structure; or the like, and then combined with a known method for producing a semiconductor device, to produce the semiconductor device of this embodiment.

[0117] The photosensitive resin composition of this embodiment is useful not only for application to semiconductor devices but also for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[0118] Other Embodiments Although the present embodiment has been described above, aspects of the present invention are not limited to the above-described first embodiment.

[0119] Another aspect of this embodiment is a compound represented by the following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２and (C) a radical polymerizable compound, wherein the negative photosensitive resin composition is spin-coated onto a wafer to a thickness of 10 μm, heated at 110° C. for 240 seconds, and then subjected to irradiation with 500 mJ / cm 2 ２ The negative photosensitive resin composition is a cured film obtained by exposing a film to i-rays and then curing the film at 230°C for 4 hours. The cured film is cut into 5 mm square pieces and subjected to thermal evolved gas mass spectrometry at a heating rate of 10°C / min. In each mass spectrum obtained by scan mode analysis, the total fragment count (TIC), obtained by adding up all m / z signals, is detected at an abundance of 200,000 or higher at a temperature of 300°C or higher.

[0120] Another aspect of this embodiment is a compound represented by the following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ and (C) a radical polymerizable compound, wherein the negative photosensitive resin composition is spin-coated onto a wafer to a thickness of 10 μm, heated at 110° C. for 240 seconds, and then subjected to irradiation with 500 mJ / cm 2 ２ and then cured at 230°C for 4 hours. The cured film is cut into 5 mm square pieces and subjected to thermal evolved gas mass spectrometry at a heating rate of 10°C / min. The temperature at which a fragment having m / z of 41 or 69 is detected with an abundance of 5,000 or more is 300°C or higher.

[0121] Furthermore, another aspect of this embodiment is a compound represented by general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ and (C) a radical-polymerizable compound, wherein the component (C) contains (C1) a compound having a fluorene skeleton, and the negative-type photosensitive resin composition is spin-coated onto a wafer to a thickness of 10 μm, heated at 110° C. for 240 seconds, and then subjected to irradiation with 500 mJ / cm 2 of fluorene. ２ The negative photosensitive resin composition has a 5% thermal weight loss temperature of 360°C or higher when exposed to i-rays and cured at 230°C for 4 hours.

[0122] Any of the above photosensitive resin compositions can achieve the following (1) and (2): (1) a resin film having good patterning properties can be produced; and (2) a resin film having high thermal stability (i.e., no defects occur in a heating step such as reflow, and no defects occur in a reliability test such as HAST) can be produced.

[0123] The preferred aspects described in Embodiment 1 may also be preferred in the photosensitive resin compositions of the above [Other Embodiments]. The optional components, cured film (cured relief pattern), method for producing a cured relief pattern, semiconductor device, and the like described in Embodiment 1 may also be referred to in the photosensitive resin compositions of the above [Other Embodiments].

[0124] The present embodiment will be described in detail below using examples. However, the present embodiment is not limited to the following examples. Regarding the examples, comparative examples, and production examples, the physical properties of the polymer and photosensitive resin composition were measured and evaluated according to the following methods.

[0125] [Measurement and Evaluation] (1) Molecular Weight The weight average molecular weight (Mw) of the polymer was measured by gel permeation chromatography (standard polystyrene equivalent) under the following conditions. The column used for the measurement was a "Shodex 805M / 806M series" manufactured by Resonaq, and standard monodisperse polystyrene was selected for the measurement. N-methyl-2-pyrrolidone (NMP) was used as the developing solvent, and a "Shodex RI-930" manufactured by Resonaq was used as the detector.

[0126] (2) Patterning of Cured Relief Patterns A photosensitive resin composition prepared by the method described below was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation) to deposit 200 nm thick Ti and 400 nm thick Cu, in that order. Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto this wafer using a coater developer (D-Spin 60A model, manufactured by SOKUDO Co., Ltd.), and then heated and dried on a hot plate at 110°C for 4 minutes to form a photosensitive resin layer approximately 8 μm thick. Using a test pattern mask, this photosensitive resin layer was subjected to 600 mJ / cm irradiation using a Prisma GHI (manufactured by Ultratech Co., Ltd.) equipped with an i-line filter. ２ The photosensitive resin layer was then spray-developed using cyclopentanone as a developer with a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation), and then rinsed with propylene glycol methyl ether acetate, to obtain a relief pattern of the photosensitive resin layer on the Cu. The wafer on which the relief pattern was formed on the Cu was then heat-treated in a temperature-programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg) at 280°C for 2 hours in a nitrogen atmosphere, to obtain a cured relief pattern of resin approximately 5 μm thick on the Cu.

[0127] The prepared cured relief pattern was observed under an optical microscope, and the size of the minimum opening pattern was determined. If the area of ​​the opening in the obtained pattern was at least half the area of ​​the corresponding pattern mask opening, it was considered resolved. The resolution was evaluated based on the length of the mask opening side (opening pattern size) corresponding to the smallest area among the resolved openings, using the following evaluation criteria: (Evaluation Criteria) S (Excellent): The minimum opening pattern size was less than 5 μm. A (Good): The minimum opening pattern size was 5 μm or more but less than 6 μm. B (Fair): The minimum opening pattern size was 6 μm or more but less than 7 μm. C (Unacceptable): The minimum opening pattern size was 7 μm or more.

[0128] (3) Adhesion to Copper Substrate After Reliability Test A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti film and a 400 nm thick Cu film in that order using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto this wafer using a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation), and then pre-baked on a hot plate at 110°C for 240 seconds, thereby forming a coating film with a thickness of 10 μm on the Cu. This coating film was then irradiated with i-line at 500 mJ / cm using an AP-200 (manufactured by Ultratech Corporation) without using a test pattern mask. ２ was irradiated with energy of

[0129] Next, the substrate was heated at 230°C for 4 hours in a temperature-rising programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.) in a nitrogen atmosphere to obtain a cured resin coating film of the resin composition having a thickness of approximately 7 µm on the Cu.

[0130] The resulting cured resin coating film was placed in a highly accelerated life testing apparatus (HASTEST PC-R8D, manufactured by Hirayama Manufacturing Co., Ltd.) and treated for 168 hours at a temperature of 130°C and a relative humidity of 85%. After treatment, the cured film was removed, and the adhesion properties between the copper substrate and the cured resin coating film were evaluated according to the cross-cut method of JIS K 5600-5-6 standard, based on the following criteria: S (Excellent): The lattice number of the cured resin coating film adhered to the copper substrate was greater than 100. A (Good): The lattice number of the cured resin coating film adhered to the copper substrate was 80 or more and 100 or less. B (Fair): The lattice number of the cured resin coating film adhered to the copper substrate was 50 or more and less than 80. C (Unacceptable): The lattice number of the cured resin coating film adhered to the copper substrate was less than 50.

[0131] (4) Thermal Weight Loss Temperature of Cured Film A cured resin coating film was obtained in the same manner as in (3). The coating film was then scraped off, and using a thermogravimetric analyzer (Shimadzu Corporation, TGA-50), the temperature was increased from room temperature at 10°C / min with nitrogen gas flowing at 50 mL / min. The temperature at which the mass of the cured film decreased by 5% (5% weight loss temperature) was measured, with the mass of the cured film at 230°C being taken as 100%. The thermal weight loss temperatures of the cured films were evaluated based on the following criteria: S (Excellent): The 5% weight loss temperature was 380°C or higher. A (Good): The 5% weight loss temperature was 360°C or higher but less than 380°C. B (Fair): The 5% weight loss temperature was 340°C or higher but less than 360°C. C (Unacceptable): The 5% weight loss temperature was less than 340°C.

[0132] (5) Peeling of copper pillars during reflow A 2000 angstrom thick chromium layer was formed on a 5-inch silicon wafer using a sputtering device manufactured by Canon Anelva Corporation, and then a 2000 angstrom thick copper layer was formed on the chromium layer. Here, a photosensitive resin laminate having a 16 μm thick polyethylene terephthalate film (support film), a 30 μm thick photosensitive resin layer, and a 23 μm thick polyethylene film (protective film) was prepared. Using an Asahi Kasei Corporation laminator AL-70, the photosensitive resin laminate was laminated so that the surface of the photosensitive resin layer was in close contact with the copper layer of the silicon wafer while peeling off the protective film. The lamination was performed at a roll temperature of 100°C and an air pressure of 3 kg / cm. ２ A 100 μm square lattice mask was placed on the silicon wafer on which the photosensitive resin laminate was laminated, and the wafer was exposed to 200 mJ / cm 2 using a parallel light exposure machine HMW-801 manufactured by Oak Corporation. ２ It was exposed with.

[0133] After peeling off the support film, the wafer was sprayed with a 1% by mass aqueous solution of sodium carbonate at 30°C for 120 seconds, and the unexposed portions of the photosensitive resin layer were developed and removed, thereby forming a resist pattern with 100 μm square depressions across the entire surface. The silicon wafer with the resist pattern formed was degreased by immersing it in an acid cleaner (FRX manufactured by Atotech Japan) at 30°C for 3 minutes, and then electrolytic solder plating was performed for 3 hours in a solder plating solution (Plutin LA fluoroborate solder bath manufactured by Meltex). The current density was 1.5 A / dm ２ The plated silicon wafer was immersed in a 3% by mass aqueous solution of sodium hydroxide at 50°C for 10 minutes to remove the resist pattern, thereby producing a silicon wafer having copper pillars. The plating height was in the range of 20±5 μm.

[0134] The photosensitive resin compositions prepared in the examples and comparative examples were applied to the silicon wafers having copper pillars prepared above using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) so that the final film thickness was approximately 30 μm, and then cured at 230 ° C. for 4 hours. Under simulated solder reflow conditions using a mesh belt continuous firing furnace (manufactured by Koyo Thermo Systems Co., Ltd., model name 6841-20AMC-36), the silicon wafers having cured films and copper pillars were subjected to reflow (260 ° C., 3 minutes). The cross section of the silicon wafer having cured films and copper pillars was cut using an FIB device (manufactured by JEOL Ltd., JIB-4000) at an acceleration voltage of 30 kV and an Ie value of 1 nA, and the degree of peeling between the copper pillar and cured film portions was observed. Copper pillar peeling during reflow was evaluated based on the following criteria. Peeling between the copper pillar portion and the cured film portion refers to the portion where the interface between the copper pillar and the cured film is exposed across the entire cross section of the silicon wafer having the cured film and copper pillar. (Evaluation Criteria) A (Good): No peeling between the copper pillar portion and the cured film portion was observed. B (Acceptable): Peeling between the copper pillar portion and the cured film portion was 1 / 10 or less of the entire cross section of the silicon wafer having the cured film and copper pillar. C (Unacceptable): Peeling between the copper pillar portion and the cured film portion was more than 1 / 10 of the entire cross section of the silicon wafer having the cured film and copper pillar.

[0135] (6) Stability of Varnish over Time A photosensitive resin composition was prepared as described below, and after leaving to stand at room temperature for 14 days, its viscosity was measured at 23°C using an E-type viscometer (Viscomate VM-150III manufactured by Toki Sangyo Co., Ltd.). This initial viscosity was designated as viscosity 1. After the initial viscosity measurement, the photosensitive resin composition was stored at 40°C for 3 days, and the viscosity was measured again under the same conditions. The viscosity after this storage was designated as viscosity 2. Using these viscosities, the stability of the varnish over time was calculated using the following formula: Viscosity change rate (%) = (|viscosity 2 - viscosity 1| / viscosity 1) × 100. The stability of the varnish over time was evaluated based on the following criteria. (Evaluation criteria) S (Excellent): The viscosity change rate was less than 3%. A (Good): The viscosity change rate was 3% or more but less than 5%.

[0136] (7) Thermally evolved gas mass spectrometry (TPD-MS) A cured resin coating film obtained by the same method as in (3) was cut into a 5 mm square sample and placed in a container. The sample was heated from room temperature to 400°C at a heating rate of 10°C / min while helium gas was flowing through the sample at a rate of 50 ml / min. The amount of gas evolved was quantified using a mass spectrometer, and the amount of volatile components per cured resin coating film was calculated. A GS-MS instrument (Shimadzu Corporation, QP2010Ultra) equipped with a heating device was used for the measurement. Based on the calculated amount of volatile components, the temperature was plotted on the horizontal axis and the abundance of each fragment on the vertical axis. The temperature (°C) at which a fragment with m / z of 41 or 69 was detected at an abundance of 5,000 or more, and the temperature (°C) at which the total of fragments with m / z of 10 to 600 (TIC; Total Ion Chromatogram) was detected at an abundance of 200,000 were determined.

[0137] [Production Examples, Examples, and Comparative Examples] <Production Example 1> (Synthesis of Polymer A-1) 155 g (0.5 mol) of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, and 135 g (1.04 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were mixed and stirred at room temperature. 79.1 g of pyridine was further mixed while stirring, and the mixture was stirred for 16 hours.

[0138] Next, under ice cooling, a solution of 203 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 ml of γ-butyrolactone was mixed into the mixture over a period of 40 minutes with stirring, followed by a suspension of 89 g (0.44 mol) of diaminodiphenyl ether (DADPE) in 280 ml of γ-butyrolactone, which was further mixed over a period of 60 minutes with stirring. After stirring the mixture at room temperature for 4 hours, 40 ml of ethyl alcohol was added and stirred for 1 hour, and then 1 liter of γ-butyrolactone was added. The precipitate that formed in the mixture was removed by filtration to obtain a reaction solution.

[0139] The resulting reaction solution was added to 4 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 30 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdery polymer (Polymer A-1). The molecular weight of Polymer A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 24,000.

[0140] <Production Example 2> (Synthesis of Polymer A-2) Polymer A-2 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 147 g (0.5 mol) of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA) was used instead of 155 g of ODPA in Production Example 1. The molecular weight of Polymer A-2 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 20,000.

[0141] <Production Example 3> (Synthesis of Polymer A-3) Polymer A-3 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 94 g (0.44 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) was used instead of 89 g of DADPE in Production Example 1. The molecular weight of Polymer A-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 26,000.

[0142] <Production Example 4> (Synthesis of Polymer A-4) Polymer A-4 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, except that 46 g (0.44 mol) of p-phenylenediamine was used instead of 89 g of DADPE in Production Example 1. The molecular weight of Polymer A-4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 19,000.

[0143] <Production Example 5> (Synthesis of Polymer A-5) Polymer A-5 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, except that 94 g (0.44 mol) of m-TB was used instead of 89 g of DADPE used in Production Example 2. The molecular weight of Polymer A-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 25,000.

[0144] <Production Example 6> (Synthesis of Polymer A-6) Polymer A-6 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, except that 176 g (0.44 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 89 g of DADPE in Production Example 1. The molecular weight of Polymer A-6 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 25,000.

[0145] <Production Example 7> (Synthesis of Polymer A-7) Polymer A-7 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 3, except that 223 g (0.44 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA) was used instead of 155 g of ODPA in Production Example 3. The molecular weight of Polymer A-7 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 25,000.

[0146] <Production Example 8> (Synthesis of Polymer A-8) Polymer A-8 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 124 g (0.4 mol) of ODPA and 29 g (0.1 mol) of BPDA were used instead of the 155 g of ODPA in Production Example 1. The molecular weight of Polymer A-8 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

[0147] <Production Example 9> (Synthesis of Polymer A-9) Polymer A-9 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 62 g (0.2 mol) of ODPA and 65 g (0.3 mol) of pyromellitic dianhydride (PMDA) were used instead of the 155 g of ODPA in Production Example 1, and 94 g (0.44 mol) of m-TB was used instead of the 89 g of DADPE. The molecular weight of Polymer A-9 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

[0148] <Production Example 10> (Synthesis of Polymer A-10) Polymer A-10 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 8, except that 94 g (0.44 mol) of m-TB was used instead of 89 g of DADPE in Production Example 8. The molecular weight of Polymer A-10 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0149] <Production Example 11> (Synthesis of Polymer A-11) Polymer A-11 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, except that 144 g (0.44 mol) of TFMB was used instead of 89 g of DADPE in Production Example 1. The molecular weight of Polymer A-11 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 30,000.

[0150] <Production Example 1C> (Synthesis of Radical Polymerizable Compound C-1) 1.0 mol of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) was charged with 187.4 g (2.6 mol) of acrylic acid, 23.8 g (0.13 mol) of p-toluenesulfonic acid, 876 g of toluene, and 2.1 g of methoquinone, and the reaction mixture was equipped with a stirrer, thermometer, condenser, and water divider. Subsequently, a dehydration esterification reaction was carried out for 3.3 hours while refluxing at 110 to 120°C. Subsequently, the reaction solution was neutralized with 10% by weight caustic soda, washed with 20% by weight saline, dried over magnesium sulfate, filtered, and 2.1 g of methoquinone was added. The toluene was removed by vacuum concentration, yielding 501 g of the target radical polymerizable compound C-1. The radical polymerizable compound C-1 is a compound having a structure represented by the general formula (3) above. Furthermore, C-1 is a compound in which the definitions in formula (3) are p1+p2=2 (p1 and p2 are 1), k1=k2=1, and n1=n2=m1=m2=0.

[0151] Production Example 2C (Synthesis of Radical Polymerizable Compound C-2) 1.0 mol of BPEF was reacted with 11 mol of ethylene oxide (EO) to obtain an EO addition product. From the hydroxyl value of the obtained product, it was confirmed that the compound was a compound in which 10.0 mol of EO was added to 1.0 mol of BPEF, that is, a compound in which 12.0 mol of EO was added to 1 mol of 9,9-(4-hydroxyphenyl)fluorene (BPF) (a compound in which the average value of p1 + p2 in the general formula (3) is 12.0).

[0152] To 1.0 mol of the EO addition product obtained above, 187.4 g (2.6 mol), 23.8 g (0.13 mol), p-toluenesulfonic acid, 876 g, and 2.1 g of methoquinone were charged, and the reactor was equipped with a stirrer, thermometer, condenser, and water divider. Subsequently, a dehydration esterification reaction was carried out for 3.3 hours while refluxing at 110 to 120°C. Subsequently, the reaction solution was neutralized with 10% by weight caustic soda, washed with 20% by weight saline, dried over magnesium sulfate, filtered, and 2.1 g of methoquinone was added. The toluene was removed by concentration under reduced pressure, yielding 920 g of the target radical polymerizable compound C-2. Radical polymerizable compound C-2 is a compound having a structure represented by the general formula (3) above. Furthermore, C-2 is defined as p1+p2=12 (p1 is 6, p2 is 6) in the general formula (3), k1=k2=1, and n1=n2=m1=m2=0.

[0153] Production Example 3C (Synthesis of Radical Polymerizable Compound C-3) 1.0 mol of BPEF was reacted with 4.0 mol of ethylene oxide (EO) to obtain an EO addition product. From the hydroxyl value of the obtained product, it was confirmed that the compound was a compound in which 3.0 mol of EO was added to 1.0 mol of BPEF, that is, a compound in which 5.0 mol of EO was added to 1 mol of 9,9-(4-hydroxyphenyl)fluorene (BPF) (a compound in which the average value of p1 + p2 in the general formula (3) is 5.0).

[0154] To 0.08 mol of the EO addition product obtained above, 74 g (0.8 mol) of epichlorohydrin and 0.8 g (0.0051 mol) of tetramethylammonium bromide (TMAB) were added. The system was purged with nitrogen, heated to approximately 50°C, and the components were mixed. Then, 9.6 g (0.24 mol) of flaky sodium hydroxide was added over 1 hour or more. After the addition was completed, the system was purged with nitrogen again, and the reaction was carried out at 60°C for 9 hours. The disappearance of the raw material compound was confirmed by high-performance liquid chromatography (HPLC). After the reaction was completed, epichlorohydrin was removed under reduced pressure at 60°C, and 130 g of toluene was added while heating to 60 to 80°C. The resulting mixture was suction filtered to remove the by-product (NaCl), and the residue was washed with toluene. To promote the ring-closure reaction to form epoxy groups, 53 g of a 30 wt % aqueous solution of sodium hydroxide was added dropwise to the filtrate, followed by stirring for 1 hour at 70°C under a nitrogen atmosphere. Then, 260 g of toluene was added to the resulting mixture, followed by extraction and washing 5 to 6 times with distilled water at an extraction temperature of 60 to 80°C. After dehydration, the mixture was concentrated at 90°C and dried under reduced pressure to obtain a glycidyl ether of 5.0 EO-added BPEF.

[0155] The above 5.0EO-added BPEF glycidyl ether (200 g), acrylic acid (45.0 g), methyl isobutyl ketone (hereinafter, MIBK) (31.2 g), and methoquinone (2.2 g) were added to a three-neck flask equipped with a Dean-Stark tube. The system was purged with nitrogen and heated to 50°C to dissolve the reagents. Thereafter, flake-shaped tetramethylammonium bromide (0.4 g) was added, and after purging with nitrogen again, the reaction was carried out for 9 hours while stirring under reflux. After completion of the reaction, the reaction solution was subjected to suction filtration, and the filtrate was concentrated and dried to obtain the desired radical polymerizable compound C-3.

[0156] <Components (B) and (D) to (J)> In the table, the following symbols respectively represent the following compounds.

[0157]

[0158] C-1: Compound synthesized in Production Example 1C C-2: Compound synthesized in Production Example 2C C-3: Compound synthesized in Production Example 3C C-4: Tris-(2-acryloxyethyl) isocyanurate: A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) C-5: Polyethylene glycol dimethacrylate: NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0159] D-1: p-toluenesulfonic acid D-2: mandelic acid D-3: diethylenetriaminepentaacetic acid

[0160] E-1: 2-acetamido-6-hydroxypurine E-2: 1H-tetrazole-5-acetic acid E-3: tetra-2-pyridinylpyrazine

[0161] F-1: p-Methoxyphenol F-2: The following structure: A compound represented by

[0162] G-1: Silane coupling agent (KBM-573, manufactured by Shin-Etsu Silicones Co., Ltd.) G-2: Tris[3-(trimethoxysilyl)propyl] isocyanurate

[0163] H-1: Titanium tetraisopropoxide H-2: Titanium tetraisopropoxide diisopropoxybis(acetylacetonate)

[0164] I-1: Polyethylene glycol dimethyl ether I-2: Pentaerythritol tetrabenzoate

[0165] J-1: N-ethyl-2-pyrrolidone J-2: γ-butyrolactone J-3: dimethyl sulfoxide J-4: 3-methoxy-N,N-dimethylpropanamide J-5: 1,3-dimethyl-2-imidazolidinone J-6: ethyl lactate

[0166] Example 1 100 g of polymer A-1 as component (A), 4.0 g of photopolymerization initiator B-1 as component (B), 20.0 g of radical polymerizable compound C-1 as component (C), 1.0 g of rust inhibitor E-1 as component (E), 0.5 g of photopolymerization inhibitor F-1 as component (F), and 0.5 g of adhesion aid G-1 as component (G) were mixed with 320 g of solvent J-2 (γ-butyrolactone) and 80 g of solvent J-3 (dimethyl sulfoxide). The viscosity of the resulting solution was adjusted to about 4.0 Pa s by further adding a small amount of the solvent, and a photosensitive resin composition was obtained.

[0167] <Examples 2 to 34 and Comparative Examples 1 to 4> As shown in the table below, the types and blending ratios of each component were changed, and photosensitive resin compositions were prepared in the same manner as in Example 1, and evaluations were performed in the same manner as in Example 1.

[0168] In addition, in the other examples including Example 1, it was confirmed that semiconductor devices could be fabricated using the cured relief patterns obtained from those photosensitive resin compositions as interlayer insulating films, and that these operated without any problems.

[0169]

[0170]

[0171]

[0172]

Claims

The following components (A) to (C): (A) a polyimide precursor and / or a polyimide; (B) a photopolymerization initiator, and (C) Radical polymerizable compound Including, the component (C) includes (C1) a compound having a fluorene skeleton, a negative photosensitive resin composition in which the mass ratio of the compound (C1) having a molecular weight of 370 or more and less than 3,000, excluding the compound having a fluorene skeleton, is 2.4 mass% or less, based on the total mass of the solid content. 　 The component (A) is a compound represented by the following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ cannot be hydrogen atoms at the same time.) 2. The negative photosensitive resin composition according to claim 1, which is a polyimide precursor having a structural unit represented by the following formula: 　 In the general formula (1), R １ , and R ２ At least one of the following general formula (2): (In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ , and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. The negative photosensitive resin composition according to claim 2, wherein the aryl group is a group represented by the formula:

3. The negative photosensitive resin composition according to claim 1, wherein the compound (C1) having a fluorene skeleton has at least two radically polymerizable groups. 　 The compound (C1) having a fluorene skeleton is represented by the following general formula (3): (In the formula, R ａ ~R ｄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, an amino group, or an aryl group, and R ｅ is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ｆ is a hydrogen atom or a methyl group, k1 and k2 are each independently an integer of 1 to 5, n1 and n2 are each independently an integer of 0 to 4, m1 and m2 are each independently an integer of 0 to 5, p1 and p2 are each independently an integer of 0 or greater, and k1+n1≦5 and k2+n2≦5. The negative photosensitive resin composition according to claim 1 or 2, having a structure represented by the following formula:

6. The negative photosensitive resin composition according to claim 5, wherein in the general formula (3), p1 and p2 each independently represent an integer of 2 or more.

3. The negative photosensitive resin composition according to claim 2, wherein the fluorine atom content per molecular weight of the structural unit represented by general formula (1), expressed as (the number of fluorine atoms contained in the structural unit represented by general formula (1) × the atomic weight of the fluorine atoms) / (the molecular weight of the structural unit represented by general formula (1)), is 13% or less. 　 Y in the general formula (1) １ In the formula (5): (In the formula, RF １ , and RF ２ each independently represents a fluorine atom or a trifluoromethyl group.

3. The negative photosensitive resin composition according to claim 1, wherein the content of units represented by the following formula (I) is less than 1 mmol%.

3. The negative photosensitive resin composition according to claim 1, wherein a mass ratio of the compound (C1) having a molecular weight of 370 or more and less than 3,000, excluding the compound having a fluorene skeleton, is 1.8 mass% or less, relative to the total mass of the solid content. 　 The R １ and R ２ The negative photosensitive resin composition according to claim 3, wherein the proportion of groups represented by the general formula (2) is 70 mol % or more.

3. The negative photosensitive resin composition according to claim 1, further comprising at least one radical polymerizable compound (C2) that does not have a fluorene skeleton. 　 The negative photosensitive resin composition according to claim 11, wherein the radical polymerizable compound (C2) having no fluorene skeleton has an isocyanuric skeleton.

13. The negative photosensitive resin composition according to claim 12, comprising 1 to 30 parts by mass of the radical polymerizable compound (C2) having an isocyanuric skeleton and not having a fluorene skeleton, relative to 100 parts by mass of the component (A). 　 The negative photosensitive resin composition according to claim 1 or 2, further comprising (D) an acidic compound. 　 In the general formula (1), X １ is represented by the following general formulas (6) to (9): (In the formula, R ６ , R ７ , and R ８ are each independently an oxygen atom, a sulfur atom, or a divalent organic group, and R ９ , and R １０ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R ９ , and R １０ may be the same or different from each other.) The negative photosensitive resin composition according to claim 2, wherein the aryl group is at least one group selected from the group consisting of: 　 In the general formula (1), Y １ is represented by the following general formulas (10) to (13): (In the formula, R １４ , R １５ , R １６ , and R １７ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R １４ , R １５ , R １６ , and R １７ may be the same or different from each other.) (In the formula, R １８ ~R ２５ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R １８ ~R ２５ may be the same or different from each other, and R ２６ is a divalent group. (In the formula, R ２７ , and R ２８ are each independently a divalent group, and R ２９ , and R ３０ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and R ２９ , and R ３０ may be the same or different from each other.) The photosensitive resin composition according to claim 2, wherein the aryl group is at least one group selected from the group consisting of: 　 The component (B) is represented by the following general formula (14) or (15): {In the formula, R ９ is a phenyl group, a tolyl group, or an alkyl group having 1 to 12 carbon atoms, and R １０ is a phenyl group, a tolyl group, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 1 to 5 carbon atoms, and R １１ is a hydrogen atom or a carboxyl group (—COOH). (In the formula, R １２ is a hydrogen atom, an alkyl ester, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. The negative photosensitive resin composition according to claim 1 or 2, having a structure represented by the following formula: 　 The following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ cannot be simultaneously hydrogen atoms.] (A) a polyamic acid ester represented by the formula: (B) a photopolymerization initiator; and (C) Radical polymerizable compound A negative photosensitive resin composition comprising: The negative photosensitive resin composition was spin-coated onto a wafer to a thickness of 10 μm, and after heating at 110° C. for 240 seconds, 500 mJ / cm ２ and then curing the cured film at 230°C for 4 hours. The cured film is cut into 5 mm square pieces and subjected to thermal evolved gas mass spectrometry at a heating rate of 10°C / min. In each mass spectrum obtained by scan mode analysis, the total fragment count (TIC) obtained by adding up all m / z signals is detected at an abundance of 200,000 or more at a temperature of 300°C or higher. 　 The following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ cannot be hydrogen atoms at the same time.) (A) a polyamic acid ester represented by the formula: (B) a photopolymerization initiator; and (C) Radical polymerizable compound A negative photosensitive resin composition comprising: The negative photosensitive resin composition was spin-coated onto a wafer to a thickness of 10 μm, and after heating at 110° C. for 240 seconds, 500 mJ / cm ２ and then curing the cured film at 230°C for 4 hours. The cured film is cut into 5 mm square pieces and subjected to thermal evolved gas mass spectrometry at a heating rate of 10°C / min. The temperature at which a fragment having m / z of 41 or 69 is detected with an abundance of 5000 or more is 300°C or higher. 　 The following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ cannot be hydrogen atoms at the same time.) (A) a polyamic acid ester represented by the formula: (B) a photopolymerization initiator, and (C) Radical polymerizable compound A negative photosensitive resin composition comprising: the component (C) includes (C1) a compound having a fluorene skeleton, The negative photosensitive resin composition was spin-coated onto a wafer to a thickness of 10 μm, and after heating at 110° C. for 240 seconds, 500 mJ / cm ２ a cured film having a 5% thermal weight loss temperature of 360°C or higher after exposure to i-rays and curing at 230°C for 4 hours; 　 The following general formula (1): (In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ , and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ , and R ２ cannot be hydrogen atoms at the same time.) (A) a polyamic acid ester represented by the formula: (B) a photopolymerization initiator; and (C1) Radical polymerizable compound having a fluorene skeleton A cured film obtained by curing a photosensitive resin composition comprising the compound (I) and having a 5% thermal weight loss temperature of 360°C or higher. 　 A step of forming a photosensitive resin layer on a substrate by applying the negative photosensitive resin composition according to claim 1 or 2 onto the substrate; exposing the photosensitive resin layer to light; developing the exposed photosensitive resin layer to form a relief pattern; forming a hardened relief pattern by heat treating the relief pattern; 1. A method for producing a cured relief pattern, comprising: 　 A semiconductor device comprising a cured relief pattern formed using the negative photosensitive resin composition according to claim 1 or 2.

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