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

Abstract

The present disclosure relates to a photosensitive resin composition and the like.　A negative-type photosensitive resin composition according to the present invention includes (A) a polyimide, (B) a solvent, and (C) a photopolymerization initiator. The (A) polyimide has a structure represented by general formula (1) and does not have a polymerizable functional group at a side chain. The product (Mw×R(FCont.)) of the weight average molecular weight (Mw) of the (A) polyimide and R as calculated from expression (b) satisfies expression (a). (b): R(FCont.)=(Mwf+1) / (Mwx+MwY-36) (in which Mwf is the total mass of the fluorine atoms that may be included in the (A) polyimide, MwX is the molecular weight of the tetracarboxylic acid dianhydride that constitutes the (A) polyimide, and MwY is the molecular weight of the diamine that constitutes the (A) polyimide). (a): 300≤Mw×R≤948.

Description

[Technical Field]

[0001] This disclosure relates to a photosensitive resin composition, a method for producing a cured relief pattern, and a cured film. [Background technology]

[0002] Conventionally, resins advantageous in terms of heat resistance, electrical properties, and mechanical properties (e.g., polyimide, polybenzoxazole, and phenolic resins) have been used as insulating materials for electronic components, as well as for passivation films, surface protective films, and interlayer insulating films of semiconductor devices. Among these, those provided in the form of photosensitive resin compositions allow for easy formation of relief patterns through coating, exposure, development, and ring-closing treatment by curing (e.g., imidization and benzoxazoleization), as well as thermal crosslinking in the composition. For this reason, such compositions have the advantage of significantly shortening the manufacturing process compared to non-photosensitive compositions, and are therefore suitably used in the fabrication of semiconductor devices.

[0003] Semiconductor devices (hereinafter sometimes simply referred to as "devices") are mounted on printed circuit boards in various ways depending on their purpose. Conventional devices were often manufactured using the wire bonding method, in which thin wires are connected from the device's external terminals (pads) to the lead frame. However, with the increasing speed of devices and the current situation where their operating frequencies reach the GHz level, differences in the wiring length (wiring distance) of each terminal during mounting have come to affect the operation of the device. Therefore, in mounting devices for high-end applications, it is necessary to precisely control the length of the mounting wiring, but the wire bonding method has found it difficult to meet this requirement.

[0004] Therefore, flip-chip mounting has been proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on it, and then the chip is flipped over and directly mounted on a printed circuit board. With this flip-chip mounting, the wiring distance can be precisely controlled, so it is sometimes used in high-end devices that handle high-speed signals, or in mobile phones and the like due to its compact mounting size, and demand for it is rapidly expanding. Recently, fan-out wafer-level packaging (FOWLP) has been proposed, in which individual chips manufactured by dicing a wafer that has undergone the previous process are placed on a support, sealed with molding resin, and then the support is peeled off and a redistribution layer is formed thereon (see, for example, Patent Document 1). FOWLP is advantageous for thinning the redistribution layer, and therefore for thinning the package, and also has many advantages from the viewpoint of high-speed transmission and cost reduction.

[0005] On the other hand, in FOWLP, the redistribution layer is often multilayered. Therefore, it has been pointed out that if the flatness of the photosensitive resin composition in the photolithography process, especially the flatness of the pre-baked film (pre-baked film) when it is pre-baked, is poor, it is easy for the depth of focus of the exposure light in the subsequent exposure process to shift, and the resolution tends to deteriorate. For this reason, the photosensitive resin composition is required to be able to realize a pre-baked film with high flatness, for example.

[0006] Furthermore, due to the structure of semiconductor packages, the wiring and the redistribution layer come into contact. The photosensitive resin composition is required to have good adhesion to metal (for example, copper if the wiring is copper wiring) and high reliability under harsh environments of high temperature and high humidity (for example, it is required to be resistant to elongation reduction and to have low ion migration).

[0007] For planarization of the rewiring layer, it is advantageous to have film flatness (in-plane uniformity) and suppression of film shrinkage that may occur during heating (curing). As methods advantageous for improving film flatness, for example, using a polyimide precursor highly soluble in a solvent and using a low molecular weight polymer are known. Also, in order to suppress the film shrinkage amount during heating, it is known that it is advantageous to use a polyimide having a closed-ring structure to form a resin composition.

[0008] For example, Patent Document 1 discloses a technique of forming a photosensitive resin composition using a polyimide precursor with a low molecular weight {for example, a weight average molecular weight (Mw) of 3,000 or more and 13,000 or less} and attempting to improve the flatness of the film. Patent Document 2 discloses a technique of using a polyfunctional (meth)acrylate compound and attempting to suppress film shrinkage during curing.

[0009] Also, as a method advantageous for improving adhesion to copper, it is known to form a photosensitive resin composition using a heterocyclic compound. For example, in Patent Document 3, a technique of attempting to improve adhesion to a substrate by forming a photosensitive resin composition using a compound having a reactive group such as an epoxy group and having a nitrogen-containing heterocyclic group which is a 5-membered ring is disclosed.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0011] However, from the standpoint of achieving a pre-baked film with excellent flatness, and from the standpoint of achieving a cured film (cured relief pattern) that can suppress changes in film thickness before and after curing, has excellent adhesion to metal wiring, and achieves low oxygen permeability, the photosensitive resin compositions described in Patent Documents 1 to 3 had room for improvement.

[0012] Therefore, the object of this disclosure is to provide a photosensitive resin composition that can realize a pre-baked film with excellent flatness, suppress changes in film thickness before and after curing, have excellent adhesion to metal wiring, and achieve low oxygen permeability in a cured film (cured relief pattern). Furthermore, an object of this disclosure is to provide a method for manufacturing a cured relief pattern and a cured film realized using such a photosensitive resin composition. [Means for solving the problem]

[0013] One aspect of the present invention is as follows: [1] (A) Polyimide, (B) Solvent, and (C) Photopolymerization initiator A negative-type photosensitive resin composition comprising, The aforementioned (A) polyimide is given by the following general formula (1): [ka] {In the formula, n is a positive integer, X is a tetravalent group with 6 to 31 carbon atoms, and Y is a divalent group.} It has a structure represented by and The (A) polyimide mentioned above does not have polymerizable functional groups in its side chains. The weight-average molecular weight (Mw) of the polyimide (A) mentioned above, The following formula (b): R(F Cont. ) = (Mw f (+1) / (Mw x +Mw Y -36)···(b) (In the formula, Mwf The total mass of fluorine atoms that may be contained in the (A) polyimide, Mw X The molecular weight of the tetracarboxylic dianhydride constituting the (A) polyimide is Mw Y (This is the molecular weight of the diamine constituting the polyimide (A) mentioned above.) The product of R calculated by and {Mw × R(F Cont. )} is expressed in the following equation (a): 300 ≤ Mw × R ≤ 948 ···(a) A photosensitive resin composition that satisfies the following conditions. [2] The photosensitive resin composition according to item 1, wherein the weight-average molecular weight of the (A) polyimide is 8,000 or more and 23,000 or less. [3] Furthermore, the photosensitive resin composition according to item 1 or 2, further comprising (D) a radical polymerizable compound. [4] The photosensitive resin composition according to item 3, wherein the (D) radical polymerizable compound comprises (D1) monofunctional monomer and (D2) polyfunctional monomer. [5] The photosensitive resin composition according to item 4, wherein the mass ratio (D1 / D2) of the monofunctional monomer (D1) to the polyfunctional monomer (D2) is greater than 0.01 and less than 0.5. [6] Furthermore, (E) Silane coupling agent, (F) Organic titanium compounds, (G) Thermal crosslinking agent, (H) Rust inhibitor, (I) Thermal polymerization initiator, and (J) Plasticizers, A photosensitive resin composition according to item 1 or 2, comprising at least one selected from the group consisting of the following. [7] With respect to 100 parts by mass of the (A) polyimide, The solvent (B) is added in 30 to 1000 parts by mass, and The (C) photopolymerization initiator is 1 to 30 parts by mass, A photosensitive resin composition according to item 1 or 2, comprising in the proportion of [amount missing]. [8] In equation (1) above, X is given by the following equations (2) to (9): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] A photosensitive resin composition according to item 1 or 2, having a structure represented by at least one selected from the group consisting of the following. [9] In equation (1) above, Y is given by the following equations (10) to (19): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [Chemical] [Chemical] [Chemical] The photosensitive resin composition according to item 1 or 2, having a structure represented by at least one selected from the group consisting of

[10] The photosensitive resin composition according to item 1 or 2, wherein the (A) polyimide has a polymerizable functional group at its terminal.

[11] The following steps: (1) A step of applying the photosensitive resin composition according to item 1 or 2 onto a substrate and forming a photosensitive resin layer on the substrate; (2) A step of exposing the photosensitive resin layer; (3) A step of developing the exposed photosensitive resin layer and forming a relief pattern; (4) A step of heat-treating the relief pattern and forming a cured relief pattern; A method for producing a cured relief pattern, comprising

[12] A cured film comprising a cured product of the photosensitive resin composition according to item 1 or 2.

[13] A negative photosensitive resin composition comprising (A) polyimide, (B) a solvent, and (C) a photopolymerization initiator, wherein the (A) polyimide has a structure represented by the following general formula (1): [Chemical] {In the formula, n is a positive integer, X is a tetravalent group having 6 to 31 carbon atoms, and Y is a divalent group.} and has a structure represented by The negative photosensitive resin composition, wherein the oxygen permeability (cc / m 2 ·24h·atm) of the cured film obtained by heating the composition in a nitrogen atmosphere at 230 °C for 2 hours is less than 1000. [Advantages of the Invention]

[0014] According to this disclosure, it is possible to provide a photosensitive resin composition that can realize a pre-baked film with excellent flatness, suppress changes in film thickness before and after curing, have excellent adhesion to metal wiring, and achieve low oxygen permeability in a cured film (cured relief pattern). Furthermore, this disclosure provides a method for manufacturing a cured relief pattern and a cured film realized using such a photosensitive resin composition. [Brief explanation of the drawing]

[0015] [Figure 1] Figure 1 is a schematic diagram illustrating the evaluation method in this embodiment. [Modes for carrying out the invention]

[0016] Embodiments of the present disclosure will be described below. In this specification, if there are multiple structures represented by the same reference numerals in the same general formula, unless otherwise specified, each structure may be selected independently and may, of course, be identical or different from one another. Even when multiple structures represented by the same reference numeral exist in different general formulas, unless otherwise specified, these structures may be selected independently and may, of course, be identical or different from one another. In this specification, various measurements are performed according to the methods described in the examples unless otherwise specified. In the drawings, scale, shape, and length may be exaggerated for clarity.

[0017] In this specification, upper or lower limits in numerical ranges described in stages may be replaced by upper or lower limits in other numerical ranges described in stages, and further, by the corresponding values ​​described in the examples. The term "process" is included not only in the sense of an independent process, but also in the sense of a process that cannot be clearly distinguished from other processes, as long as the function of that process is achieved.

[0018] [Photosensitive resin composition (negative type photosensitive resin composition)] The photosensitive resin composition of this embodiment (hereinafter also simply referred to as "photosensitive resin composition") comprises (A) polyimide, (B) solvent, and (C) photopolymerization initiator. The photosensitive resin composition may optionally further contain, in addition to the above components, at least one component selected from the group consisting of (D) radical polymerizable compound, (E) silane coupling agent, (F) organotitanium compound, (G) thermal crosslinking agent, (H) rust inhibitor, (I) thermal polymerization initiator, and (J) plasticizer. The photosensitive resin composition may also optionally further contain components other than the above components (A) to (J). These components (A) to (J), as well as other components, may be used individually or in combination of two or more.

[0019] The photosensitive resin composition is (A) Polyimide, (B) Solvent, and (C) Photopolymerization initiator This is a negative-type photosensitive resin composition containing [a specific compound / substance]. Such photosensitive resin composition, (A) Polyimide is given by the following general formula (1): [ka] {In the formula, n is a positive integer, X is a tetravalent group with 6 to 31 carbon atoms, and Y is a divalent group.} It has a structure represented by and (A) Polyimides do not have polymerizable functional groups in their side chains. (A) The weight-average molecular weight (Mw) of the polyimide, The following formula (b): R(F Cont. ) = (Mw f (+1) / (Mw x +Mw Y -36)···(b) (In the formula, Mw f (A) The total mass of fluorine atoms that may be contained in the polyimide, Mw X(A) The molecular weight of the tetracarboxylic dianhydride constituting the polyimide, Mw Y (A) This is the molecular weight of the diamine that makes up the polyimide. The product of R calculated by and {Mw × R(F Cont. )} is expressed in the following equation (a): 300 ≤ Mw × R ≤ 948 ···(a) It satisfies the condition.

[0020] The conventional technology had room for improvement in the following ways: For example, in the above-mentioned Patent Document 1, during the curing of the photosensitive resin composition, the ring closure of the polyimide precursor (the polyimide precursor described in Patent Document 1) may affect film shrinkage, making it difficult to obtain a highly flat redistribution layer. Furthermore, Patent Document 2 states that the interaction between the polymer and the copper interface may be inhibited due to the influence of polyfunctional (meth)acrylate (the polyfunctional (meth)acrylate described in Patent Document 2), and in this case, adhesion to copper tends to decrease. Furthermore, Patent Document 3 states that the condensation of polyfunctional (meth)acrylates may be suppressed due to the influence of a heterocyclic compound having a reactive group (the heterocyclic compound described in Patent Document 3), which could lead to a deterioration in oxygen permeability.

[0021] In recent years, with the diversification of package mounting technologies, the types of support materials have increased, and the redistribution layers have become multilayered. This has led to a demand for highly planar insulating materials used in wiring formation (e.g., insulating layers obtained using photosensitive resin compositions). For planarization of photosensitive resin compositions, polyfunctional (meth)acrylates are sometimes used, as well as soluble polyimides. In the former case, the interaction between the polymer and copper may be inhibited, and in the latter case, solubility in the solvent may decrease. For these reasons, it is conceivable to use fluorine atoms, which have good solubility in the solvent, for planarization of photosensitive resin compositions. However, in photosensitive resin compositions made using polymers containing fluorine atoms, the resulting film density may decrease. In this case, the oxygen permeability and water vapor permeability of the resulting film tend to be high, and therefore, there is a concern that short circuits may occur during reliability testing.

[0022] On the other hand, according to this embodiment, it is possible to realize a pre-baked film with excellent flatness, a cured film (cured relief pattern) that can suppress changes in film thickness before and after curing, has excellent adhesion to metal wiring, and achieves low oxygen permeability. Furthermore, according to a preferred embodiment of this product, it is possible to provide a photosensitive resin composition that can realize a cured film with excellent resistance (chemical resistance) to chemicals used in the manufacturing process of metal wiring, and also a photosensitive resin composition that can realize a cured film with excellent resolution.

[0023] ≪(A) Polyimide≫ The photosensitive resin composition is (A) polyimide, as shown in formula (1): [ka] {In the formula, n is a positive integer, X is a tetravalent group with 6 to 31 carbon atoms, and Y is a divalent group with 6 to 40 carbon atoms.} It is preferable to include a polyimide represented by [formula]. This makes it easier to achieve the effects in this embodiment. Furthermore, the tetravalent group and the divalent group in the formula may each be an organic group. Here, "organic group" means a group containing carbon.

[0024] (A) Polyimide is synthesized from a tetracarboxylic dianhydride and a diamine. Therefore, in formula (1), X represents a structure derived from the tetracarboxylic dianhydride, and Y represents a structure derived from the diamine. From the viewpoint of chemical resistance, it is preferable that X and Y do not contain ester structures in their main chain skeletons.

[0025] (A) The weight-average molecular weight (Mw) of the polyimide, The following formula (b): R(F Cont. )=(Mw f (+1) / (Mw x +Mw Y -36)···(b) The product of R calculated by and {Mw × R(F Cont. )} is expressed in the following formula (a): 300 ≤ Mw × R ≤ 948 ···(a) It satisfies the condition.

[0026] (A) The weight-average molecular weight (Mw) of the polyimide is measured according to the method described in the examples. In equation (b), Mw f (A) is the total mass of fluorine atoms that may be contained in polyimide, in particular the total mass of fluorine atoms that may be contained in the tetracarboxylic dianhydride and diamine that constitute polyimide, and Mw x (A) is the molecular weight of the tetracarboxylic dianhydride constituting the polyimide, and Mw Y (A) is the molecular weight of the diamine that makes up the polyimide. The mass of the fluorine atom is "19".

[0027] Generally, polyimides have a rigid, planar resin structure, and therefore, by applying thermal energy through heating, they form an ordered structure. This makes them prone to high thermomechanical properties. On the other hand, due to their rigid, planar structure, their solubility in solvents may decrease, which can lead to reduced moldability. In this regard, introducing fluorine atoms into the polyimide skeleton, particularly into the skeletons corresponding to tetracarboxylic dianhydrides and / or diamines, tends to improve solubility in solvents. On the other hand, the decrease in resin density due to the bulkiness of the fluorine atoms tends to reduce barrier properties against gases (oxygen and / or water vapor, etc.). Therefore, when used for protecting conductors such as copper and aluminum, and as an interlayer insulating film, corrosion may occur due to high oxygen permeability and / or water vapor permeability. For this reason, when introducing fluorine atoms into polyimide (A), it is necessary to consider the amount introduced, and it may also be necessary to devise methods for controlling the amount of fluorine atoms in the resin and methods for introducing them into the resin. For example, in order to maintain solubility in solvents, it is necessary to consider the molecular weight of the resin in accordance with the amount of fluorine atoms introduced, and consequently, to balance the amount of fluorine atoms introduced with the molecular weight of the resin.

[0028] The flatness of the pre-baked film of the photosensitive resin composition is likely to be favorable when (A) the weight-average molecular weight (Mw) of the polyimide is small and when the amount of fluorine atoms introduced is large. On the other hand, the oxygen permeability of the cured film tends to be favorable when the amount of introduced fluorine atoms is small, and the thermomechanical properties, and consequently the adhesion to metal wiring, tend to be favorable when the weight-average molecular weight (Mw) of (A) polyimide is large.

[0029] Therefore, from the perspective of achieving a pre-baked film with excellent flatness, and from the perspective of achieving a cured film (cured relief pattern) that can suppress changes in film thickness before and after curing, has excellent adhesion to metal wiring, and achieves low oxygen permeability, there is significance in focusing on the balance between the amount of fluorine atoms introduced and the molecular weight of the resin, and this significance is expressed as the product (Mw × R).

[0030] By controlling the product (Mw × R) within a predetermined numerical range, it becomes possible to achieve both good solubility in solvents and good oxygen permeability. Furthermore, by controlling the product (Mw × R) within a predetermined numerical range, the mechanical properties of the cured film improve, resulting in excellent copper adhesion. The product (Mw × R) is between 300 and 948, and from the viewpoint of oxygen permeability, it is preferably between 300 and 900, more preferably between 300 and 800, and even more preferably between 400 and 700. If the product (Mw × R) is less than 300, it is unfavorable in terms of adhesion to metal wiring, and if it exceeds 948, it is unfavorable in terms of the flatness of the pre-baked film and / or low oxygen permeability. In relation to the product (Mw × R), the lower limit "300" has technical significance in achieving the effects of the present invention, particularly in satisfying the thermomechanical properties necessary to ensure reliability in semiconductor PKG devices, and the upper limit "948" has technical significance in ensuring the storage stability of the liquid photosensitive resin composition and reliability in semiconductor PKG devices.

[0031] Here, this embodiment is R(F Cont. (Mw f (+1) and (Mw x +Mw Y They are also paying attention to the ratio of -36). R(F Cont. A large R(F) means, for example, that there is a high proportion of raw materials containing fluorine atoms, and also R(F) Cont. A small value of ) means, for example, that the proportion of raw materials containing fluorine atoms is small. Raw materials containing fluorine atoms do not need to be used. If the total mass of fluorine atoms in the polyimide is below the detection limit, Mw f It can be treated as 0. Mw f When it is 0, "Mw f The value "+1" is treated as the smallest value, i.e., "1". "Mw x +Mw Y Regarding "-36", "Mw x +MwY The "36" subtracted from " corresponds to the tetracarboxylic dianhydride, the diamine, and the component not included in the repeating unit (2 mol of water molecules). In other words, R(F Cont. This can also be understood as relating to the total mass of fluorine atoms per repeating unit.

[0032] (A) Weight-average molecular weight (Mw) of polyimide, Mw f , Mw x , and Mw Y This can be controlled by appropriately selecting the types of raw materials that make up the (A) polyimide, specifically tetracarboxylic dianhydride and diamine, and by appropriately changing their proportions.

[0033] In equation (1) above, X is as follows: (2) to (9): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] Examples of structures include those represented by at least one selected from the group consisting of the following:

[0034] From the viewpoint of suitably suppressing the oxygen permeability of the cured film, X preferably has a structure represented by at least one selected from the group consisting of formulas (2) to (8). From the viewpoint of the chemical resistance of the cured film, it is more preferable that X has a structure represented by at least one selected from the group consisting of formulas (2), (3), (5), (7), and (8). It is even more preferable that X has a structure represented by at least one selected from the group consisting of formulas (2) and (3), and at least one selected from (7) and (8). Furthermore, X may have the structure represented by formula (9) from the viewpoint of ensuring the total mass of fluorine atoms contained in (A) polyimide.

[0035] In equation (1) above, Y is as shown in equations (10) to (19) below: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] Examples of structures include those represented by at least one selected from the group consisting of the following:

[0036] From the viewpoint of suitably suppressing the oxygen permeability of the cured film, Y preferably has a structure represented by at least one selected from the group consisting of formulas (10) to (16) and (19), and from the viewpoint of chemical resistance, it is more preferable that Y has a structure represented by at least one selected from the group consisting of formulas (10), (12), (13), and (19), thereby suppressing the shrinkage of the cured film. It is even more preferable that Y has a structure represented by formulas (12), (13), and (19), and it is particularly preferable that Y has a structure represented by formulas (12) and (13). From the viewpoint of ensuring the total mass of fluorine atoms contained in (A) polyimide, Y may have the structure represented by formula (17) and / or formula (18). Furthermore, because the polyimide (A) described above does not have side-chain polymerizable groups, the photosensitive resin composition of this embodiment exhibits excellent copper adhesion.

[0037] (A) The molecular weight distribution (Mw / Mn) of the polyimide is preferably between 1.0 and 1.8. From the viewpoint of manufacturing efficiency of the molecular weight distribution, the lower limit is more preferably 1.15 or higher, and even more preferably 1.25 or higher. From the viewpoint of resolution, the upper limit is more preferably 1.7 or lower, and even more preferably 1.6 or lower.

[0038] (A) The weight-average molecular weight (Mw) of the polyimide is preferably 8,000 or more and 23,000 or less from the viewpoint of the mechanical properties of the cured film and the flatness of the spin-coated film (coated film). From the viewpoint of the mechanical properties of the cured film, the lower limit is preferably 8,000 or more, more preferably 10,000 or more, even more preferably 12,000 or more, and particularly preferably 18,000 or more. (B) From the viewpoint of solubility in the solvent and the flatness of the spin-coated film (coated film), it is preferably 23,000 or less, more preferably 20,000 or less, and even more preferably 16,000 or less.

[0039] (A) From the viewpoint of mechanical properties, chemical resistance, and resolution, polyimide is preferably end-chain polypolymerizable functional groups (end functional groups).

[0040] ≪Method for producing polyimide≫ (A) An example of a method for producing polyimide is: A step of reacting a tetracarboxylic dianhydride with a diamine to obtain a polyamic acid; and, A process to obtain polyimide by dehydrating and cyclizing polyamic acid by heating, and by chemical imidation using a catalyst; The above manufacturing method may be used as needed. A step of introducing a desired functional group (e.g., a polymerizable functional group) to the end of a polyimide, preferably at the end of the main chain; It may have.

[0041] When polyamic acid is dehydrated and cyclized by heating, the heating temperature is preferably 150°C or higher, and more preferably 160°C or higher, from the viewpoint of allowing the cyclization reaction to proceed smoothly. Furthermore, from the viewpoint of suppressing side reactions at high temperatures, the temperature is preferably 200°C or lower, and more preferably 180°C.

[0042] When polyamic acids are dehydrated and cyclized using a catalyst, examples of catalysts include base catalysts, specifically, pyridine acetate anhydride and triethylamine acetate anhydride.

[0043] Examples of tetracarboxylic dianhydrides include pyromellitic anhydride (PMDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,4'-oxydiphthalic anhydride, 4,4'-biphenylic acid dianhydride (BPDA), 3,4'-biphenylic acid dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic acid anhydride (BPADA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6' Examples include '-tetracarboxylic dianhydride (CpODA), bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic anhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA).

[0044] Examples of diamines include 4,4'-diaminodiphenyl ether (DADPE), 3,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene (APB), 1,4-bis(4-aminophenoxy)benzene (TPEQ), 2-phenoxybenzene-1,4-diamine, 9,9-bis(4-aminophenyl)fluorene (BAFL), and 6-(4-aminophenoxy)biphenyl-3-amine (PDPE). Examples include ), 3,3'-diphenyl-4,4'-bis(4-aminophenoxy)biphenyl (APBP-DP), 2,2-bis[3-phenyl-4-(4-aminophenoxy)phenyl]propane (DAOPPA), 2,2'-dimethylbenzidine (m-TB), 2,2'-bis(trifluoromethyl)benzidine (TFMB), and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP).

[0045] <Method for producing polyimides having polymerizable functional groups at the ends of the main chain> By reacting the polyimide obtained by the above method with a compound having a polymerizable functional group at its terminal end, a polyimide having a polymerizable functional group at its terminal end can be obtained. The terminal structure of the polyimide before the introduction of the polymerizable functional group may be a carboxyl group or an acid anhydride group derived from a tetracarboxylic dianhydride, or an amino group derived from a diamine.

[0046] The compound having a polymerizable functional group at its terminus is preferably at least one selected from the group consisting of isocyanate compounds, chloride compounds, and alcohol compounds having the polymerizable functional group. Examples of polymerizable functional groups include (meth)acryloyl groups.

[0047] Examples of compounds having polymerizable functional groups at their termini include isocyanate compounds such as 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate; chloride compounds such as acryloyl chloride and methacryloyl chloride; and alcohol compounds such as 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate: HEMA), 2-hydroxyethyl acrylate, 4-hydroxyethyl methacrylate, and 4-hydroxyethyl acrylate.

[0048] Isocyanate compounds react with the amino groups of dehydrated, ring-closed polyimides to form urea bonds. Chloride compounds react with the amino groups of dehydrated, ring-closed polyimides to form amide bonds. Alcohol compounds react with the carboxyl groups or acid anhydride groups of dehydrated, ring-closed polyimides to form ester bonds. Isocyanate compounds, chloride compounds, and / or alcohol compounds may react with the terminal, preferably the main chain terminal, of the dehydrated, ring-closed polyimide.

[0049] One method for reacting an isocyanate compound with the amino group of a dehydrated, ring-closed polyimide is to mix the two and stir the mixture at room temperature. One method for reacting a chloride compound with the amino group of a dehydrated, ring-closed polyimide is to cool the dehydrated, ring-closed polyimide solution with ice and then add the chloride compound dropwise. Methods for reacting an alcohol-based compound with a carboxyl group or acid anhydride group of a dehydrated, ring-closed polyimide include using a condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC) and an esterification catalyst such as p-toluenesulfonic acid.

[0050] These reactions make it easier to reduce interactions caused by polar functional groups by substituting polymer-terminal polar groups with polymerizable functional groups, and in this case, the flatness of the pre-baked film tends to improve. Examples of polymerizable functional groups (terminal functional groups) include the following formula: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] {In the formula, * indicates the binding site with the end of (A) polyimide.} It is preferable to have a structure represented by at least one selected from the group consisting of the following. From the viewpoint of resolution and suppression of curing shrinkage, it is preferable to have a radical polymerizable functional group at the end of the main chain of the polymer.

[0051] (A) In the production of polyimide, a reaction solvent may be used to carry out the reaction efficiently in a homogeneous system. The reaction solvent should be one that can uniformly dissolve or suspend the tetracarboxylic dianhydride, the diamine, and an optional component (for example, a compound having a polymerizable functional group at its terminus). Examples of reaction solvents include γ-butyrolactone (GBL), dimethyl sulfoxide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide.

[0052] (A) Polyimide may be purified by known methods, such as those described in Japanese Patent Publication No. 2012-194520. Examples of purification methods include reprecipitation by adding the (A) polyimide solution dropwise to water to remove unreacted substances, filtration to remove condensing agents and the like that are insoluble in the reaction solvent, and removal of the catalyst using an ion exchange resin. After these purification methods, (A) polyimide may be dried by known methods, in which case it may be isolated in powder form.

[0053] (A) Polyimide may be present in the photosensitive resin composition in an amount of, for example, 35% by mass, preferably 20-70% by mass, and more preferably 25-65% by mass. Also, (A) polyimide may be present in an amount of, for example, 50% by mass or more, preferably 55-90% by mass, and more preferably 60-80% by mass, relative to the solid content of the photosensitive resin composition.

[0054] (B) Solvent (B) The solvent can dissolve or suspend (A) the polyimide and (C) the photopolymerization initiator. Examples of (B) solvents include γ-butyrolactone (GBL), dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, N,N-dimethylacetacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide.

[0055] (B) The solvent can be appropriately selected depending on the thickness of the coating film of the photosensitive resin composition and the viscosity of the composition. (B) The solvent can be used in a ratio of, for example, 30 to 1,000 parts by mass, preferably 140 to 1,000 parts by mass, per 100 parts by mass of (A) polyimide.

[0056] (B) The higher the solubility of (A) polyimide in the solvent, the more likely it is that the flatness of the pre-baked film will improve. On the other hand, the higher the solubility of (A) polyimide, the more likely it is that solvent will remain in the pre-baked film, which tends to increase the shrinkage rate of the cured film. When an alcohol without an olefinic double bond is included, the proportion of the alcohol without an olefinic double bond in the total solvent is preferably 5 to 50% by mass. From the viewpoint of the storage stability of the photosensitive resin composition, a proportion of 10% by mass or more is more preferable. Furthermore, from the viewpoint of the solubility of (A) polyimide, a proportion of 30% by mass or less is more preferable.

[0057] (C) Photopolymerization initiator (C) Photopolymerization initiators are compounds that can initiate polymerization by active light, preferably compounds that generate radicals by active light and can polymerize compounds containing ethylenically unsaturated groups, etc. Examples of initiators that generate radicals by active light include benzophenone, N-alkylaminoacetophenone, oxime esters, acridine, and phosphine oxide, as well as compounds containing structures such as rophine.Examples of the above include, for instance, benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, acrylic benzophenone, 4-benzoyl-4'-methyldi Aromatic ketones such as phenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin, and ethyl benzoin; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) (manufactured by BASF Japan Ltd., Irgacure) Oxe02), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., PBG305), 1-(6-O-methylbenzoyl-9-ethylcarbazole-3-yl)-(3-cyclopentylacetone)-1-oxime acetate (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., TR-PBG-304), Product name: TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9- Oxime ester compounds such as [Tyl-6-(2-Furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (manufactured by Nikko Chemtec Co., Ltd., product name: TR-PBG-326), NCI-831 (trade name, manufactured by ADEKA Corporation); benzyl derivatives such as benzyldimethylketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds;Examples include phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and chlorophyll compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0058] Among the above (C) photopolymerization initiators, oxime ester compounds are preferred from the viewpoint of resolution, and more preferably oxime esters having a diphenyl sulfide structure represented by the following general formula (28) or a carbazole structure represented by the following general formula (29). From the viewpoint of surface curability, the photosensitive resin composition of this embodiment is even more preferably to contain an oxime ester having a carbazole structure. [ka] [ka] {In the formula, R1 represents a hydrocarbon group having 1 to 10 carbon atoms, and * represents a bond with another structure.}

[0059] (C) The proportion of the photopolymerization initiator is preferably 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of (A) polyimide. From the viewpoint of photocurability, the proportion is more preferably 2 parts by mass or more. Furthermore, from the viewpoint of good curability including the bottom of the relief pattern, it is more preferably 20 parts by mass or less.

[0060] (D) Radical polymerizable compounds From the viewpoint of improving the resolution of the cured relief pattern and suppressing film shrinkage during heating, the photosensitive resin composition may optionally contain radical polymerizable compounds.

[0061] As the radical polymerizable compound, (meth)acrylate compounds that readily undergo radical polymerization reactions with (C) a photopolymerization initiator are preferred. The radical polymerizable compound more preferably comprises a (D1) monofunctional monomer containing one polymerizable functional group in the molecule and a (D2) polyfunctional monomer containing two or more polymerizable functional groups in the molecule. The polymerizable functional group is preferably a (meth)acryloyl group.

[0062] (D1) Examples of monofunctional monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl (meth)acrylate, butoxydiethylene glycol methacrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, m-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate, 4-methacryloyloxybenzophenone, EO-modified paracumylphenol acrylate, nonylphenoxyethyl acrylate, 6-acrylamidohexanoic acid, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy(meth)acrylate, methoxypolyethylene glycol (meth)acrylate (for example, product name "AM-90G", manufactured by Shin Nakamura Chemical Industry Co., Ltd.), etc.

[0063] (D2) Examples of polyfunctional monomers include, Diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and other di(meth)acrylates of ethylene glycol or polyethylene glycol, di(meth)acrylates of propylene glycol or polypropylene glycol, di(meth)acrylate or tri(meth)acrylate of glycerol, cyclohexane di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, (meth)acrylamide, its derivatives, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate or tri Examples include di(meth)acrylate, pentaerythritol di(meth)acrylate, tri(meth)acrylate or tetra(meth)acrylate, ethylene oxide or propylene oxide adducts of these compounds, urethane acrylates such as EBECRYL230 (product name, manufactured by Daicel Ornex), EBECRYL8402 (product name, manufactured by Daicel Ornex), EBECRYL8465 (product name, manufactured by Daicel Ornex), EBECRYL8667 (product name, manufactured by Daicel Ornex), EBECRYL4740 (product name, manufactured by Daicel Ornex), KRM9276 (product name, manufactured by Daicel Ornex), and compounds of tris-(2-hydroxyethyl) isocyanurate acrylate.

[0064] Among radical polymerizable compounds, it is preferable to include (D2) polyfunctional monomers from the viewpoint of suppressing membrane shrinkage, and it is even more preferable to include compounds having three or more polymerizable functional groups in the molecule. The mass ratio (D1 / D2) of the monofunctional monomer (D1) to the polyfunctional monomer (D2) is preferably greater than 0.01 and less than 0.5. From the viewpoint of the flatness of the pre-baked film, the mass ratio is preferably greater than 0.02, and from the viewpoint of the flatness of the cured film, it is preferably less than 0.5. From a similar viewpoint, the mass ratio is more preferably between 0.05 and 0.45, and even more preferably between 0.1 and 0.4.

[0065] The proportion of the radical polymerizable compound in the photosensitive resin composition is preferably 0.5 to 100 parts by mass per 100 parts by mass of (A) polyimide. From the viewpoint of photocurability, the lower limit is more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass. From the viewpoint of good curability, including copper adhesion and the bottom of the pattern, the upper limit is more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less.

[0066] (E) Silane coupling agent To improve the adhesion of the cured relief pattern to the substrate, the photosensitive resin composition may optionally contain a silane coupling agent.

[0067] Examples of silane coupling agents include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name KBM803, manufactured by Chisso Corporation: product name Cyra Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, manufactured by Azmax Corporation: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.5C), and mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldieth Examples include xymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, and 4-mercaptobutyltripropoxysilane.

[0068] Furthermore, examples of silane coupling agents include N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS3610, manufactured by Azmax Co., Ltd.: product name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: product name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl) Urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax: trade name) Other examples include SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax: product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax: product name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax: product name SLA0599.2), etc.

[0069] Furthermore, examples of silane coupling agents include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and tetrax(m Toxiethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[ 3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyln-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol,Other examples include methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

[0070] Among silane coupling agents, the following general formula (30) is preferred from the viewpoint of adhesion to the substrate and storage stability: [ka] {where, R 10 R is at least one selected from the group consisting of substituents including epoxy groups, phenylamino groups, ureido groups, isocyanate groups, and isocyanuric groups. 11 R is an alkyl group having 1 to 4 carbon atoms. 12 is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, a is an integer from 1 to 3, and i is an integer from 1 to 6. It is preferable to have a structure represented by .

[0071] In formula (30), a is preferably 2 or 3, and more preferably 3, from the viewpoint of adhesion to the metal redistribution layer. i is preferably 1 to 4 from the viewpoint of adhesion to the metal redistribution layer, and may be 2 to 5 from the viewpoint of resolution.

[0072] R 10 Among the above, from the viewpoint of resolution and adhesion of the metal redistribution layer, it is preferable that the substituent is selected from the group consisting of substituents containing a phenylamino group and substituents containing a ureido group, and substituents containing a phenylamino group are more preferable. 11 , and R 12 The alkyl groups having 1 to 4 carbon atoms listed above include, independently, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups.

[0073] Examples of silane coupling agents containing epoxy groups include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

[0074] Examples of silane coupling agents containing a phenylamino group include N-phenyl-3-aminopropyltrimethoxysilane. Examples of silane coupling agents containing a ureido group include 3-ureidopropyltrialkoxysilane. Examples of silane coupling agents containing an isocyanate group include 3-isocyanatetopropyltriethoxysilane.

[0075] The proportion of the silane coupling agent in the photosensitive resin composition may be 0.2 to 10 parts by mass per 100 parts by mass of (A) polyimide, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, from the viewpoint of copper adhesion. From the viewpoint of suppressing the generation of foreign matter due to precipitation, preferably 8 parts by mass or less, and more preferably 6 parts by mass or less.

[0076] (F) Organic titanium compounds To improve the chemical resistance of the cured film, the photosensitive resin composition may optionally contain an organotitanium compound.

[0077] Suitable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Specific examples include titanium(IV) oxide acetylacetonate, titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedione), titanium diisopropoxide bis(2,4-pentanedione), titanium diisopropoxide bis(tetramethylheptanedione), titanium diisopropoxide bis(ethylacetoacetate), titanium diisopropoxide bis(acetylacetonate), etc.

[0078] II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc.

[0079] III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 Examples include -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium.

[0080] IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0081] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc.

[0082] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0083] VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0084] In particular, from the viewpoint of better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethyl acetate), titanium tetra(n-butoxide), and bis(η 5 At least one compound selected from the group consisting of -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium and titanium(IV) oxide acetylacetonate is preferred.

[0085] If the negative-type photosensitive resin composition contains an organic titanium compound, the proportion may be 0.05 parts by mass or more and 10 parts by mass or less per 100 parts by mass of (A) polyimide. From the viewpoint of heat resistance and chemical resistance of the cured film, 0.5 parts by mass or more is preferred, and from the viewpoint of storage stability of the photosensitive resin composition, 2 parts by mass or less is preferred.

[0086] (G) Thermal crosslinking agent From the viewpoint of the flatness of the pre-baked film and the chemical resistance of the cured film, the photosensitive resin composition may optionally contain a thermal crosslinking agent.

[0087] A thermal crosslinking agent is a compound that undergoes an addition reaction or condensation polymerization reaction upon heating. These reactions occur in combinations of (A) polyimide and the thermal crosslinking agent, with other thermal crosslinking agents, and with other components described later, and the reaction temperature is preferably 150°C or higher.

[0088] Examples of thermal crosslinking agents include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds. From the viewpoint of suppressing film shrinkage, it is preferable that the thermal crosslinking agent contains nitrogen atoms.

[0089] Examples of alkoxymethyl compounds include the following compounds: [ka] [ka] These are some examples.

[0090] Examples of epoxy compounds include 4-hydroxybutyl acrylate glycidyl ether, epoxy compounds containing a bisphenol A type group, and hydrogenated bisphenol A diglycidyl ether (e.g., Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.).

[0091] Examples of thermal crosslinking agents include epoxy resins. Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexydienebisphenol type epoxy resin), tetramethylbisphenol F type epoxy resin, and other bisphenol type epoxy resins; Novolac epoxy resins such as phenol novolac type epoxy resins, brominated phenol novolac type epoxy resins, cresol novolac type epoxy resins, tetraphenol group ethane type novolac type epoxy resins, and novolac type epoxy resins having a condensed ring aromatic hydrocarbon structure; Biphenyl-type epoxy resin; Aalkyl epoxy resins such as xylylene-type epoxy resins and biphenylaralkyl-type epoxy resins; Epoxy resins having a naphthalene skeleton, such as naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthalenediol type epoxy resin, 2- to 4-functional epoxy type naphthalene resin, binaphthyl type epoxy resin, and naphthalene aralkyl type epoxy resin; Anthracene-type epoxy resin; Phenoxy epoxy resin; Dicyclopentadiene type epoxy resin; Norbornene-type epoxy resin; Adamantane-type epoxy resin; Fluorene-type epoxy resins, phosphorus-containing epoxy resins, alicyclic epoxy resins, aliphatic chain epoxy resins, bisphenol A novolac-type epoxy resins, bixylenol-type epoxy resins, trihydroxyphenylmethane-type epoxy resins, stilbene-type epoxy resins, tetraphenyloleethane-type epoxy resins, triglycidyl isocyanurate-type epoxy resins, and other heterocyclic epoxy resins; Glycidylamines such as N,N,N',N'-tetraglycidylmetoxylendiamine, N,N,N',N'-tetraglycidylbisaminomethylcyclohexane, and N,N-diglycidylaniline; Copolymers of glycidyl (meth)acrylate and compounds having ethylenically unsaturated double bonds; Epoxy resin having a butadiene structure; Diglycidyl ether of bisphenol; Diglycidyl ether of naphthalenediol; Glycidyl ethers of phenols; These are some examples.

[0092] Furthermore, examples of epoxy compounds or epoxy resins include n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ethers such as bisphenol A (or F) glycidyl ether, diglycidyl esters of adipic acid, diglycidyl esters of o-phthalate, and other glycidyl ethers. Steryl, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis(2,3-epoxycyclopentyl) ether, and alicyclic epoxy resins such as Daicel's Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, and Epolid GT401; Aliphatic polyglycidyl ethers such as 2,2'-(((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxiran)) (for example, Techmore VG3101L from Printec: such products are trifunctional epoxy resins), Epolite 100MF (manufactured by Kyoeisha Chemical Industry Co., Ltd.), Epiol TMP (manufactured by NOF Corporation); 1,1,3,3,5,5-Hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)trisiloxane (e.g., DMS-E09 (manufactured by Gellet)); Other examples include:

[0093] Examples of oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, and bis(3-ethyl-3-oxetanylmethyl) Examples include diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicate, phenol novolac type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei, trade name), OXT221 (manufactured by Toagosei, trade name), etc.

[0094] Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), and 4-methyl-N,N'-1,3 Examples include -phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, or 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane.

[0095] Examples of allyl compounds include allyl alcohol, allylanisole, allyl benzoate, allyl cinnamate, N-alyloxyphthalimide, allylphenol, allylphenylsulfone, allylurea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, 1,3,5-benzenetricarboxylic acid triallyl, trimellitate triallyl, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0096] Examples of blocked isocyanate compounds include hexamethylene diisocyanate-based blocked isocyanates (e.g., Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G from Asahi Kasei Corporation, Takenate B-882N from Mitsui Chemicals, Inc., and 7960, 7961, 7982, 7991, and 7992 from Baxenden, etc.) and tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 from Mitsui Chemicals, Inc.). Examples include 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N from Mitsui Chemicals, Inc., Bronate PMD-OA01 and PMD-MA01 from Daiei Sangyo Co., Ltd.), 1,3-bis(isocyanate-methyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N from Mitsui Chemicals, Inc., Coronate BI-301, 2507 and 2554 from Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (e.g., 7950, 7951 and 7990 from Baxenden).

[0097] Among these, from the viewpoint of storage stability, blocked isocyanate compounds or bismaleimide compounds are preferred for thermal crosslinking. From the viewpoint of mechanical properties and chemical resistance, thermal crosslinking agents having two or more crosslinkable functional groups in one molecule are preferred.

[0098] The proportion of the thermal crosslinking agent in the photosensitive resin composition is preferably 0.2 to 40 parts by mass per 100 parts by mass of (A) polyimide. From the viewpoint of chemical resistance, the proportion is more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more. Furthermore, from the viewpoint of storage stability of the photosensitive resin composition, the proportion is more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

[0099] (H) Rust inhibitor When forming a cured film on a substrate made of copper or a copper alloy using a photosensitive resin composition, the photosensitive resin composition may optionally contain a rust inhibitor to improve adhesion. Examples of rust inhibitors include azole compounds and purine compounds.

[0100] Examples of 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-(3,5-di- Examples include 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, 3-mercapto-1,2,4-triazole, 1H-tetrazol, 5-methyl-1H-tetrazol, 5-phenyl-1H-tetrazol, 5-amino-1H-tetrazol, 1-methyl-1H-tetrazol, and 1H-tetrazol-5-acetic acid.

[0101] Particularly preferred are, for example, 5-amino-1H-tetrazole, toltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, and 1H-tetrazole-5-acetic acid.

[0102] Examples of purine compounds 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-aminopurine. Examples include noadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and derivatives thereof.

[0103] If the photosensitive resin composition contains a rust inhibitor, the proportion is preferably 0.01 parts by mass or more and 20 parts by mass or less per 100 parts by mass of (A) polyimide. From the viewpoint of suppressing discoloration of the copper or copper alloy surface when the photosensitive resin composition is formed on copper or a copper alloy, the proportion is more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more. Furthermore, from the viewpoint of photosensitivity, the proportion is more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

[0104] (I) Thermal polymerization initiator The photosensitive resin composition may optionally contain a thermal polymerization initiator from the viewpoint of suppressing film shrinkage. The thermal polymerization initiator is a compound that can initiate polymerization by heat, preferably a compound that generates radicals by heat.

[0105] Examples of thermal polymerization initiators include, Organic peroxides such as dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxyketals; Azo polymerization initiators such as azonitriles, azoesters, and azoamides; These include dialkyl peroxides and diacyl peroxides (e.g., dicumyl peroxide) are preferred from the viewpoint of chemical resistance.

[0106] If the photosensitive resin composition contains a thermal polymerization initiator, the proportion is preferably 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of (A) polyimide. From the viewpoint of suppressing film shrinkage, the proportion is more preferably 0.5 parts by mass or more. Furthermore, from the viewpoint of the storage stability of the photosensitive resin composition, the proportion is more preferably 5 parts by mass or less.

[0107] (J) Plasticizer The photosensitive resin composition may optionally contain a plasticizer to improve the flatness of the pre-baked film and, consequently, to further enhance adhesion to copper. The plasticizer is a compound that improves the fluidity of the (A) polyamide-imide precursor resin when the relief pattern formed using the photosensitive resin composition is heated (cured). Including a plasticizer makes it easier to suppress the change in film thickness during curing.

[0108] Examples of plasticizers include polycarboxylic acid ester plasticizers, sulfonamide plasticizers, phosphate ester plasticizers, polyester plasticizers, and polyalkylene glycol plasticizers.

[0109] Examples of polycarboxylic acid ester plasticizers include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, heptyl benzoate, n-octyl benzoate, nonyl benzoate, isononyl benzoate, isodecyl benzoate, 2-ethylhexyl benzoate, isodecyl benzoate, butyl benzyl benzoate, cyclopropyl benzoate, cyclobutyl benzoate, cyclopentityl benzoate, cyclohexyl benzoate, cycloheptyl benzoate, allyl benzoate, butyl benzyl benzoate, phenyl benzoate, and other benzoic acid esters. Dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, diheptyl phthalate, dinormaloctyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, bis(2-ethylhexyl) phthalate, diisodecyl phthalate, butylbenzyl phthalate, dicyclopropyl phthalate, dicyclobutyl phthalate, dicyclopentityl phthalate, dicyclohexyl phthalate, dicycloheptyl phthalate, diallyl phthalate, bisbutylbenzyl phthalate, diphenyl phthalate, etc. Trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, tripentyl trimellitate, triheptyl trimellitate, trin-normal octyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, tris(2-ethylhexyl) trimellitate, triisodecyl trimellitate, trisbutylbenzyl trimellitate, tricyclopropyl trimellitate, tricyclobutyl trimellitate, tricyclopentyl trimellitate Trimellitate esters such as tricyclohexyl trimellitate, tricycloheptyl trimellitate, trialyl trimellitate, tributylbenzyl trimellitate, triphenyl trimellitate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dipentyl adipate, diheptyl adipate, dinormaloctyl adipate, dinonyl adipate, diisononyl adipate, diisodecyl adipate, bis(2-ethylhexyl) adipate, diisodecyl adipate, butylbenzyl adipate,Adipic acid esters such as dicyclopropyl adipate, dicyclobutyl adipate, dicyclopentityl adipate, dicyclohexyl adipate, dicycloheptyl adipate, diallyl adipate, bisbutylbenzyl adipate, diphenyl adipate, trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, tripentyl trimellitate, triheptyl trimellitate, trin-nor-octyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, Triisodecyl trimellitate, tris(2-ethylhexyl) trimellitate, triisodecyl trimellitate, trisbutylbenzyl trimellitate, tricyclopropyl trimellitate, tricyclobutyl trimellitate, tricyclopentityl trimellitate, tricyclohexyl trimellitate, tricycloheptyl trimellitate, trialyl trimellitate, trisbutylbenzyl trimellitate, triphenyl trimellitate, and other trimellitate esters, dimethyl sebacate, diethyl sebacate, dipropyl sebacate, Sebacate esters such as dibutyl sebacate, dipentyl sebacate, diheptyl sebacate, dinormaloctyl sebacate, dinonyl sebacate, diisononyl sebacate, diisodecyl sebacate, bis(2-ethylhexyl) sebacate, diisodecyl sebacate, butyl benzyl sebacate, dicyclopropyl sebacate, dicyclobutyl sebacate, dicyclopentityl sebacate, dicyclohexyl sebacate, dicycloheptyl sebacate, diallyl sebacate, bisbutyl benzyl sebacate, and diphenyl sebacate. Examples include dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, diheptyl succinate, din-octyl succinate, dinonyl succinate, diisononyl succinate, diisodecyl succinate, bis(2-ethylhexyl) succinate, diisodecyl succinate, butyl benzyl succinate, dicyclopropyl succinate, dicyclobutyl succinate, dicyclopentityl succinate, dicyclohexyl succinate, dicycloheptyl succinate, diallyl succinate, bis-butyl benzyl succinate, and diphenyl succinate.

[0110] Examples of sulfonamide-based plasticizers include aromatic sulfonamide-based plasticizers, specifically N-butylbenzenesulfonamide, p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-ethyl-o-toluenesulfonamide, Nn-butylbenzenesulfonamide, and N-cyclohexyl-p-toluenesulfonamide. N-butylbenzenesulfonamide is preferred.

[0111] Examples of phosphate ester plasticizers include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, and 2-ethylhexyldiphenyl phosphate.

[0112] Examples of polyester-based plasticizers include, Polyesters composed of acid components such as adipic acid, terephthalic acid, isophthalic acid, and diphenyldicarboxylic acid, and diol components such as propylene glycol, 1,3-butanediol, 1,4-butanediol, ethylene glycol, and diethylene glycol; Polyesters composed of hydroxycarboxylic acids such as polycaprolactone; These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or with an epoxy compound or the like.

[0113] Examples of polyalkylene glycol-based 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; End-locking compounds such as the terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds mentioned above; These are some examples.

[0114] Other plasticizers include, for example, Glycerin fatty acid esters such as glycerin monoacetomolaurate, glycerin diacetomolaurate, and glycerin monoacetomostearate; fatty acid amides such as stearic acid amide; aliphatic carboxylic acid esters such as butyl oleate; oxy acid esters such as methyl acetylricinoleate and butyl acetylricinoleate; pentaerythritol; various sorbitols; These are some examples.

[0115] If the photosensitive resin composition contains a plasticizer, the proportion is preferably 0.5 parts by mass or more and 40 parts by mass or less per 100 parts by mass of (A) polyimide. From the viewpoint of the flatness of the coating film when the photosensitive composition is applied, the proportion is more preferably 1 part by mass or more. Furthermore, from the viewpoint of suppressing film shrinkage, the proportion is more preferably 30 parts by mass or less.

[0116] Components other than those listed above (A) to (J) (other components) The photosensitive resin composition may further optionally contain components other than those listed above (A) to (J). Examples of other components include hindered phenol compounds, adhesion aids, sensitizers, thermal polymerization inhibitors, surfactants, and thermal base generators.

[0117] From the viewpoint of suppressing discoloration of the copper surface, the photosensitive resin composition may optionally contain a hindered phenol compound. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butyl Phenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenyl) (Nol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4, 6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethyl Benzyl)-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, Examples include 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-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.

[0118] Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0119] If the photosensitive resin composition contains a hindered phenol compound, the proportion is preferably 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of (A) polyimide. From the viewpoint of preventing discoloration and corrosion of copper or copper alloy when the photosensitive resin composition is formed on copper or copper alloy, the proportion is more preferably 0.5 parts by mass or more. Furthermore, from the viewpoint of photosensitivity, the proportion is more preferably 10 parts by mass or less.

[0120] From the viewpoint of improving the adhesion between the cured film and the substrate, the photosensitive resin composition may optionally contain adhesive aids other than silane coupling agents. Examples of such adhesive aids include aluminum-based adhesive aids.

[0121] Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0122] If the photosensitive resin composition contains an adhesive aid, the proportion is preferably 0.01 parts by mass or more and 25 parts by mass or less per 100 parts by mass of (A) polyimide. From the viewpoint of adhesion, the proportion is more preferably 0.5 parts by mass or more. Furthermore, from the viewpoint of storage stability of the photosensitive resin composition, the proportion is more preferably 20 parts by mass or less.

[0123] The photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamyridane indano n, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone Examples include ethyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene.

[0124] If the photosensitive resin composition contains a sensitizer, the proportion is preferably 0.1 parts by mass or more and 25 parts by mass or less per 100 parts by mass of (A) polyimide.

[0125] The photosensitive resin composition may optionally contain a thermal polymerization inhibitor, particularly when stored in a solvent-containing solution, to improve the stability of viscosity and photosensitivity.

[0126] Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0127] The photosensitive resin composition may optionally contain surfactants from the viewpoint of film flatness. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants.

[0128] Fluorine-based surfactants are those that contain a fluorine atom in their molecule. Examples of fluorine-based surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl alcohols, perfluoroalkyl alkylene oxide adducts, and perfluoroalkyl phosphate esters. More specifically, these are all trade names such as Megafac F-114, Megafac F-251, Megafac F-253, Megafac F-281, Megafac F-410, Megafac F-430, Megafac F-477, Megafac F-510, Megafac F-551, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-557, Megafac F-558, Megafac F-559, Megafac F-560, Megafac F-561, Megafac F-562, Megafac F-563, Megafac F-565, Mega Fuck F-568, Mega Fuck F-569, Mega Fuck F-570, Mega Fuck F-572, Mega Fuck F-574, Mega Fuck F-575, Mega Fuck F-576, Mega Fuck R-40, Mega Fuck R-40-LM, Mega Fuck R-41, Mega Fuck R-94, Mega Fuck RS-56, Mega Fuck RS-72-K, Mega Fuck RS-75, Mega Fuck RS-76-E, Mega Fuck RS-76-NS, Mega Fuck RS-78, Mega Fuck RS-90, Megafuck DS-21 (manufactured by DIC), FC-4430, FC-4432 (manufactured by 3M Japan), Surflon S-211, Surflon S-221, Surflon S-231, Surflon S-232, Surflon S-233, Surflon S-241, Surflon S-242, Surflon S-243, Surflon S-420, Surflon S-431, Surflon S-386, Surflon S-611, Surflon S-647, Surflon S-651, Surflon S-653, Examples include Surflon S-656, Surflon S-658, Surflon S-693, Surflon S-CFJ, and Surflon FPE-50 (all manufactured by AGC Seimi Chemical Co., Ltd.).

[0129] Silicone-based surfactants are preferably those that have a disiloxane structure as a non-polar site. Examples of silicone-based surfactants include polyether-modified silicones, such as linear polyether-modified silicones, linear alkyl-comodified polyether-modified silicones, branched polyether-modified silicones, and branched alkyl-comodified polyether-modified silicones. More specifically, these are all product names: KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6204, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, KP-301, KP-306, KP-109, KP-310, KP-310B, KP-323, KP-326, KP-341, KP-10 4. KP-110, KP-112 (all manufactured by Shin-Etsu Chemical Co., Ltd.); DBE-224, DBE-621, DBE-712, DBE-814, DBE-821, DBE-921, DBP-732, YAD-122, YBD-125, YMS-T31, CMS-626, CMS-222, DBP-534, CMS-832, DBP-C22, QMS-435, ABP-263, DMS-R05, DMS-R11, DMS-R18, DMS-R22, DMS-R31 (all manufactured by Gelest);BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315 N, BYK-320, BYK-322, BYK-323, BYK-325 N, BYK-326, BYK-327, BYK-330, BYK-331, BYK-332, BYK-333, BYK-342, BYK-345, BYK-34 6, BYK-347, BYK-348, BYK-349, BYK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358 N, BYK-359, BYK-360 P, BYK-361 N, BYK-364 P, BYK-366 P, BYK-368 P, BYK-370, BYK-375, BYK-377, BYK-378, BYK-381, BYK-390, BYK-392, BYK-394, BYK-399, BYK-UV 3500, BYK-UV 3505, BYK-UV 3510, BYK-UV 3530, BYK-UV 3535, BYK-UV 3570, BYK-UV 3575, BYK-UV 3576 (all manufactured by Big Chemie Japan); Newcol 2302, Newcol 2303, Newcol 2305, Newcol 2307, Newcol 2308, Newcol 2308-HEN, Newcol 2310, Newcol 2312, Newcol 2314, Newcol 2318, Newcol 2320, Newcol 2327(20), Newcol 2330, Newcol 2344, New Examples include -Call 2360, NewCall 2399-S, NewCall 2399-S(25) (all manufactured by Nippon Emulsifier Co., Ltd.); DMC6038, OW1500, SPG128VP, L03, L033, L053, L066 (all manufactured by Asahi Kasei Wacker Silicone Co., Ltd.); SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (all manufactured by Toray Dow Corning Co., Ltd.).

[0130] Surfactants may have crosslinking groups within their molecules. Examples of such surfactants include silicone-based surfactants and fluorine-based surfactants that have crosslinking groups within their molecules.

[0131] Examples of crosslinkable groups include thermally crosslinkable groups such as epoxy groups, N-methylolamide groups, oxazoline groups, and allyl groups, as well as ultraviolet (UV) crosslinkable groups (for example, vinyl groups, (meth)acryloyl groups, and epoxy groups). More specifically, examples of surfactants having crosslinking groups within their molecules include, all by trade name, Megafac RS-75-A, Megafac RS-72-K, Megafac RS-75-NS, Megafac RS-78, Megafac RS-90, Megafac RS-56 (all manufactured by DIC Corporation); and BYK-UV3500, BYK-UV3505, BYK-UV3530, BYK-UV3570, BYK-UV3575, BYK-UV3576 (all manufactured by BYChemie Corporation).

[0132] The above-mentioned surfactant may be a surfactant in which the fluorine-containing group is removed by heat treatment. An example of such a surfactant is Megafac DS-21 (manufactured by DIC Corporation), which is sold under a trade name.

[0133] If the photosensitive resin composition contains a surfactant, the proportion is preferably 0.001 parts by mass or more and 1 part by mass or less, and more preferably 0.01 parts by mass or more and 0.1 parts by mass or less, per 100 parts by mass of (A) polyimide.

[0134] Furthermore, according to a further embodiment of this embodiment, (A) Polyimide, (B) Solvent, and (C) Photopolymerization initiator A negative-type photosensitive resin composition comprising, The aforementioned (A) polyimide is given by the following general formula (1): [ka] {In the formula, n is a positive integer, X is a tetravalent group with 6 to 31 carbon atoms, and Y is a divalent group.} It has a structure represented by and does not have polymerizable functional groups in its side chains. It is possible to provide a composition in which the oxygen permeability of the cured film obtained by heating the negative photosensitive resin composition at 230°C for 2 hours is less than 1000. With such a composition, the metal wiring is protected from oxidation in the atmosphere during the reliability test. Therefore, in the reliability test performed by applying a voltage such as bHAST, ion diffusion is suppressed, and an electronic device with high insulation reliability can be manufactured. The above oxygen permeability (cc / m 2 ·24h·atm) is preferably less than 500 or less than 200. The oxygen permeability can be measured by the method described in the examples below. The oxygen permeability may be more than 0.

[0135] <Method for manufacturing a cured relief pattern> The method for manufacturing a cured relief pattern of the present disclosure is (1) A step of applying the negative photosensitive resin composition of the present disclosure described above onto a substrate to form a photosensitive resin layer on the substrate (resin layer forming step); (2) A step of exposing the photosensitive resin layer (exposure step); (3) A step of developing the exposed photosensitive resin layer to form a relief pattern (relief pattern forming step); (4) A step of heat-treating the relief pattern to form a cured relief pattern (cured relief pattern forming step) and includes.

[0136] (1) Resin layer forming step In this step, the negative photosensitive resin composition of the present disclosure is applied onto a substrate, and if necessary, dried thereafter to form a photosensitive resin layer. As the coating method, methods conventionally used for coating negative photosensitive resin compositions, for example, methods of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc., methods of spray coating with a spray coater, etc. can be used.

[0137] If necessary, the coating containing the negative-type photosensitive resin composition can be dried. Drying methods include air drying, heating with an oven or hot plate, and vacuum drying. Specifically, in the case of air drying or heating, drying can be performed at a temperature of 20°C to 150°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the substrate.

[0138] (2) Exposure process In this process, the photosensitive resin layer formed above is exposed to ultraviolet light or the like, either through a patterned photomask or reticle, or directly, using an exposure device such as a contact aligner, mirror projection, or stepper. This exposure causes the polymerizable functional groups of (A) polyimide contained in the negative-type photosensitive resin composition to crosslink due to the action of (C) photopolymerization initiator. This crosslinking makes the exposed areas insoluble in the developer solution described later, thus enabling the formation of a relief pattern.

[0139] Subsequently, if necessary, post-exposure baking (PEB), pre-development baking, or both may be performed using any combination of temperature and time, for purposes such as improving photosensitivity. The baking conditions are preferably a temperature of 40°C to 120°C and a time of 10 seconds to 240 seconds, but are not limited to this range as long as they do not impair the properties of the negative-type photosensitive resin composition of this disclosure.

[0140] (3) Relief pattern formation process In this process, the unexposed portion of the photosensitive resin layer after exposure is developed and removed to form a relief pattern. Any method can be selected from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, or the immersion method with ultrasonic treatment. After development, post-development baking may be performed using any combination of temperature and time, if necessary, to adjust the shape of the relief pattern.

[0141] As the developing solution used for development, for example, a good solvent for the negative-type photosensitive resin composition, or a combination of a good solvent and a poor solvent is preferred. Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Suitable poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative-type photosensitive resin composition. Two or more solvents, for example, several types, can also be used in combination.

[0142] (4) Hardened relief pattern formation process In this process, the relief pattern obtained by development is heat-treated to dilute the photosensitive component, thereby forming a cured relief pattern made of polyimide. Various methods can be selected for the heat treatment, such as using a hot plate, using an oven, or using a heating oven with a temperature programmable. The heat treatment can be carried out, for example, at 160°C to 350°C for 30 minutes to 5 hours. The temperature for the heat treatment is preferably 300°C or lower, more preferably 250°C or lower. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used. A cured film containing the cured product of the negative-type photosensitive resin composition disclosed herein is also one of the present inventions.

[0143] <Semiconductor device> This disclosure also provides a semiconductor device having a cured relief pattern obtained from the negative-type photosensitive resin composition described above. More specifically, a semiconductor device is provided having a substrate which is a semiconductor element and a cured relief pattern. The cured relief pattern may be manufactured using the negative-type photosensitive resin composition described above by the method for manufacturing the cured relief pattern described above.

[0144] This disclosure also provides a method for manufacturing a semiconductor device, which uses a semiconductor element as a substrate and includes the method for manufacturing a cured relief pattern of this embodiment as part of the process. In this case, the cured relief pattern formed by the method for manufacturing a cured relief pattern of this disclosure can be formed as a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and can be manufactured by combining it with a known method for manufacturing a semiconductor device.

[0145] <Display device> This disclosure also provides a display device comprising a display element and a cured film provided on the upper part of the display element, wherein the cured film is the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or it may be laminated with another layer in between. The cured film can be applied, for example, to surface protective films, insulating films, planarization films, etc., of TFT liquid crystal display elements and color filter elements; protrusions for MVA type liquid crystal display devices; partitions for the cathodes of organic EL elements; etc.

[0146] In addition to applications in semiconductor devices as described above, the negative-type photosensitive resin composition of this disclosure is also useful for applications such as interlayer insulating films in multilayer circuits, cover coats for flexible copper-clad sheets, solder resist films, and liquid crystal alignment films.

[0147] <Method for producing a negative-type photosensitive resin composition> The method for producing the negative-type photosensitive resin composition of this disclosure may include the steps of: producing (A) polyimide by the method of this disclosure as described in "(A) Method for producing polyimide" above; and mixing (A) polyimide, (B) solvent, and (C) photopolymerization initiator to obtain a negative-type photosensitive resin composition. Optionally, it may further contain an additive selected from the monomer (radical polymerization compound) having the (D) polymerizable functional group described above, (E) silane coupling agent, (F) organic titanium compound, (G) thermal crosslinking agent, (H) rust inhibitor, (I) thermal polymerization initiator, and (J) plasticizer, and other components.

Examples

[0148] While referring to the examples, this embodiment will be described more specifically. This embodiment is not limited to only the examples. The physical properties regarding the examples were measured and evaluated according to the following methods.

[0149] [Measurement and Evaluation] (1-1) Weight average molecular weight (Mw), number average molecular weight (Mn) The weight average molecular weight (Mw) and number average molecular weight (Mn) of each resin in the examples and comparative examples were measured under the following conditions using gel permeation chromatography (GPC). Also, (Mw) / (Mn) was calculated and treated as the molecular weight distribution.

[0150] As the solvent, N-methyl-2-pyrrolidone {manufactured by Fujifilm Wako Pure Chemical Corporation, dissolved by adding 30 mmol / L of lithium bromide monohydrate (manufactured by Fujifilm Wako Pure Chemical Corporation, purity 99.5%) and 50 mmol / L of phosphoric acid (manufactured by Fujifilm Wako Pure Chemical Corporation, for high performance liquid chromatography) immediately before GPC measurement} was used. Here, a calibration curve for calculating the weight average molecular weight (Mw) was created using standard polystyrene (Easical Type PS-1, manufactured by Agilent Technologies).

[0151] (Conditions) Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation) Column: 2 Tsk gel Super HM-H / 1 Tsk gel Super H-RC (manufactured by Tosoh Corporation) connected in series Flow rate: 0.5 mL / min Column temperature: 40 °C Detector: UV-8320 (UV-VIS: Ultraviolet-Visible Absorbance Spectrometer, manufactured by Tosoh Corporation)

[0152] (1-2) Total mass of fluorine atoms (Mw f ) Total mass of fluorine atoms (Mw f (A) may be determined based on the raw material components for producing polyimide.

[0153] (2) Cured relief pattern used to evaluate the flatness of the pre-baked film A photosensitive resin composition, prepared by the method described below, was rotary coated onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625 ± 25 μm) using a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation), and then pre-baked on a hot plate at 110°C for 180 seconds. This coating was then subjected to a 300 mJ / cm² test using a Prisma GHI (manufactured by Ultratech Corporation) with a test pattern mask. 2 The coating was irradiated with energy. Next, the coating was spray-developed using cyclopentanone as the developer for a time equal to 1.4 times the time it took for the unexposed areas to completely dissolve and disappear, using a coater developer (D-Spin 60A, manufactured by SOKUDO). After that, a relief pattern was obtained on the Si by rotating spray (washing) with propylene glycol methyl ether acetate for 10 seconds.

[0154] A wafer with a relief pattern formed on Si was heat-treated at 230°C for 2 hours in a nitrogen atmosphere using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh). This resulted in a cured relief pattern on Si consisting of a resin composition approximately 15 μm thick and having vias (circular openings) with a diameter of 26 μm.

[0155] Figure 1(a) is a schematic diagram showing an example of the configuration of the obtained hardened relief pattern. As shown in the figure, the hardened relief pattern 1 is constructed on a Si wafer (not shown) that constitutes the xy plane, and has circular openings (vias) 10 that open in the z direction. Here, the hardened relief pattern 1 has 3 × 3 vias 10 (a total of 9 vias formed by arranging 3 in the x direction and 3 in the y direction).

[0156] On the resulting hardened relief pattern, 200 nm thick Ti and 400 nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva).

[0157] (3) Flatness of the pre-baked film The flatness (in-plane uniformity) of the pre-baked film was evaluated as follows. On the relief pattern obtained by the method described in (2) above, a photosensitive resin composition prepared by the method described later was applied by spin coating using a coater developer (D-Spin 60A type, manufactured by SOKUDO Corporation) to a film thickness of 7 μm after drying, and then dried at 110°C for 180 seconds to form a pre-baked film. This resulted in obtaining a substrate with a pre-baked film (film-coated substrate).

[0158] The obtained film-coated substrate was split along a virtual line passing through the center of the via, and its cross-section was polished. A cross-sectional SEM image was then obtained. By observing this image, the surface irregularities of the photosensitive resin composition film were evaluated based on the following criteria.

[0159] (Evaluation Criteria) "Excellent": Less than 1.0 μm "Good": 1.0 μm or larger, less than 2.0 μm "Acceptable": 2.0 μm or more and less than 4.0 μm "Not possible": 4.0μm or more

[0160] The numerical value for surface irregularities (average of the heights of two points) was calculated as follows: In other words, the difference between the total thickness of the hardened relief pattern obtained by the method described in (2) above, and the pre-baked film formed on that pattern, and the thickness of the pre-baked film formed on the via was calculated as a numerical value for surface irregularity.

[0161] Figure 1(b) is a schematic diagram showing an example of the cross-sectional configuration of the above-mentioned film-coated substrate. As shown in the figure, the pre-baked film 2 is formed to cover the vias 10 in the cured relief pattern 1, and surface irregularities can be observed at positions corresponding to the vias 10. In this embodiment, the "numerical value of unevenness" was determined for the cross-section obtained by cutting the film-coated substrate along a virtual line L (here, line AA in the x-direction) that passes through the center C of via 10C, which is the central via among the 3x3 vias 10, and then polishing the resulting cross-section. Specifically, the "numerical value of unevenness" was calculated as the difference between the total thickness T(1+2) of the hardened relief pattern film thickness T1 and the pre-baked film T2 formed on that pattern, and the film thickness T3 of the pre-baked film formed on the via. Figure 1(b) above, "The thickness T3 of the pre-baked film formed on the via" corresponds to the lowest height of via 10C located in the center of the 3x3 grid. The "total thickness T(1+2)" corresponds to the average of the maximum height TL at the left edge of via 10C and the maximum height TR at the right edge of via 10C. Here, The maximum height TL corresponds to the highest point at the convex portion between via 10C and via 10L, which is located to the left of via 10C. The maximum height TR corresponds to the highest point at the convex portion between via 10C and via 10R, which is located to the right of via 10C. In other words, in Figure 1(b), the "numerical value of unevenness" is calculated as the difference between "{(TL+TR) / 2}" and "TC".

[0162] (4) Change in film thickness before and after heating (curing) On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, 625±25μm thick), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO), and then pre-baked on a hot plate at 110°C for 180 seconds to form a coating film approximately 7.5μm thick. This coating film was then exposed to 800mJ / cm² using a PrismaGHI S / N5503 (manufactured by Ultratech) 1:1 projection exposure system equipped with a gh-line cut filter. 2 The entire surface was exposed to light at the specified exposure level. Subsequently, the coating film formed on the wafer was spray-developed using cyclopentanone in a developing machine (D-SPIN636 model, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan). After washing with propylene glycol methyl ether acetate, it was dried by spin-drying. The film thickness after development and drying was measured, and the resulting film thickness was defined as film thickness 1. This developed and dried film was further heat-treated in a temperature-controlled curing furnace (VF-2000 model, manufactured by Koyo Lindbergh) under a nitrogen atmosphere at 230°C for 2 hours to obtain a cured film (polyimide film). The film thickness of the cured film was measured, and the resulting film thickness was defined as film thickness 2. Using these film thicknesses, the following formula: Rate of change (%) = (film thickness 2 / film thickness 1) × 100 The rate of change in film thickness before and after heating was calculated and evaluated based on the following criteria.

[0163] (Evaluation Criteria) "Excellent": Film thickness change rate before and after heating is 95% or more. "Good": Film thickness change rate before and after heating is 92% or more and less than 95%. "Acceptable": Film thickness change rate before and after heating is 90% or more but less than 92%. "Not acceptable": Film thickness change rate before and after heating is less than 90%

[0164] (5) Copper adhesion On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, 625±25μm thick), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO), and then pre-baked on a hot plate at 110°C for 180 seconds to form a coating film on the Cu. This coating film was subjected to a test using a Prisma GHI (manufactured by Ultratech) at a concentration of 800mJ / cm² without using a test pattern mask. 2 The material was irradiated with energy. Next, using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh), a cured film consisting of a resin composition with a thickness of approximately 7 μm was obtained on the Cu by heating at 230°C for 2 hours under a nitrogen atmosphere. The adhesion between the copper substrate and the cured film was evaluated based on the following criteria, in accordance with the cross-cut method of JIS K 5600-5-6 standard.

[0165] (Evaluation Criteria) "Excellent": The number of grid cells in the cured film adhering to the substrate exceeds 100. "Good": The number of grid cells in the cured film adhering to the substrate is between 80 and 100. "Acceptable": The number of grid cells in the cured film adhering to the substrate is 50 or more but less than 80. "Not acceptable": The number of grid cells in the cured film adhering to the substrate is less than 50.

[0166] (6) Hardened relief pattern used for measuring oxygen permeability A 100 nm thick layer of Al was sputtered onto a 6-inch silicon wafer (Fujimi Electronics Industries, 625 ± 25 μm thick) using a sputtering apparatus (L-440S-FHL model, Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, SOKUDO Corporation), and then pre-baked on a hot plate at 110°C for 180 seconds to form a coating film on the Al. The resulting photosensitive resin film was then subjected to a test using a Prisma GHI (Ultratech Corporation) at a concentration of 800 mJ / cm² without using a test pattern mask. 2 The sample was exposed to light, and then heated in a temperature-controlled curing furnace (VF-2000 model, manufactured by Koyo Lindbergh) under a nitrogen atmosphere at 230°C for 2 hours. This resulted in a cured film made of a resin composition with a thickness of approximately 7 μm being obtained on the Al.

[0167] (7) Oxygen permeability The cured film on Al obtained by (6) above was treated with 10% hydrochloric acid to obtain a self-supporting polyimide film. The oxygen permeability of the obtained self-supporting film (polyimide film) was measured under the following conditions. Furthermore, the average value of the obtained oxygen permeability results (n=6) was calculated and evaluated based on the following criteria.

[0168] (conditions) Equipment used: GTR-10XF (manufactured by GTR Tech Co., Ltd.) Measurement method: JIS K-7126-2 (isobaric / GC method) Measurement conditions: Temperature and humidity 23℃·65%RH / Gas type: Oxygen / Cell diameter: 35mmΦ Transmission area 9.62cm 2

[0169] (Evaluation Criteria) "Excellent": Oxygen permeability (cc / m 2 (24h ATM) Less than 200 "Good": Oxygen permeability (cc / m³) 2 (24-hour ATM) 200 to less than 500 "Acceptable": Oxygen permeability (cc / m 224-hour ATM) 500 to less than 1000 "Not possible": Oxygen permeability (cc / m 2 ·24h·atm)1000 or more

[0170] (8) Fabrication of a hardened relief pattern on Cu On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, 625±25μm thick), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO), and a coating film was formed by pre-baking on a hot plate at 110°C for 180 seconds. This coating film was then subjected to a 300mJ / cm² test using a Prisma GHI (manufactured by Ultratech) with a test pattern mask. 2 The coating was irradiated with energy. Next, the coating film was spray-developed using a coater developer (D-Spin 60A, manufactured by SOKUDO) with cyclopentanone as the developer for a time equal to 1.4 times the time it took for the unexposed areas to completely dissolve and disappear. Then, a relief pattern was obtained on the Cu by rotating spray (washing) with propylene glycol methyl ether acetate for 10 seconds.

[0171] A wafer with a relief pattern formed on Cu was heated in a nitrogen atmosphere at 230°C for 2 hours using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh), thereby forming a cured relief pattern on the Cu consisting of a resin composition with a film thickness of approximately 5 μm.

[0172] (9) Resolution of hardened relief patterns on Cu The hardened relief pattern obtained by (8) above was observed with an optical microscope, and the size of the minimum aperture pattern was determined. For the minimum aperture pattern, a pattern was considered resolved if the aperture area of ​​the obtained pattern was at least half the mask aperture area of ​​the corresponding pattern. Among the resolved apertures, the length of the mask aperture side corresponding to the one with the minimum area was treated as the resolution, and the resolving power was evaluated based on the following criteria.

[0173] (Evaluation Criteria) "Excellent": Less than 7 μm "Good": 7μm or larger and less than 10μm "Acceptable": 10 μm or more and less than 15 μm "Not possible": 15μm or more

[0174] (10) Chemical resistance test On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Corporation), and a photosensitive resin layer was formed by heating and drying on a hot plate at 110°C for 3 minutes. This photosensitive resin layer was subjected to a 500mJ / cm² test using a Prisma GHI (manufactured by Ultratech Corporation) equipped with an i-line filter, using a test pattern mask. 2 The wafer was irradiated with energy. Next, the coating film formed on the wafer was spray-developed using cyclopentanone in a developing machine (D-SPIN636 model, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan). Then, the unexposed areas were developed and removed by rinsing with propylene glycol methyl ether acetate to obtain a relief pattern of polyimide or a polyimide precursor.

[0175] A wafer with a relief pattern formed on it was heated in a temperature-controlled curing furnace (VF-2000 model, manufactured by Koyo Lindbergh) under a nitrogen atmosphere at 230°C for 2 hours to obtain a cured relief pattern made of resin with a thickness of approximately 5 μm. The obtained polyimide pattern was immersed in a solution consisting of 1 wt% potassium hydroxide, 39 wt% 3-methoxy-3-methyl-1-butanol, and 60 wt% dimethyl sulfoxide at 50°C for 10 minutes. After washing with water and air drying, the polyimide coating was evaluated by measuring the film thickness and observing it under an optical microscope. The dissolution rate per unit minute (DR) was calculated from the measured film thickness, and the chemical resistance of the coating after immersion was determined according to the evaluation criteria below.

[0176] (Evaluation Criteria) "Excellent": The change in coating film thickness compared to before immersion is within ±3%, and no cracks occurred. "Good": The change in coating film thickness compared to before immersion is greater than ±3% but within ±5%, and no cracks occurred. "Acceptable": The change in coating film thickness compared to before immersion is greater than ±5% but within ±7%, and no cracks occur. "Unacceptable": The change in coating film thickness compared to before immersion exceeds ±7%, or cracks occur.

[0177] Each abbreviation represents the compound name shown below. ODPA: 4,4'-Oxydiphthalic acid dianhydride BPDA: 4,4'-biphenylic acid dianhydride BPADA: 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride PMDA: Pyromellitic anhydride BCD: Bicyclo[2.2.2.]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BPAF: 9,9-Bis(3,4-dicarboxyphenyl)fluorenedioxide anhydride 6 FDA: 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride PDPE: 4,4'-diamino-2-phenyldiphenyl ether m-TB: 4,4'-dimethylbiphenyl-4,4'-diamine TFMB: 2,2'-bis(trifluoromethyl)benzidine HFBAPP: 4,4'-(hexafluoroisopropylidene)bis(4-aminophenoxy)benzene TPEQ: 1,4-bis(4-aminophenoxy)benzene DADPE: 4,4'-diaminodiphenyl ether HEMA: 2-hydroxyethyl methacrylate DCC: Dicyclohexylcarbodiimide NMP: N-methylpyrrolidone GBL: γ-Butyrolactone

[0178] <Synthesis Example 1> ((A) Synthesis of Polyimide A-1) A Dean-Stark extractor was attached, and 200.0 g of NMP and 22.1 g (0.08 mol) of PDPE were added to a nitrogen-purged three-necked flask. Then, 31.0 g (0.10 mol) of ODPA and 48.4 g of toluene were mixed in, and the mixture was heated to 180°C. The Dean-Stark extractor was used to confirm that the theoretical amount of water and the added toluene had been extracted. The heating was then stopped, and the mixture was allowed to cool to room temperature. This yielded the reaction solution.

[0179] The resulting reaction solution was mixed with 800 g of ethyl alcohol to obtain a precipitate consisting of crude polymer. The crude polymer was filtered off, and then mixed with 300 g of GBL to obtain a crude polymer solution. The crude polymer solution was added dropwise to 3 kg of water to precipitate the polymer, and the resulting precipitate was filtered off. Subsequently, the solution was vacuum dried to obtain a powdered polymer (polyimide A-1). The molecular weight of polyimide A-1 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 13,600, and the Mw / Mn ratio was 1.54.

[0180] <Synthesis Example 2> ((A) Synthesis of Polyimide A-2) Polyimide A-2 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 52.0 g of BPADA. The molecular weight of polyimide A-2 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 15,200, and the Mw / Mn ratio was 1.58.

[0181] <Synthesis Example 3> ((A) Synthesis of Polyimide A-3) Polyimide A-3 was obtained using the same method as in Synthesis Example 1, except that ODPA in Synthesis Example 1 was replaced with 10.9 g of PMDA and 15.5 g of ODPA. The molecular weight of polyimide A-3 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 16,000, with an Mw / Mn ratio of 1.61.

[0182] <Synthesis Example 4> ((A) Synthesis of Polyimide A-4) Polyimide A-4 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 24.8 g of BCD. The molecular weight of polyimide A-4 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 8,800, and the Mw / Mn ratio was 1.41.

[0183] <Synthesis Example 5> ((A) Synthesis of Polyimide A-5) Polyimide A-5 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 24.8 g of BCD and PDPE with 24.6 g. The molecular weight of polyimide A-5 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 12,800, with an Mw / Mn ratio of 1.52.

[0184] <Synthesis Example 6> ((A) Synthesis of Polyimide A-6) Polyimide A-6 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 24.8 g of BCD and 25.5 g of PDPE. The molecular weight of polyimide A-6 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 24,200, with an Mw / Mn ratio of 1.72.

[0185] <Synthesis Example 7> ((A) Synthesis of Polyimide A-7) Polyimide A-7 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 19.6 g of CBDA. The molecular weight of polyimide A-7 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 16,800, with an Mw / Mn ratio of 1.62.

[0186] <Synthesis Example 8> ((A) Synthesis of Polyimide A-8) Polyimide A-8 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 11.8 g of CBDA and 8.7 g of PMDA. The molecular weight of polyimide A-8 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 15,600, with an Mw / Mn ratio of 1.58.

[0187] <Synthesis Example 9> ((A) Synthesis of Polyimide A-9) Polyimide A-9 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with BPAF 45.8g, PDPE 13.3g, and m-TB 6.8g. The molecular weight of polyimide A-9 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 11,600, and the Mw / Mn ratio was 1.49.

[0188] <Synthesis Example 10> ((A) Synthesis of Polyimide A-10) Polyimide A-10 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 6.5 g of PMDA and 21.7 g of ODPA, and PDPE was replaced with 15.5 g and TFMB 6.0 g. The molecular weight of polyimide A-10 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 11,600, and the Mw / Mn ratio was 1.54.

[0189] <Synthesis Example 11> ((A) Synthesis of Polyimide A-11) Polyimide A-11 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 6.5 g of PMDA and 21.7 g of ODPA, and PDPE was replaced with 15.5 g and HFBAPP 9.7 g. The molecular weight of polyimide A-11 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 10,640, with an Mw / Mn ratio of 1.56.

[0190] <Synthesis Example 12> ((A) Synthesis of Polyimide A-12) Polyimide A-12 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 24.8 g of BCD and PDPE with 31.1 g. The molecular weight of polyimide A-12 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 12,000, with an Mw / Mn ratio of 1.51.

[0191] <Synthesis Example 13> ((A) Synthesis of Polyimide A-13) A Dean-Stark extractor was attached, and 200 g of GBL and 24.6 g of PDPE were added to a nitrogen-purged three-necked flask. Then, 24.8 g of BCD and 48.4 g of toluene were mixed in, and the mixture was heated to 180°C. The Dean-Stark extractor was used to confirm that the theoretical amount of water and the added toluene had been extracted. The heating was then stopped and the mixture was allowed to cool to room temperature. This yielded the reaction mixture.

[0192] Next, a solution of 18.6 g of DCC and 18.6 g of GBL was mixed with the above reaction mixture while stirring under ice cooling, and then 12.0 g of HEMA was added. 5.3 g of 4-dimethylaminopyridine was then added and the mixture was stirred at room temperature. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0193] The resulting reaction solution was mixed with 500 g of ethyl alcohol to obtain a precipitate consisting of crude polymer. After filtering off the crude polymer, 300 g of GBL was mixed in to obtain a crude polymer solution. The crude polymer solution was added dropwise to 3 kg of water to precipitate the polymer, and the resulting precipitate was filtered off. Subsequently, the polymer was dried under vacuum to obtain a powder (polyimide A-13). The molecular weight of polyimide A-13 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 13,200, and the Mw / Mn ratio was 1.52.

[0194] <Synthesis Example 14> ((A) Synthesis of Polyimide A-14) A Dean-Stark extractor was attached, and 200 g of GBL and 31.1 g of PDPE were added to a nitrogen-purged three-necked flask. Then, 24.8 g of BCD and 48.4 g of toluene were mixed in, and the mixture was heated to 180°C. The theoretical amount of water and the added toluene were confirmed to have been extracted using the Dean-Stark extractor. The heating was then stopped and the mixture was cooled to room temperature. This yielded the reaction mixture. The obtained reaction mixture was mixed with 7.2 g of Karenz MOI (trade name; manufactured by Showa Denko Corporation) and stirred to obtain the reaction solution.

[0195] The resulting reaction solution was mixed with 500 g of ethyl alcohol to obtain a precipitate consisting of crude polymer. After filtering off the crude polymer, 300 g of GBL was added to obtain a crude polymer solution. The crude polymer solution was added dropwise to 3 kg of water to precipitate the polymer, and the resulting precipitate was filtered off. Subsequently, the solution was vacuum-dried to obtain a powdered polymer (polyimide A-14). The molecular weight of polyimide A-14 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 12,320, with an Mw / Mn ratio of 1.51.

[0196] <Synthesis Example 15> ((A) Synthesis of Polyimide A-15) Polyimide A-15 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with BPADA 52.0 g and PDPE with TPEQ 36.5 g. The molecular weight of polyimide A-15 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 12,400, with an Mw / Mn ratio of 1.52.

[0197] <Synthesis Example 16> ((A) Synthesis of Polyimide A-16) Polyimide A-16 was obtained using the same method as in Synthesis Example 1, except that PDPE was replaced with 25.0 g of 2-phenoxybenzene-1,4-diamine. The molecular weight of polyimide A-16 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 14,000, with an Mw / Mn ratio of 1.56.

[0198] <Synthesis Example 17> ((A) Synthesis of Polyimide A-17) Polyimide A-17 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with BPDA (29.4 g) and PDPE (23.0 g). The molecular weight of polyimide A-17 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 20,000, with an Mw / Mn ratio of 1.63.

[0199] <Synthesis Example 18> ((A) Synthesis of Polyimide A-18) Polyimide A-18 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 12.4 g of BCD and 10.9 g of PMDA, and PDPE was replaced with 32.2 g. The molecular weight of polyimide A-18 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 23,000, with an Mw / Mn ratio of 1.67.

[0200] <Synthesis Example 19> ((A) Synthesis of Polyimide A-19) Polyimide A-19 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with BCD 12.4g and PMDA 10.9g, and PDPE 33.1g. The molecular weight of polyimide A-19 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 21,200, and the Mw / Mn ratio was 1.64.

[0201] <Synthesis Example 20> ((A) Synthesis of Polyimide A-20) Polyimide A-20 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 11.8 g of CBDA and 12.4 g of ODPA, and PDPE was replaced with 24.0 g of 2-phenoxybenzene-1,4-diamine. The molecular weight of polyimide A-20 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 19,000, with an Mw / Mn ratio of 1.60.

[0202] <Synthesis Example 21> ((A) Synthesis of Polyimide A-21) Polyimide A-21 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with BCD 12.4g and ODPA 15.5g, and PDPE was replaced with BAFL 29.0g. The molecular weight of polyimide A-20 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 18,500, with an Mw / Mn ratio of 1.59.

[0203] <Synthesis Example 22> ((A) Synthesis of Polyimide A-22) Polyimide A-22 was obtained using the same method as in Synthesis Example 1, except that ODPA was replaced with 44.4 g of 6-FDA and PDPE with 29.1 g of TFMB. The molecular weight of polyimide A-22 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 24,000, with an Mw / Mn ratio of 1.52.

[0204] <Synthesis Example 23> ((A) Synthesis of Polyimide A-23) Polyimide A-23 was obtained using the same method as in Synthesis Example 1, except that PDPE was replaced with 30.4 g of TFMB. The molecular weight of polyimide A-23 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 40,000, with an Mw / Mn ratio of 1.82.

[0205] <Synthesis Example 24> (Synthesis of Polyimide Precursor Polymer A-24) 31.0 g of ODPA was placed in a 1-liter separable flask as the acid component, and then 26.2 g of HEMA and 81.7 g of GBL were added and mixed. The reaction mixture was obtained by mixing in 16.3 g of pyridine while stirring at room temperature. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and then left to stand for another 16 hours.

[0206] Next, the solution of 41.3g of DCC and 41.3g of GBL was mixed with the reaction mixture over 40 minutes under ice cooling while stirring. Furthermore, the solution of 15.0g of DADPE as the diamine component and 75.1g of GBL was mixed with the reaction mixture over 60 minutes while stirring. After stirring at room temperature for 2.5 hours, 15g of ethyl alcohol was added and stirred for 30 minutes, then 97g of GBL was mixed in to obtain the reaction mixture. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0207] The resulting reaction solution was mixed with 800 g of ethyl alcohol to obtain a precipitate consisting of crude polymer. After filtering off the crude polymer, 300 g of GBL was added to obtain a crude polymer solution. The crude polymer solution was added dropwise to 3 kg of water to precipitate the polymer, and the resulting precipitate was filtered off. Subsequently, the polymer was dried under vacuum to obtain a powder (polyimide A-24). The molecular weight of polyimide A-24 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 13,600, and the Mw / Mn ratio was 1.49.

[0208] [Preparation of photosensitive resin composition] <Examples 1-56 and Comparative Examples 1-3> A resin composition solution was prepared by mixing (A) polyimide, (B) solvent, (C) photopolymerization initiator, (D) radical polymerizable compound, (E) silane coupling agent, (F) organotitanium compound, (G) thermal crosslinking agent, (H) rust inhibitor, (I) thermal polymerization initiator, and (J) plasticizer in the proportions shown in the table. The proportions listed in the table are parts by mass of each component when component (A) is 100 parts by mass.

[0209] The obtained solutions were filtered through a polyethylene filter with pores of 0.2 μm to obtain the resin compositions of Examples 1 to 56 and Comparative Examples 1 to 3. The symbols in the table represent the following components, respectively.

[0210] B-1: γ-Butyrolactone B-2: Dimethyl sulfoxide B-3: N-methyl-2-pyrrolidone B-4:3-Methoxy-N,N-dimethylpropanamide C-1:TR-PBG-3057 (product name, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) C-2: Irugacure OXE02 (product name, manufactured by BASF Japan) D-1: 2-(o-phenylphenoxy)ethyl acrylate D-2:AM-90G (product name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) D-3: Dicyclopentanyl acrylate D-4: Tris-(2-acryloxyethyl)isocyanurate D-5: Ditrimethylolpropanetetraacrylate D-6: Tetraethylene glycol dimethacrylate E-1: N-phenyl-3-aminopropyltrimethoxysilane E-2: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane F-1: Titanium diisopropoxide bis(ethylacetoacetate) F-2: Titanium diisopropoxide bis(acetylacetonate) G-1: 1,3,4,6-Tetrakis(methoxymethyl)glycoluryl G-2: 1,3-bis(methoxymethyl)urea G-3:3-functional epoxy resin VG3101L (product name, manufactured by Printec Co., Ltd.) G-4: 3,3'-Diethyl-5,5'-Dimethyl-4,4'-Bis(maleimide)diphenylmethane H-1:8-azaadenine H-2:5-amino-1H-tetrazol H-3:3-mercapto-1,2,4-triazole H-4:1H-tetrazole-5-acetic acid I-1: Dicumyl peroxide J-1: Disparon 1711EF (Product name, manufactured by Kusunoki Kasei Co., Ltd.) [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6]

[0211] In Table 6, "a / b" indicates the ratio of the number of moles of the acid component (a) to the number of moles of the diamine acid component (b).

[0212] The example demonstrated that it is possible to achieve both flatness and low oxygen permeability of the pre-baked film, resulting in a better balance compared to Comparative Examples 1 and 2. Furthermore, because the example uses a soluble polyimide with a pre-closed ring structure, it was confirmed that the change in film thickness before and after curing can be suppressed compared to the case where the polyimide precursor used in Comparative Example 3 is used as component (A). [Industrial applicability]

[0213] By using the present invention, a photosensitive resin composition can be obtained that exhibits excellent flatness of the pre-baked film, copper adhesion, and low oxygen permeability, and that can form a cured relief pattern with suppressed film shrinkage due to heating (curing). Furthermore, by using the present invention, a method for manufacturing a cured relief pattern using such a photosensitive resin composition and a cured film can be obtained. The present invention can be suitably used, for example, in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards. [Explanation of Symbols]

[0214] 1: Hardened relief pattern 2: Pre-baked film 10: Via

Claims

1. (A) Polyimide, (B) Solvent, and (C) Photopolymerization initiator A negative-type photosensitive resin composition comprising, The aforementioned (A) polyimide is given by the following general formula (1): 【Chemistry 1】 {In the formula, n is a positive integer, X is a tetravalent group with 6 to 31 carbon atoms, and Y is a divalent group.} It has a structure represented by, In equation (1) above, X is the same as in equations (2) to (9) below: 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 Having a structure represented by at least one selected from the group consisting of, In equation (1) above, Y is given by the following equations (10) to (19): 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 Having a structure represented by at least one selected from the group consisting of, The (A) polyimide mentioned above does not have polymerizable functional groups in its side chains. The weight-average molecular weight (Mw) of the polyimide (A) and, The following equation (b): R (F) Ｃｏｎｔ. ) =(M / ｆ +1) / (M / ｘ +Mw Ｙ -36)・・・(b) (In the formula, Mw ｆ This is the total mass of fluorine atoms that may be contained in the (A) polyimide, Mw Ｘ The molecular weight, Mw, of the tetracarboxylic dianhydride constituting the (A) polyimide is... Ｙ (This is the molecular weight of the diamine constituting the polyimide (A) mentioned above.) The product of R calculated by and {Mw × R(F Ｃｏｎｔ. )} is expressed in the following formula (a): 300≦Mw×R≦948...(a) A photosensitive resin composition that satisfies the following conditions.

2. The photosensitive resin composition according to claim 1, wherein the weight-average molecular weight of the (A) polyimide is 8,000 or more and 23,000 or less.

3. The photosensitive resin composition according to claim 1 or 2, further comprising (D) a radical polymerizable compound.

4. The photosensitive resin composition according to claim 3, wherein the (D) radical polymerizable compound comprises (D1) a monofunctional monomer and (D2) a polyfunctional monomer.

5. The photosensitive resin composition according to claim 4, wherein the mass ratio (D1 / D2) of the monofunctional monomer (D1) to the polyfunctional monomer (D2) is greater than 0.01 and less than 0.

5.

6. Furthermore, (E) Silane coupling agent, (F) Organic titanium compounds, (G) Thermal crosslinking agent, (H) Rust inhibitor, (I) Thermal polymerization initiator, and (J) Plasticizers, The photosensitive resin composition according to claim 1 or 2, comprising at least one selected from the group consisting of the following.

7. With respect to 100 parts by mass of the (A) polyimide, The solvent (B) is added in an amount of 30 to 1000 parts by mass, and The (C) photopolymerization initiator is 1 to 30 parts by mass, A photosensitive resin composition according to claim 1 or 2, comprising in the proportion of .

8. The photosensitive resin composition according to claim 1 or 2, wherein the (A) polyimide has polymerizable functional groups at its terminals.

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

10. A cured film comprising a cured product of the photosensitive resin composition according to claim 1 or 2.

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