Negative photosensitive resin composition and production method of the same

Abstract

To provide a negative photosensitive resin composition that gives high chemical resistance and resolution and can suppress generation of voids at an interface of a Cu layer in contact with a resin layer after a high-temperature storage test, and to provide a method for forming a cured relief pattern using the negative photosensitive resin composition of the present invention, the above composition and the above method being utilized for a fan-out type semiconductor package that has attracted attention in recent years, in which a chip encapsulation body larger than a chip size of a semiconductor chip is formed by covering the semiconductor chip with an encapsulation material, a wire redistribution layer is further formed to reach an area of the semiconductor chip and the encapsulation material, the wire redistribution layer is formed into a thin film, and the number of external connection terminals can be reduced since the wire redistribution layer can be formed to the area of the encapsulation material.SOLUTION: A negative photosensitive resin composition comprises: (A) a polyimide precursor; a specific compound (for example, (B1) an active esterifying agent, (B2) a thermosetting agent, (B3) a tertiary amine compound and / or a guanidine compound, (B4) an acidic compound, or (B5) a nitrogen-containing compound); and (C) a photopolymerization initiator.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a negative photosensitive resin composition and a method for producing the same.

Background Art

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

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

[0004] Therefore, a flip-chip mounting method has been proposed in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is turned over and directly mounted on a printed circuit board (see, for example, Patent Document 1). In this flip-chip mounting method, since the wiring distance can be accurately controlled, it is adopted for high-end devices that handle high-speed signals and for devices such as mobile phones due to their small mounting size, and the demand for it is rapidly expanding. When materials such as polyimide, polybenzoxazole, and phenolic resin are used for flip-chip mounting, after the pattern of the resin layer is formed, a metal wiring layer forming process is performed. The metal wiring layer is usually formed by plasma etching the surface of the resin layer to roughen the surface, forming a metal layer serving as a seed layer for plating with a thickness of 1 μm or less by sputtering, and then forming the metal layer by electrolytic plating using the metal layer as an electrode. At this time, generally, titanium (Ti) is used as the metal for the seed layer, and copper (Cu) is used as the metal for the redistribution layer formed by electrolytic plating.

[0005] Regarding such a metal redistribution layer, it is required that the adhesion between the redistributed metal layer and the resin layer be high after the reliability test. Examples of the reliability test include a high-temperature storage test in which the sample is stored in air at a temperature of 125°C or higher for 100 hours or more; a high-temperature operation test in which the operation is confirmed while applying a voltage with the wiring connected and storing in air at a temperature of about 125°C for 100 hours or more; a temperature cycle test in which the sample is cycled between a low-temperature state of about -65°C to -40°C and a high-temperature state of about 125°C to 150°C in air; a high-temperature and high-humidity storage test in which the sample is stored in a water vapor atmosphere at a temperature of 85°C or higher and a humidity of 85% or higher; a high-temperature and high-humidity bias test in which the same test as the high-temperature and high-humidity storage test is performed while applying a voltage with the wiring connected; and a solder reflow test in which the sample is passed through a 260°C solder reflow furnace in air or nitrogen multiple times, etc.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, conventionally, in the above-mentioned reliability tests, in the case of the high-temperature storage test, there has been a problem that voids are generated at the interface of the rewired Cu layer in contact with the resin layer after the test. When voids are generated at the interface between the Cu layer and the resin layer, the adhesion between the two decreases.

[0008] In addition to the void problem, the metal rewiring layer is required to have chemical resistance, and the demand for miniaturization is also increasing. For this reason, in particular, the photosensitive resin composition used for forming the rewiring layer of a semiconductor is required to suppress the generation of voids and exhibit high chemical resistance and resolution.

[0009] The present invention has been devised in view of such a conventional situation, and an object of the present invention is to provide a negative photosensitive resin composition (hereinafter, also simply referred to as "photosensitive resin composition" in this specification) that can obtain high chemical resistance and resolution and suppress the generation of voids at the interface of the Cu layer in contact with the resin layer after a high-temperature storage test. Another object of the present invention is to provide a method for forming a cured relief pattern using the negative photosensitive resin composition of the present invention. In recent years, fan-out type semiconductor packages have attracted attention. In a fan-out type semiconductor package, a chip encapsulant larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with an encapsulant. Further, a rewiring layer extending to the regions of the semiconductor chip and the encapsulant is formed. The rewiring layer is formed with a thin film thickness. Also, since the rewiring layer can be formed up to the region of the encapsulant, the number of external connection terminals can be increased.

Means for Solving the Problems

[0010] The inventors of the present invention have found that the above problems can be solved by combining a specific photosensitive resin with a specific compound (for example, (B1) an active esterifying agent, (B2) a thermosetting agent, (B3) a tertiary amine compound and / or a guanidine compound, (B4) an acidic compound, or (B5) a nitrogen-containing compound) and a photopolymerization initiator, and have thus completed the present invention. That is, the present invention is as follows. [1] (A) A polyimide precursor; (B) An active esterifying agent; and (C) A photopolymerization initiator A negative photosensitive resin composition containing the same. [2] The (B) active esterifying agent is at least one selected from the group consisting of bis(pentafluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, di(N-succinimidyl) carbonate, pentafluorophenol, 1-hydroxy-7-azabenzotriazole, and 4-nitrophenyl trifluoroacetate, as described in [1]. The negative photosensitive resin composition according to [1]. [3] The (A) polyimide precursor is represented by the following general formula (2): [Chemical formula] {In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a monovalent organic group.} The negative photosensitive resin composition according to [1] or [2], which contains a polyimide precursor having a structural unit represented by the formula. [4] In the general formula (2), at least one of R1 and R2 is represented by the following general formula (3): [Chemical formula] {In the formula, L1, L2, and L3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.} The negative photosensitive resin composition according to [3], which is a monovalent organic group represented by [5] In the general formula (2), X1 is the following general formula (20a): [Chemical formula] The negative photosensitive resin composition according to [3] or [4], which contains a structure represented by [6] In the general formula (2), X1 is the following general formula (20b): [Chemical formula] The negative photosensitive resin composition according to [3] or [4], which contains a structure represented by [7] In the general formula (2), Y1 is the following general formula (21b): [Chemical formula] The negative photosensitive resin composition according to any one of [3] to [6], which contains a structure represented by [8] The (A) polyimide precursor is the following general formula (4): [Chemical formula] {In the formula, R1, R2, and n1 are as defined above.} The negative photosensitive resin composition according to [3] or [4], which contains a polyimide precursor having a structural unit represented by [9] The (A) polyimide precursor is the following general formula (5): [Chemical formula] {In the formula, R1, R2, and n1 are as defined above.} The negative photosensitive resin composition according to [3] or [4], comprising a polyimide precursor having a structural unit represented by

[10] wherein the (A) polyimide precursor is represented by the following general formulas (4) and (5):

Chemical formula

Chemical formula

[11] The negative photosensitive resin composition according to

[10] , wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5).

[12] 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) active esterifying agent based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor The negative photosensitive resin composition according to any one of [1] to

[11] .

[13] A method for producing a polyimide, comprising a step of converting the negative photosensitive resin composition according to any one of [1] to

[12] into a polyimide.

[14] (1) A step of applying the negative photosensitive resin composition according to any one of [1] to

[12] onto a substrate to form a photosensitive resin layer on the substrate; (2) A step of exposing the photosensitive resin layer; (3) Developing the photosensitive resin layer after exposure to form a relief pattern; (4) Heat-treating the relief pattern to form a cured relief pattern; A method for producing a cured relief pattern, comprising:

[15] (A) A polyimide precursor; (B) A thermosetting agent; and (C) A photoinitiator A negative photosensitive resin composition comprising:

[16] The negative photosensitive resin composition according to

[15] , wherein the (B) thermosetting agent is at least one selected from the group consisting of benzoxazine, epoxy resin, and oxetane resin.

[17] The negative photosensitive resin composition according to

[15] or

[16] , wherein the (B) thermosetting agent is benzoxazine.

[18] The (A) polyimide precursor is represented by the following general formula (2):

Chemical formula

[15] to

[17] , comprising a polyimide precursor having a structural unit represented by the formula.

[19] In the general formula (2), at least one of R1 and R2 is represented by the following general formula (3):

Chemical formula

[18] , which is a monovalent organic group represented by the formula.

[20] In the general formula (2), X1 is the following general formula (20a): [Chemical formula] The negative photosensitive resin composition according to

[18] or

[19] , which contains a structure represented by

[21] In the general formula (2), X1 is the following general formula (20b): [Chemical formula] The negative photosensitive resin composition according to

[18] or

[19] , which contains a structure represented by

[22] In the general formula (2), Y1 is the following general formula (21b): [Chemical formula] The negative photosensitive resin composition according to any one of

[18] to

[21] , which contains a structure represented by

[23] The (A) polyimide precursor is the following general formula (4): [Chemical formula] {In the formula, R1, R2, and n1 are as defined above.} The negative photosensitive resin composition according to

[18] or

[19] , which contains a polyimide precursor having a structural unit represented by

[24] The (A) polyimide precursor is the following general formula (5): [Chemical formula] {In the formula, R1, R2, and n1 are as defined above.} The negative photosensitive resin composition according to

[18] or

[19] , which contains a polyimide precursor having a structural unit represented by

[25] The (A) polyimide precursor is the following general formulas (4) and (5): [Chemical formula] {In the formula, R1, R2, and n1 are as defined above, and may be the same as or different from R1, R2, and n1 in General Formula (5).} [Chemical formula] {In the formula, R1, R2, and n1 are as defined above, and may be the same as or different from R1, R2, and n1 in General Formula (4).} The negative photosensitive resin composition according to any one of

[18] to

[24] , which simultaneously contains a structural unit represented by the following formula.

[26] The negative photosensitive resin composition according to

[25] , wherein the (A) polyimide precursor is a copolymer of the structural units represented by General Formulas (4) and (5).

[27] 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) thermosetting agent based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor The negative photosensitive resin composition according to any one of

[15] to

[26] , which contains the following components.

[28] A method for producing a polyimide, which includes a step of converting the negative photosensitive resin composition according to any one of

[15] to

[27] into a polyimide.

[29] (1) A step of applying the negative photosensitive resin composition according to any one of

[15] to

[27] on a substrate to form a photosensitive resin layer on the substrate; (2) A step of exposing the photosensitive resin layer; (3) A step of developing the exposed photosensitive resin layer to form a relief pattern; (4) A step of heat-treating the relief pattern to form a cured relief pattern A method for producing a cured relief pattern, which includes the following steps.

[30] (A) Polyimide precursor; (B) The following general formula (B-1): [Chemical formula] {In the formula, Ra and Rb are each independently a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom, Rc is each independently a monovalent organic group which may contain a heteroatom, and m represents an integer of 0 to 5.} At least one selected from the group consisting of a tertiary amine compound represented by the formula and a guanidine compound; and (C) Photoinitiator; A negative photosensitive resin composition containing the same.

[31] In the general formula (B-1), the negative photosensitive resin composition according to

[30] , wherein Ra and Rb are at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[32] The guanidine compound is represented by the following general formula (B-2): [Chemical formula] {In the formula, Rd represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom.} The negative photosensitive resin composition according to

[30] , which is a compound represented by the formula.

[33] The (A) polyimide precursor is represented by the following general formula (2): [Chemical formula] {In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a monovalent organic group.} The negative photosensitive resin composition according to any one of

[30] to

[32] , which contains a polyimide precursor having a structural unit represented by the formula.

[34] In the general formula (2), at least one of R1 and R2 is a monovalent organic group represented by the following general formula (3): [Chemical formula] {In the formula, L1, L2, and L3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.} The negative photosensitive resin composition according to

[33] , wherein the composition is a monovalent organic group represented by the formula.

[35] In the general formula (2), when X1 is the following general formula (20a): [Chemical formula] The negative photosensitive resin composition according to

[33] or

[34] , which contains a structure represented by the formula.

[36] In the general formula (2), when X1 is the following general formula (20b): [Chemical formula] The negative photosensitive resin composition according to

[33] or

[34] , which contains a structure represented by the formula.

[37] In the general formula (2), when Y1 is the following general formula (21b): [Chemical formula] The negative photosensitive resin composition according to any one of

[33] to

[36] , which contains a structure represented by the formula.

[38] The (A) polyimide precursor is a polyimide precursor having a structural unit represented by the following general formula (4): [Chemical formula] {In the formula, R1, R2, and n1 are as defined above.} The negative photosensitive resin composition according to

[33] or

[34] , which contains a polyimide precursor having a structural unit represented by the formula.

[39] The (A) polyimide precursor is a polyimide precursor having a structural unit represented by the following general formula (5): [Chemical formula] {In the formula, R1, R2, and n1 are as defined above.} The negative photosensitive resin composition according to

[33] or

[34] , comprising a polyimide precursor having a structural unit represented by

[40] The (A) polyimide precursor is represented by the following general formulas (4) and (5): [Chemical formula] {In the formula, R1, R2, and n1 are each as defined above, and may be the same as or different from R1, R2, and n1 in general formula (5).} [Chemical formula] {In the formula, R1, R2, and n1 are each as defined above, and may be the same as or different from R1, R2, and n1 in general formula (4).} The negative photosensitive resin composition according to any one of

[33] to

[39] , simultaneously containing structural units represented by

[41] The negative photosensitive resin composition according to

[40] , wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5).

[42] 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) tertiary amine compound and / or guanidine compound based on 100 parts by mass of the (A) polyimide precursor, and 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor The negative photosensitive resin composition according to any one of

[30] to

[41] , comprising

[43] A method for producing a polyimide, comprising a step of converting the negative photosensitive resin composition according to any one of

[30] to

[42] into a polyimide.

[44] (1) Applying the negative photosensitive resin composition according to any one of

[30] to

[42] onto a substrate to form a photosensitive resin layer on the substrate; (2) Exposing the photosensitive resin layer; (3) Developing the exposed photosensitive resin layer to form a relief pattern; (4) Heat-treating the relief pattern to form a cured relief pattern A method for manufacturing a cured relief pattern including the above steps.

[45] The following components: (A) A polyimide precursor; (B-1) An acidic compound having two or more phenolic hydroxyl groups or carboxyl groups in its structure; and (C) A photoinitiator A negative photosensitive resin composition containing the above components.

[46] The negative photosensitive resin composition according to

[45] , wherein the (B-1) acidic compound is at least one acidic compound selected from the group consisting of methyl gallate, methylene disalicylic acid, o-coumaric acid, and phthalic acid.

[47] The negative photosensitive resin composition according to

[45] or

[46] , wherein the (B-1) acidic compound is methylene disalicylic acid or o-coumaric acid.

[48] The following components: (A) A polyimide precursor; (B-2) An acidic compound having one group selected from a phenolic hydroxyl group or a carboxyl group in its structure, and having one or more groups selected from -NH-CO-A1 or -CO-NH2 (A1 is an organic group having 1 to 4 carbon atoms); and (C) A photoinitiator A negative photosensitive resin composition containing the above components.

[49] The (B-2) acidic compound is represented by the following general formula (1):

Chemical formula

[48] .

[50] The (A) polyimide precursor is represented by the following general formula (2):

Chemical formula

[45] to

[49] , comprising a polyimide precursor having a structural unit represented by the formula.

[51] In the general formula (2), at least one of R1 and R2 is represented by the following general formula (3):

Chemical formula

[50] , which is a monovalent organic group represented by the formula.

[52] In the general formula (2), when X1 is represented by the following general formula (20a):

Chemical formula

[50] or

[51] , which contains a structure represented by the formula.

[53] In the general formula (2), when X1 is represented by the following general formula (20b):

Chemical formula

[50] or

[51] , comprising a structure represented by

[54] In the general formula (2), Y1 is the following general formula (21b):

Chemical formula

Chemical formula

[50] to

[53] , comprising a structure represented by

[55] The (A) polyimide precursor is the following general formula (4):

Chemical formula

[50] or

[51] , comprising a polyimide precursor having a structural unit represented by

[56] The (A) polyimide precursor is the following general formula (5):

Chemical formula

[50] or

[51] , comprising a polyimide precursor having a structural unit represented by

[57] The (A) polyimide precursor is the following general formula (4):

Chemical formula

[50] to

[56] , which simultaneously contains a structural unit represented by the formula.

[58] The negative photosensitive resin composition according to

[57] , wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5).

[59] 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B-1) acidic compound based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor, The negative photosensitive resin composition according to any one of

[45] to

[47] , which contains the above components.

[60] 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B-2) acidic compound based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor, The negative photosensitive resin composition according to

[48] or

[49] , which contains the above components.

[61] A method for producing a polyimide, which includes a step of converting the negative photosensitive resin composition according to any one of

[45] to

[60] into a polyimide.

[62] (1) A step of applying the negative photosensitive resin composition according to any one of

[45] to

[60] onto a substrate to form a photosensitive resin layer on the substrate; (2) A step of exposing the photosensitive resin layer; (3) Developing the photosensitive resin layer after exposure to form a relief pattern; (4) Heat-treating the relief pattern to form a cured relief pattern; A method for producing a cured relief pattern, comprising the above steps.

[63] (A) A polyimide precursor; (B) At least one nitrogen-containing compound selected from the group consisting of biuret compounds, carbazole compounds, indole compounds, hydantoin compounds, uracil derivatives, and barbituric acid compounds; and (C) A photoinitiator A negative photosensitive resin composition containing the above components.

[64] The negative photosensitive resin composition according to

[63] , wherein the (B) nitrogen-containing compound is at least one selected from the group consisting of biuret compounds, carbazole compounds, and indole compounds.

[65] The negative photosensitive resin composition according to

[63] or

[64] , wherein the (B) nitrogen-containing compound is a biuret compound.

[66] The (A) polyimide precursor is represented by the following general formula (2):

Chemical formula

[63] to

[65] , containing a polyimide precursor having a structural unit represented by the above formula.

[67] In the general formula (2), at least one of R1 and R2 is represented by the following general formula (3):

Chemical formula

[66] , which is a monovalent organic group represented by

[68] In the general formula (2), when X1 is the following general formula (20a):

Chemical formula

[66] or

[67] , which contains a structure represented by

[69] In the general formula (2), when X1 is the following general formula (20b):

Chemical formula

[66] or

[67] , which contains a structure represented by

[70] In the general formula (2), when Y1 is the following general formula (21b):

Chemical formula

[66] to

[69] , which contains a structure represented by

[71] The (A) polyimide precursor is the following general formula (4):

Chemical formula

[66] or

[67] , which contains a polyimide precursor having a structural unit represented by

[72] The (A) polyimide precursor is the following general formula (5):

Chemical formula

[66] or

[67] , which contains a polyimide precursor having a structural unit represented by

[73] wherein the (A) polyimide precursor is represented by the following general formulas (4) and (5):

Chemical formula

Chemical formula

[66] to

[72] , which simultaneously contains a structural unit represented by

[74] The negative photosensitive resin composition according to

[73] , wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5).

[75] 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) nitrogen-containing compound based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor, The negative photosensitive resin composition according to any one of

[63] to

[74] , which contains

[76] A method for producing a polyimide, which includes a step of converting the negative photosensitive resin composition according to any one of

[63] to

[75] into a polyimide.

[77] (1) A step of applying the negative photosensitive resin composition according to any one of

[63] to

[75] on a substrate to form a photosensitive resin layer on the substrate; (2) A step of exposing the photosensitive resin layer; (3) Developing the photosensitive resin layer after exposure to form a relief pattern; (4) Heat-treating the relief pattern to form a cured relief pattern; A method for manufacturing a cured relief pattern, comprising the above steps. [Advantages of the Invention]

[0011] According to the present invention, a negative photosensitive resin composition can be provided that exhibits high chemical resistance and resolution, and suppresses the generation of voids at the interface between the Cu layer and the resin layer after a high temperature storage test. Further, a method for forming a cured relief pattern using the negative photosensitive resin composition can be provided. [Embodiments for Carrying Out the Invention]

[0012] Hereinafter, embodiments for carrying out the present invention (hereinafter abbreviated as "embodiments") will be described in detail. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the invention. Throughout this specification, structures represented by the same reference numerals in the general formula may be the same as each other or different from each other when there are a plurality of them in the molecule.

[0013] [First Aspect] The first aspect according to this embodiment will be described. [Negative Photosensitive Resin Composition] The negative photosensitive resin composition according to this embodiment contains: (A) A polyimide precursor; (B1) An active esterifying agent; and (C) A photopolymerization initiator. It contains the above components.

[0014] From the viewpoint of obtaining high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) a polyimide precursor, 0.1 to 30 parts by mass of (B1) an active esterifying agent based on 100 parts by mass of the (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) a photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor.

[0015] (A) Polyimide precursor The (A) polyimide precursor in the present embodiment is a resin component contained in the negative photosensitive resin composition and is converted into polyimide by subjecting it to a heat cyclization treatment. The polyimide precursor is represented by the following general formula (2):

Chemical formula

[0016] At least one of R1 and R2 is preferably a monovalent organic group represented by the following general formula (3):

Chemical formula

[0017] Although n1 in the general formula (2) is not limited as long as it is an integer of 2 to 150, from the viewpoints of the photosensitive characteristics and mechanical characteristics of the negative photosensitive resin composition, an integer of 3 to 100 is preferable, and an integer of 5 to 70 is more preferable. In general formula (2), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties. More preferably, it is an aromatic group or an alicyclic aliphatic group in which a -COOR1 group, a -COOR2 group, and a -CONH- group are ortho to each other. As the tetravalent organic group represented by X1, specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (20): [Chemical formula] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorinated hydrocarbon group having 1 to 10 carbon atoms, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.} Examples of the group having the structure represented by the formula include, but are not limited to, these. Also, the structure of X1 may be one type or a combination of two or more types. The X1 group having the structure represented by the above formula (20) is preferable from the viewpoint of achieving both heat resistance and photosensitive properties. Among the structures represented by the above formula (20), as the X1 group, the following formula (20A) or (20B): [Chemical formula] The structure represented by the formula is more preferable from the viewpoints of chemical resistance, resolution, and void suppression after a high-temperature storage test. The following formula (20a) or (20b): [Chemical formula] [Chemical formula] The structure represented by the formula is particularly preferable.

[0018] In the above general formula (2), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties. For example, the following formula (21): [Chemical formula] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.} Examples of the structure represented by include, but are not limited to, these. Also, the structure of Y1 may be one kind or a combination of two or more kinds. The Y1 group having the structure represented by the above formula (21) is preferable from the viewpoint of achieving both heat resistance and photosensitive characteristics. As the Y1 group, among the structures represented by the above formula (21), the following formula (21A) or (21B):

Chemical formula

Chemical formula

Chemical formula

[0019] In the above general formula (3), L1 is preferably a hydrogen atom or a methyl group, and L2 and L3 are preferably hydrogen atoms from the viewpoint of photosensitive characteristics. Also, m1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitive characteristics.

[0020] In one embodiment, the (A) polyimide precursor is represented by the following general formula (4):

Chemical formula

[0021] In one embodiment, the polyimide precursor (A) is represented by the following general formula (5):

Chemical formula

[0022] Preparation method of the polyimide precursor (A) (A) The polyimide precursor is obtained by first reacting a tetracarboxylic dianhydride containing a tetravalent organic group X1 in the general formula (2) above with alcohols having a photopolymerizable unsaturated double bond and optionally alcohols having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester form), and then subjecting this to amide polycondensation with diamines containing a divalent organic group Y1 in the general formula (2) above.

[0023] (Preparation of acid / ester form) In this embodiment, examples of the tetracarboxylic dianhydride containing a tetravalent organic group X1, which is preferably used for preparing the (A) polyimide precursor, include the tetracarboxylic dianhydride represented by the general formula (20) above, and for example, pyromellitic dianhydride, diphenyl ether-3,3’,4,4’-tetracarboxylic dianhydride, benzophenone-3,3’,4,4’-tetracarboxylic dianhydride, biphenyl-3,3’,4,4’-tetracarboxylic dianhydride, diphenyl sulfone-3,3’,4,4’-tetracarboxylic dianhydride, diphenylmethane-3,3’,4,4’-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. Preferably, pyromellitic dianhydride, diphenyl ether-3,3’,4,4’-tetracarboxylic dianhydride, benzophenone-3,3’,4,4’-tetracarboxylic dianhydride, and biphenyl-3,3’,4,4’-tetracarboxylic dianhydride can be mentioned, but it is not limited thereto. These can of course be used alone, or two or more of them can be mixed and used.

[0024] In this embodiment, examples of the alcohols having a photopolymerizable unsaturated double bond, which are suitably used for preparing the polyimide precursor, include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.

[0025] It is also possible to use a partial mixture of the alcohols having a photopolymerizable unsaturated double bond with alcohols having no unsaturated double bond, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, and the like.

[0026] Further, as the polyimide precursor, a non-photosensitive polyimide precursor prepared only from the alcohols having no unsaturated double bond may be mixed with the photosensitive polyimide precursor and used. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

[0027] The above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohols are stirred and dissolved in a solvent as described below in the presence of a basic catalyst such as pyridine at a temperature of 20 to 50 ° C for 4 to 10 hours and mixed, whereby the esterification reaction of the acid anhydride proceeds and a desired acid / ester form can be obtained.

[0028] (Preparation of Polyimide Precursor) To the above acid / ester form (typically a solution in a solvent described later), a suitable dehydrating condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. is added and mixed under ice-cooling to convert the acid / ester form into a polyacid anhydride. Then, a diamine containing a divalent organic group Y1 preferably used in this embodiment, which is separately dissolved or dispersed in a solvent, is dropped and added, and amide polycondensation is carried out to obtain the target polyimide precursor. Alternatively, after the acid / ester form is converted into an acid chloride by using thionyl chloride or the like, the target polyimide precursor can be obtained by reacting it with a diamine compound in the presence of a base such as pyridine.

[0029] Examples of diamines containing the divalent organic group Y1 preferably used in this embodiment include diamines having the structure represented by the above general formula (21), such as p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and those in which a part of the hydrogen atoms on these benzene rings are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,Examples include, but are not limited to, 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

[0030] After completion of the amide polycondensation reaction, the water-absorbing by-products of the dehydrating condensing agent coexisting in the reaction solution are filtered off as necessary, and then a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component. Further, by repeating operations such as redissolution and reprecipitation, the polymer is purified and vacuum dried to isolate the target polyimide precursor. To improve the purification degree, the polymer solution may be passed through a column filled with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0031] The molecular weight of the above (A) polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, when measured by the polystyrene-equivalent weight-average molecular weight by gel permeation chromatography. When the weight-average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The weight-average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

[0032] (B1) Active esterifying agent The (B1) active esterifying agent in this embodiment is not limited as long as it is a compound capable of converting a carboxylic acid, a carboxylic acid ester, or the like into a highly active ester compound. Specifically, bis(pentafluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, di(N-succinimidyl) carbonate, pentafluorophenol, 4-nitrophenyl trifluoroacetate, 1-hydroxy-7-azabenzotriazole, etc. can be exemplified. Among these, from the viewpoint of suppressing Cu voids, 1-hydroxy-7-azabenzotriazole and pentafluorophenol are preferable. When the above active esterifying agent is used, good chemical resistance, resolution, and Cu void suppression effect can be obtained. Without being bound by theory, regarding the reason for obtaining good chemical resistance, it is considered that by using the active esterifying agent, imidization proceeds at a lower temperature during heating, making it easier for the packing of the polyimide to proceed and improving the chemical resistance. Also, the reason for obtaining good resolution is unclear, but it is considered that the active esterifying agent before heating is easily dissolved by the developer during development when blended with the polyimide precursor, suppressing the residue. In addition, the reason for showing the Cu void suppression effect is not clear, but it is considered that the active esterifying agent generates polar functional groups (such as hydroxyl groups) during heating, and this hydroxyl group strongly interacts with Cu ions, suppressing the diffusion of Cu and as a result suppressing Cu voids.

[0033] The above active esterifying agent in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. By blending in the range of 0.1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the (A) polyimide precursor, a negative photosensitive resin composition particularly excellent in the Cu void suppression effect, resolution improvement, and chemical resistance improvement effects can be obtained.

[0034] (C) Photoinitiator The (C) photoinitiator used in this embodiment will be described. The photoinitiator is preferably a free radical photoinitiator, and examples thereof include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether; oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-aryl glycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide, etc. are preferably included, but are not limited thereto. Among the above photoinitiators, oximes are more preferable from the viewpoint of light sensitivity in particular.

[0035] The compounding amount of the (C) photoinitiator in the negative photosensitive resin composition is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. The above compounding amount is 0.1 part by mass or more from the viewpoint of light sensitivity or patterning property, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

[0036] The negative photosensitive resin composition of this embodiment may further contain components other than the above components (A) to (C). Examples of components other than components (A) to (C) include, but are not limited to, solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organotitanium compounds, adhesion aids, sensitizers, photopolymerizable unsaturated monomers, thermal polymerization inhibitors, and the like. Among these, the nitrogen-containing heterocyclic compound as an optional component is a compound other than the "nitrogen-containing compound" described in the fifth aspect described later.

[0037] Solvent Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. can be used. Among them, from the viewpoints of resin solubility, stability of the resin composition, and adhesion to the substrate, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

[0038] Among such solvents, those that can completely dissolve the resulting polymer are particularly preferred. Examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma-butyrolactone, and the like.

[0039] In the photosensitive resin composition of the present embodiment, the amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0040] Nitrogen-containing heterocyclic compound When forming a cured film on a substrate made of copper or a copper alloy using the photosensitive resin composition of the present embodiment, in order to suppress discoloration on the copper, the negative photosensitive resin composition may optionally contain a nitrogen-containing heterocyclic compound. Examples of the nitrogen-containing heterocyclic compound include azole compounds and purine derivatives.

[0041] 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-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like.

[0042] Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or as a mixture of two or more.

[0043] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azadenine, 5-azadenine, 8-azadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, etc. and their derivatives.

[0044] When the photosensitive resin composition contains the above azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the (A) polyimide precursor, from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound is 0.1 part by mass or more based on 100 parts by mass of the (A) polyimide precursor, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, discoloration of the copper or copper alloy surface is suppressed. On the other hand, when it is 20 parts by mass or less, it has excellent photosensitivity.

[0045] Hindered phenol compound In addition, in order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(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, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like can be mentioned, but are not limited thereto. 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 and the like are particularly preferred.,

[0046] The compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polyimide precursor (A). When the compounding amount of the hindered phenol compound is 0.1 part by mass or more based on 100 parts by mass of the polyimide precursor (A), for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented. On the other hand, when it is 20 parts by mass or less, it has excellent photosensitivity.

[0047] Organic titanium compound The negative photosensitive resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound, a photosensitive resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

[0048] Examples of usable organic titanium compounds include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII): I) Titanium chelate compounds: Among them, titanium chelates having two or more alkoxy groups are more preferable because of the storage stability of the negative photosensitive resin composition and the ability to obtain good patterns. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), and the like. II) Tetraalkoxytitanium 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 tetrasteariloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, and the like. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate, and the like.

[0049] Among them, the organotitanium compound is preferably at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound, from the viewpoint of exhibiting better chemical resistance. Titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

[0050] When the organotitanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the (A) polyimide precursor. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is achieved.

[0051] Adhesion aid In order to improve the adhesion between the film formed using the negative photosensitive resin composition of this embodiment and the substrate, the negative photosensitive resin composition may optionally contain an adhesion promoter. Examples of the adhesion promoter include silane coupling agents such as γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3’-bis(N-[3-triethoxysilyl]propylamide)-4,4’-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and aluminum ethylacetoacetate diisopropylate.

[0052] Among these adhesion promoters, it is more preferable to use a silane coupling agent from the viewpoint of adhesion strength. When the photosensitive resin composition contains an adhesion promoter, the blending amount of the adhesion promoter is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0053] Examples of silane coupling agents include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Silace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Co., Ltd.: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea,N-(3-Methoxydipropoxysilylpropyl)urea, N-(3-Trimethoxysilylethyl)urea, N-(3-Ethoxydimethoxysilylethyl)urea, N-(3-Tripropoxysilylethyl)urea, N-(3-Tripropoxysilylethyl)urea, N-(3-Ethoxydipropoxysilylethyl)urea, N-(3-Dimethoxypropoxysilylethyl)urea, N-(3-Methoxydipropoxysilylethyl)urea, N-(3-Trimethoxysilylbutyl)urea, N-(3-Triethoxysilylbutyl)urea, N-(3-Tripropoxysilylbutyl)urea, 3-(m-Aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-Aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-Aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.1), Aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), 2-(Trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: 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, Tetrakis(methoxyethoxysilane), 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-butylphenylsilanediol, 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, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, etc. are mentioned, but not limited thereto. These may be used alone or in combination of multiple.

[0054] As the silane coupling agent, among the above-mentioned silane coupling agents, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following formula:

Chemical formula

[0055] When used as the compounding amount in the photosensitive resin composition in the case of using a silane coupling agent, 0.01 to 20 parts by mass is preferable with respect to 100 parts by mass of the (A) polyimide precursor.

[0056] Sensitizer The negative photosensitive resin composition of this embodiment may optionally contain a sensitizer in order to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combinations of, for example, 2 to 5 types.

[0057] When the photosensitive resin composition contains a sensitizer to improve photosensitivity, the blending amount is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

[0058] Photopolymerizable unsaturated monomer The negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. Such monomers are preferably (meth)acrylic compounds that undergo radical polymerization by a photopolymerization initiator, and are not particularly limited to the following, but include ethylene glycol or polyethylene glycol mono- or diacrylates and methacrylates such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, propylene glycol or polypropylene glycol mono- or diacrylates and methacrylates, glycerol mono-, di- or triacrylates and methacrylates, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate, neopentyl glycol diacrylate and dimethacrylate, bisphenol A mono- or diacrylates and methacrylates, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di- or triacrylates and methacrylates, pentaerythritol di-, tri- or tetraacrylates and methacrylates, and compounds such as ethylene oxide or propylene oxide adducts of these compounds.

[0059] When the photosensitive resin composition contains the above monomer having a photopolymerizable unsaturated bond to improve the resolution of the relief pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

[0060] Thermal polymerization inhibitor Further, the negative photosensitive resin composition of the present embodiment may optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition particularly during storage in a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, and the like.

[0061] <Method for Manufacturing Cured Relief Pattern and Semiconductor Device> The present invention also provides a method for manufacturing a cured relief pattern, comprising: (1) a step of applying the negative photosensitive resin composition of the above-described present embodiment onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) a step of heat-treating the relief pattern to form a cured relief pattern.

[0062] (1) Photosensitive Resin Layer Formation Step In this step, the negative photosensitive resin composition of the present invention is applied onto a base material and, if necessary, dried thereafter to form a photosensitive resin layer. As the coating method, methods conventionally used for coating 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.

[0063] If necessary, the coating film containing the photosensitive resin composition can be dried. As the drying method, methods such as air drying, heat drying by an oven or a hot plate, and vacuum drying are used. Specifically, when performing air drying or heat drying, drying can be performed under the conditions of 20°C to 140°C for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on the substrate.

[0064] (2) Exposure process In this process, the photosensitive resin layer formed above is exposed to ultraviolet light source or the like through a photomask or reticle having a pattern or directly using an exposure apparatus such as a contact aligner, a mirror projection, or a stepper.

[0065] Thereafter, for the purpose of improving photosensitivity and the like, if necessary, post-exposure bake (PEB) and / or pre-development bake may be performed according to an arbitrary combination of temperature and time. Regarding the range of the bake conditions, the temperature is preferably 40°C to 120°C and the time is preferably 10 seconds to 240 seconds, but it is not limited to this range as long as the characteristics of the photosensitive resin composition of the present invention are not inhibited.

[0066] (3) Relief pattern formation process In this process, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As the developing method for developing the photosensitive resin layer after exposure (irradiation), an arbitrary method can be selected and used from conventionally known photoresist developing methods, such as the spin spray method, the paddle method, the dipping method with ultrasonic treatment, etc. Further, after development, if necessary, a post-development bake may be performed according to an arbitrary combination of temperature and time for the purpose of adjusting the shape of the relief pattern.

[0067] As the developer used for development, for example, a good solvent for the negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. Examples of the good solvent include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When the good solvent and the poor solvent are mixed and used, 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 photosensitive resin composition. Also, two or more kinds of each solvent, for example, several kinds can be combined and used.

[0068] (4) Curing Relief Pattern Formation Step In this step, the relief pattern obtained by the above development is heated to disperse the photosensitive component, and (A) the polyimide precursor is imidized to convert it into a cured relief pattern made of polyimide. As the method of heat curing, for example, various methods such as those using a hot plate, those using an oven, and those using a temperature-programmable heating oven can be selected. The heating can be carried out, for example, under the conditions of 170 °C to 400 °C for 30 minutes to 5 hours. As the atmospheric gas during heat curing, air may be used, or an inert gas such as nitrogen or argon can also be used.

[0069] <Polyimide> The structure of the polyimide contained in the cured relief pattern formed from the above polyimide precursor composition is represented by the following general formula (8). [Chemical formula] {In the formula, X 1 and Y 1 are the same as X1 and Y1 in the general formula (2), and m is a positive integer.} For the same reason, preferred X1 and Y1 in the general formula (2) are also preferred in the polyimide of the general formula (8). The number of repeating units m in the general formula (8) may be any positive integer and is not particularly limited, but may be an integer of 2 to 150, or an integer of 3 to 140. A method for producing a polyimide including a step of converting the negative photosensitive resin composition described above into a polyimide is also an aspect of the present invention.

[0070] <Semiconductor device> In the present embodiment, a semiconductor device having a cured relief pattern obtained by the method for producing a cured relief pattern described above is also provided. Therefore, a semiconductor device having a base material that is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the method for producing a cured relief pattern described above can be provided. Further, the present invention can also be applied to a method for producing a semiconductor device that uses a semiconductor element as a base material and includes the method for producing a cured relief pattern described above as part of a process. The semiconductor device of the present invention can be manufactured by forming the cured relief pattern formed by the method for producing a cured relief pattern as a surface protection film, an interlayer insulating film, a rewiring insulating film, a protection film for a flip chip device, or a protection film of a semiconductor device having a bump structure, and combining it with a known method for manufacturing a semiconductor device.

[0071] <Display device> In the present embodiment, a display device including a display element and a cured film provided on top of the display element, wherein the cured film is the cured relief pattern described above, is provided. Here, the cured relief pattern may be laminated directly in contact with the display element, or may be laminated with another layer interposed therebetween. For example, examples of the cured film include a surface protection film, an insulating film, and a planarizing film for a thin film transistor (TFT) liquid crystal display element and a color filter element, protrusions for a multi-domain vertical alignment (MVA) type liquid crystal display device, and partitions for an organic electroluminescence (EL) element cathode.

[0072] In addition to the application to the semiconductor device as described above, the negative photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad laminates, solder resist films, and liquid crystal alignment films.

[0073] [Second Aspect] The second aspect according to this embodiment will be described. <Negative Photosensitive Resin Composition> The negative photosensitive resin composition according to this embodiment is (A) Polyimide precursor; (B2) Thermosetting agent; and (C) Photoinitiator and contains.

[0074] From the viewpoint of obtaining high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor, 0.1 to 30 parts by mass of (B2) thermosetting agent based on 100 parts by mass of (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) photoinitiator based on 100 parts by mass of (A) polyimide precursor.

[0075] (A) Polyimide precursor In this embodiment, as the (A) polyimide precursor, those shown in the first aspect can be used.

[0076] (B2) Thermosetting agent The (B2) thermosetting agent in this embodiment is not limited as long as it is a compound capable of promoting curing by heating. Among them, from the viewpoint of adhesion to the encapsulant, benzoxazine, epoxy resin, and oxetane resin are preferable, and benzoxazine is more preferable. Examples of benzoxazine include those having a structure represented by the following general formula (10) or (11) can be mentioned. [Chemical Formula] [Chemical Formula] Examples of the epoxy resin include aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and naphthalene epoxy resin, and alicyclic epoxy resins such as 3’,4’-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and ε-caprolactone-modified 3’,4’-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. Examples of the alicyclic epoxy resin include the following general formula (12): [Chemical formula] and the like can also be mentioned. Examples of the oxetane resin include 3-allyloxyoxetane and 3-oxetanyl p-toluenesulfonate.

[0077] When the above-mentioned thermosetting agent is used, good chemical resistance, resolution, and Cu void suppression effect can be obtained. Without being bound by theory, regarding the reason for obtaining good chemical resistance, it is considered that the penetration of the chemical solution is suppressed by forming a higher-order network after thermal crosslinking, thereby improving the chemical resistance. Also, the reason for obtaining good resolution is unclear, but it is considered that the thermosetting agent before heat curing is easily dissolved by the developing solution during development and the residue is suppressed because it is blended with the polyimide precursor. In addition, the reason for showing the Cu void suppression effect is not clear, but it is considered that the thermosetting agent generates a hydroxyl group or the like by heating, and this hydroxyl group strongly interacts with Cu ions, suppressing the diffusion of Cu and as a result suppressing Cu voids.

[0078] The above-mentioned thermosetting agent in the negative-type photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. By blending in the range of 0.1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the (A) polyimide precursor, a negative-type photosensitive resin composition having particularly excellent Cu void suppression effect, improved resolution, and improved chemical resistance can be obtained.

[0079] (C) Photoinitiator In this embodiment, as the (C) photoinitiator, those shown in the first aspect can be used.

[0080] Other components In this embodiment, as the other components, such as solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organotitanium compounds, adhesion aids, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors, those shown in the first aspect can be used.

[0081] [Method for manufacturing cured relief pattern and semiconductor device] In this embodiment, for the method for manufacturing a cured relief pattern and the semiconductor device, those the same as those shown in the first aspect can be applied.

[0082] [Polyimide] In this embodiment, as the polyimide, those the same as those shown in the first aspect can be applied.

[0083] [Semiconductor device] In this embodiment, as the semiconductor device, those the same as those shown in the first aspect can be applied.

[0084] [Display device] In this embodiment, as the display device, those the same as those shown in the first aspect can be applied.

[0085] The negative photosensitive resin composition according to this embodiment is, like the negative photosensitive resin composition shown in the first aspect, useful not only for application to the above semiconductor device but also for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad boards, solder resist films, and liquid crystal alignment films. The preferable configurations, numerical ranges, or steps shown in the first aspect can also be treated as preferable configurations, numerical ranges, or steps in this embodiment.

[0086] [Third aspect] The third aspect according to this embodiment will be described. <Negative photosensitive resin composition> The negative photosensitive resin composition according to this embodiment is (A) Polyimide precursor; (B3) The following general formula (B-1):

Chemical formula

[0087] From the viewpoint of obtaining a high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B3) above-mentioned tertiary amine compound and / or guanidine compound based on 100 parts by mass of the (A) polyimide precursor, and 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor.

[0088] (A) Polyimide precursor In this embodiment, as the (A) polyimide precursor, those shown in the first aspect can be used.

[0089] (B3) Tertiary amine compound and / or guanidine compound The (B3) tertiary amine compound in this embodiment is the following general formula (B-1):

Chemical formula

[0090] The guanidine compound in this embodiment is not limited as long as it has a guanidine structure. Among these, from the viewpoint of storage stability of the resin composition, the following general formula (B-2):

Chemical formula

[0091] When the above tertiary amine compound and / or guanidine compound is used, good chemical resistance, resolution, and Cu void suppression effect can be obtained. Without being bound by theory, regarding the reason for obtaining good chemical resistance, it is considered that after heat curing, the nitrogen atom and the polyimide resin form a higher-order network, suppressing the penetration of the chemical solution and improving the chemical resistance. Also, the reason for obtaining good resolution is unclear, but it is considered that the above tertiary amine compound and / or guanidine compound before heat curing is easily dissolved by the developing solution during development and the residue is suppressed when blended with the polyimide precursor. In addition, the reason for showing the Cu void suppression effect is not clear, but it is considered that the nitrogen atom of the above compound strongly interacts with Cu ions, suppressing the diffusion of Cu and as a result suppressing Cu voids.

[0092] The above tertiary amine compound or guanidine compound in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. By blending in the range of 0.1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the (A) polyimide precursor, a negative photosensitive resin composition particularly excellent in the Cu void suppression effect, resolution improvement, and chemical resistance improvement effects can be obtained.

[0093] (C) Photoinitiator In the present embodiment, as the (C) photoinitiator, those shown in the first aspect can be used.

[0094] Other components In the present embodiment, as other components, solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, adhesion aids, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors shown in the first aspect can be used.

[0095] <Method for manufacturing a cured relief pattern and semiconductor device> In this embodiment, the method for manufacturing a cured relief pattern and the semiconductor device can be the same as those shown in the first aspect.

[0096] <Polyimide> In this embodiment, the polyimide can be the same as that shown in the first aspect.

[0097] <Semiconductor device> In this embodiment, the semiconductor device can be the same as that shown in the first aspect.

[0098] <Display device> In this embodiment, the display device can be the same as that shown in the first aspect.

[0099] The negative photosensitive resin composition according to this embodiment is, like the negative photosensitive resin composition shown in the first aspect, useful not only for application to the semiconductor device as described above, but also for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad laminates, solder resist films, and liquid crystal alignment films. The preferable configurations, numerical ranges, or processes shown in the first aspect can also be treated as preferable configurations, numerical ranges, or processes in this embodiment.

[0100] [Fourth aspect] The fourth aspect according to this embodiment will be described. <Negative photosensitive resin composition> The negative photosensitive resin composition according to this embodiment (A) A polyimide precursor; (B4) An acidic compound; and (C) A photoinitiator is included. (B4) As the acidic compound, there may be mentioned (B-3) an acidic compound having two or more phenolic hydroxyl groups or carboxyl groups in the structure, or (B-4) an acidic compound having one group selected from a phenolic hydroxyl group or a carboxyl group in the structure and having one or more groups selected from -NH-CO-A1 or -CO-NH2 (A1 is an organic group having 1 to 4 carbon atoms).

[0101] From the viewpoint of obtaining a high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) a polyimide precursor, 0.1 to 30 parts by mass of (B4) an acidic compound based on 100 parts by mass of the (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) a photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor.

[0102] (A) Polyimide precursor In the present embodiment, as the (A) polyimide precursor, those shown in the first aspect can be used.

[0103] (B4) Acidic compound (B-3) The (B-3) acidic compound in the present embodiment is an acidic compound having two or more phenolic hydroxyl groups or carboxyl groups in the structure. The acidic compound according to the present embodiment may have two or more carboxyl groups in the structure, may have two or more phenolic hydroxyl groups, or may have both a carboxyl group and a phenolic hydroxyl group. Among these, from the viewpoints of developability and Cu void suppression, a compound having both a carboxyl group and a phenolic hydroxyl group is preferable.

[0104] Examples of the compound having two or more carboxyl groups according to this embodiment include phthalic acid, pyromellitic acid, 2,3-naphthalenedicarboxylic acid, trimellitic acid, benzene pentacarboxylic acid, 4-methylphthalic acid, 4-trifluoromethylphthalic acid, 4-methoxyphthalic acid, 1,3,5-tribenzenecarboxylic acid, isophthalic acid, 5-methylisophthalic acid, terephthalic acid, 1,4-naphthaleneterephthalic acid, 2,5-dimethylterephthalic acid, 3,4-pyridinedicarboxylic acid, and the like. Among these compounds, from the viewpoint of chemical resistance, phthalic acid, isophthalic acid, and terephthalic acid are preferable.

[0105] Examples of the compound having two or more phenolic hydroxyl groups according to this embodiment include catechol, pyrogallol, 2,3-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1,2,4-trihydroxybenzene, hexahydroxybenzene, 4-methylcatechol, 3-methoxycat e chol, methyl gallate, 5-methylpyrogallol, 2,3,4-trihydroxybenzaldehyde, resorcinol, 1,3-dihydroxynaphthalene, 5-methoxyresorcinol, 2,4-dihydroxybenzamide, 3,5-dihydroxybenzamide, and the like. Among these compounds, from the viewpoint of chemical resistance, methyl gallate, 1,2,4-trihydroxybenzene, 2,4-dihydroxybenzamide, and 3,5-dihydroxybenzamide are preferable.

[0106] Examples of the compound having both a phenolic hydroxyl group and a carboxyl group according to this embodiment include methylene disalicylate, o-coumaric acid, 2-hydroxybenzoic acid, 4-methylsalicylic acid, 4-hydroxyisophthalic acid, 4-hydroxyphthalic acid, 5-hydroxyisophthalic acid, and the like. Among these, from the viewpoint of chemical resistance, methylene disalicylate and o-coumaric acid are preferable.

[0107] (B-4) As another embodiment, (B-4) the acidic compound has one group selected from a phenolic hydroxyl group or a carboxyl group in the structure, and has one or more groups selected from -NH-CO-A1 or -CO-NH2 (where A1 is an organic group having 1 to 4 carbon atoms).

[0108] (B-4) From the viewpoint of chemical resistance, the acidic compound is represented by the following general formula (1):

Chemical formula

[0109] Although A1 is an organic group having 1 to 4 carbon atoms, from the viewpoint of chemical resistance, it is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. Although A2 is a hydroxyl group or a carboxyl group, from the viewpoint of sensitivity, it is preferably a carboxyl group. Although A3 is a group selected from -NH-CO-A1 or -CO-NH2, from the viewpoint of chemical resistance, -NH-CO-A1 is more preferable. Although A4 is a monovalent group, it is more preferably a monovalent organic group, and even more preferably an alkyl group having 1 to 4 carbon atoms. Although m2 is 1 or 2, it is more preferably 1. Although m3 is an integer from 0 to 4, it is more preferably 0 or 1.

[0110] As the acidic compound having one group selected from a phenolic hydroxyl group or a carboxyl group and having one or more -NH-CO-A1 in the structure according to this embodiment, 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, 4-acetamidobenzoic acid, 5-acetamido-2-aminobenzoic acid, 2-acetamido-5-bromobenzoic acid, 2-(acetoacetamido)benzoic acid, 2-acetamido-6-nitrobenzoic acid, 2-acetamidophenol, 3-acetamidophenol, 4-acetamidophenol, 2-acetamido-4-methylphenol can be mentioned. Among these compounds, from the viewpoint of chemical resistance, 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, 4-acetamidobenzoic acid, 2-acetamidophenol, 3-acetamidophenol, 4-acetamidophenol are preferable, and from the viewpoint of sensitivity, 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, 4-acetamidobenzoic acid are more preferable.

[0111] As the acidic compound having one group selected from a phenolic hydroxyl group or a carboxyl group and having one or more -CO-NH2 in the structure according to this embodiment, phthalamic acid, terephthalamic acid, 2-hydroxybenzamide, 2-hydroxy-4-methoxybenzamide, 4-hydroxybenzamide, 5-acetyl-2-hydroxybenzamide, 5-chloro-2-hydroxybenzamide, 3-hydroxybenzamide can be mentioned. Among these compounds, from the viewpoint of chemical resistance, phthalamic acid, terephthalamic acid, 2-hydroxybenzamide, 3-hydroxybenzamide, 4-hydroxybenzamide are preferable.

[0112] When the above-mentioned (B4) acidic compound is used, good chemical resistance, resolution, and Cu void suppression effect can be obtained. Without being bound by theory, regarding the reason for obtaining good chemical resistance, it is considered that after thermosetting, it interacts with the polyimide part through hydrogen bonding or the like to form a higher-order network, suppressing the penetration of the chemical solution and improving the chemical resistance. Also, although the reason for obtaining good resolution is unclear, it is considered that the acidic compound before heat curing is easily dissolved by the developing solution during development and the residue is suppressed because it is blended with the polyimide precursor. In addition, although the reason for showing the Cu void suppression effect is not clear, it is considered that the carboxyl group, phenolic hydroxyl group, and / or amide group in the acidic compound strongly interact with Cu ions, suppressing the diffusion of Cu and as a result suppressing Cu voids.

[0113] The above-mentioned acidic compound in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. By blending in the range of 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, a negative photosensitive resin composition particularly excellent in the Cu void suppression effect, resolution improvement, and chemical resistance improvement effects can be obtained.

[0114] (C) Photoinitiator In the present embodiment, as the (C) photoinitiator, those shown in the first aspect can be used.

[0115] Other components In the present embodiment, as other components, solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organotitanium compounds, adhesion aids, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors shown in the first aspect can be used.

[0116] <Method for manufacturing a cured relief pattern and semiconductor device> In the present embodiment, the method for manufacturing a cured relief pattern and the semiconductor device shown in the first aspect can be applied.

[0117] <Polyimide> In this embodiment, the same polyimide as that shown in the first aspect can be applied.

[0118] <Semiconductor device> In this embodiment, the same semiconductor device as that shown in the first aspect can be applied.

[0119] <Display device> In this embodiment, the same display device as that shown in the first aspect can be applied.

[0120] The negative photosensitive resin composition according to this embodiment is similar to the negative photosensitive resin composition shown in the first aspect. In addition to being applied to the semiconductor device as described above, it is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad laminates, solder resist films, and liquid crystal alignment films. The preferred configurations, numerical ranges, or processes shown in the first aspect can also be treated as preferred configurations, numerical ranges, or processes in this embodiment.

[0121] [Fifth aspect] The fifth form according to this embodiment will be described. <Negative photosensitive resin composition> The negative photosensitive resin composition according to this embodiment (A) Polyimide precursor; (B5) At least one nitrogen-containing compound selected from the group consisting of biuret, carbazole, indole, hydantoin, uracil derivatives, and barbituric acid; and (C) Photoinitiator contains.

[0122] From the viewpoint of obtaining high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor, at least one nitrogen-containing compound selected from the group consisting of 0.1 to 30 parts by mass of (B5) biuret, carbazole, indole, hydantoin, uracil derivative and barbituric acid based on 100 parts by mass of the (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor.

[0123] (A) Polyimide precursor In this embodiment, as the (A) polyimide precursor, those shown in the first aspect can be used.

[0124] (B5) Nitrogen-containing compound The (B5) nitrogen-containing compound in this embodiment is selected from biuret compounds, carbazole compounds, indole compounds, hydantoin compounds, uracil derivatives, and barbituric acid compounds. The biuret compound according to this embodiment is not limited as long as it has a biuret structure (R-NH-CO-NR’-CO-NH-R’’). R, R’, and R’’ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Among them, the following structure (biuret) in which all of R, R’, and R’’ are hydrogen atoms is preferred. [Chemical formula]

[0125] The carbazole compound according to this embodiment is not limited as long as it has a carbazole structure. Examples of such compounds include carbazole, 3,6-diaminocarbazole, 3,6-dimethylcarbazole, 3-methyl-9H-carbazole, 3-phenyl-9H-carbazole, 3-t-butyl-9H-carbazole, 3,6-diethynylcarbazole, 2-methoxycarbazole, and the like. Among them, from the viewpoint of chemical resistance, carbazole and 3,6-diaminocarbazole are preferred.

[0126] The indole compound according to this embodiment is not limited as long as it has an indole structure. Examples of such compounds include indole, 6-aminoindole, 5-aminoindole, 4-aminoindole, 5-methylindole, 7-methylindole, indole-5-carboxaldehyde, 5-hydroxyindole, 5-nitroindole, methyl indole-5-carboxylate, 6-methoxyindole, 3-acetylindole, and the like. Among these, from the viewpoint of drug resistance, indole, 6-aminoindole, 5-aminoindole, and 4-aminoindole are preferable.

[0127] The hydantoin compound according to this embodiment is not limited as long as it has a hydantoin structure. Examples of such compounds include hydantoin, 5,5-dimethylhydantoin, 5-methylhydantoin, 5-ethylhydantoin, 5-phenylhydantoin, 5-(4-hydroxyphenyl)hydantoin, and the like. Among these, from the viewpoint of drug resistance, hydantoin, 5-methylhydantoin, and 5-(4-hydroxyphenyl)hydantoin are preferable.

[0128] The uracil derivative according to this embodiment is not limited as long as it is uracil, its tautomer, or its derivative. Examples of such compounds include uracil (also known as pyrimidine-2,4(1H,3H)-dione), hydroxypyrimidinone, 2,4-dihydroxypyrimidine, nucleosides derived from uracil (such as uridine), 5-methyl-substituted products (thymine), fluorouracil, uridylic acid, and the like. Among these, from the viewpoint of drug resistance, uracil is preferable.

[0129] The barbituric acid compound according to this embodiment is not limited as long as it has a barbituric acid structure. Examples of such compounds include violuric acid, barbituric acid, alloxan, allobarbital, cyclobarbital, and the like. Among these, from the viewpoint of drug resistance, violuric acid and barbituric acid are preferable.

[0130] When the above nitrogen-containing compound is used, good chemical resistance, resolution, and Cu void suppression effect can be obtained. Without being bound by theory, regarding the reason for obtaining good chemical resistance, it is considered that after thermosetting, it interacts with the polyimide part to form a higher-order network, suppressing the penetration of the chemical solution and improving the chemical resistance. Also, the reason for obtaining good resolution is unclear, but it is considered that the nitrogen-containing compound before heat curing is easily dissolved by the developing solution during development and the residue is suppressed because it is blended with the polyimide precursor. In addition, the reason for showing the Cu void suppression effect is not clear, but it is considered that the nitrogen-containing compound generates a urea derivative or the like by heating, and this functional group strongly interacts with Cu ions, suppressing the diffusion of Cu and as a result suppressing Cu voids. From the viewpoints described above, as the (B5) nitrogen-containing compound, a biuret compound, a carbazole compound, and an indole compound are more preferable, and a biuret compound is even more preferable.

[0131] The blending amount of the above nitrogen-containing compound in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. By blending the nitrogen-containing compound in the range of 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, a negative photosensitive resin composition particularly excellent in the Cu void suppression effect, resolution improvement, and chemical resistance improvement effects can be obtained.

[0132] (C) Photoinitiator In this embodiment, as the (C) photoinitiator, those shown in the first aspect can be used.

[0133] Other components In this embodiment, as other components, solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, adhesion aids, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors shown in the first aspect can be used. However, as described above, the nitrogen-containing heterocyclic compound as the other component is a compound other than the (B5) nitrogen-containing compound in the present embodiment.

[0134] <Method for manufacturing a cured relief pattern and semiconductor device> In the present embodiment, the method for manufacturing a cured relief pattern and the semiconductor device can apply the same ones as those shown in the first aspect.

[0135] <Polyimide> In the present embodiment, the polyimide can apply the same ones as those shown in the first aspect.

[0136] <Semiconductor device> In the present embodiment, the semiconductor device can apply the same ones as those shown in the first aspect.

[0137] <Display device> In the present embodiment, the display device can apply the same ones as those shown in the first aspect.

[0138] The negative photosensitive resin composition according to the present embodiment is, like the negative photosensitive resin composition shown in the first aspect, useful not only for applications to the semiconductor devices as described above, but also for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper clad laminates, solder resist films, and liquid crystal alignment films. The preferable configurations, numerical ranges, or steps shown in the first aspect can also be treated as preferable configurations, numerical ranges, or steps in the present embodiment.

[0139] [Combinations of aspects] According to each of the above aspects, it is possible to provide a negative photosensitive resin composition that can obtain high chemical resistance and resolution and suppress the generation of voids at the interface between the Cu layer and the resin layer after a high temperature storage test, and it is also possible to provide a method for forming a cured relief pattern using the negative photosensitive resin composition. Furthermore, the above-described aspects can be combined with each other. That is, (B1) an active esterifying agent, (B2) a thermosetting agent, (B3) a tertiary amine compound and / or a guanidine compound, (B4) an acidic compound, and (B5) a nitrogen-containing compound can be used in combination with each other. When combining the above-described aspects with each other, the total mass of (B1) an active esterifying agent, (B2) a thermosetting agent, (B3) a tertiary amine compound and / or a guanidine compound, (B4) an acidic compound, and (B5) a nitrogen-containing compound in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. By blending in the range of 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, a negative photosensitive resin composition particularly excellent in the Cu void suppression effect, resolution improvement, and chemical resistance improvement effects can be obtained.

Examples

[0140] Hereinafter, the present embodiment will be specifically described by way of examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the polymer or the negative photosensitive resin composition were measured and evaluated according to the following methods. Hereinafter, the first aspect will be described.

[0141] <Measurement and Evaluation Methods> (1) Weight-average molecular weight The weight-average molecular weight (Mw) of each resin was measured under the following conditions using gel permeation chromatography (standard polystyrene conversion). Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40°C Columns: Two in series of Shodex KD-806M manufactured by Showa Denko K.K., or Shodex 805M / 806M in series manufactured by Showa Denko K.K. Standard monodisperse polystyrene: Shodex STANDARD SM- manufactured by Showa Denko K.K. 105 Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL / min.

[0142] (2) Fabrication of cured relief pattern on Cu On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625 ± 25 μm), 200 nm thick Ti and 400 nm thick Cu were sputtered in this order using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A type, manufactured by SOKUDO), and pre-baked on a hot plate at 110 °C for 180 seconds to form a coating film with a thickness of about 7 μm. This coating film was irradiated with energy of 500 mJ / cm 2 using a mask with a test pattern by plasma GHI (manufactured by Ultratech). Then, this coating film was spray-developed with a coater developer (D-Spin60A type, manufactured by SOKUDO) using cyclopentanone as a developer and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The wafer with the relief pattern formed on Cu was heat-treated at the cure temperature shown in Table 1 for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg) to obtain a cured relief pattern composed of a resin with a thickness of about 4 - 5 μm on Cu.

[0143] (3) Resolution evaluation of cured relief pattern on Cu The cured relief pattern obtained by the above method was observed under an optical microscope to determine the size of the minimum opening pattern. At this time, if the area of the opening of the obtained pattern was 1 / 2 or more of the corresponding pattern mask opening area, it was regarded as resolved, and the length of the mask opening side corresponding to the one with the minimum area among the resolved openings was defined as the resolution. Those with a resolution of less than 10 μm were rated as "excellent", those with a resolution of 10 μm or more and less than 14 μm were rated as "good", those with a resolution of 14 μm or more and less than 18 μm were rated as "acceptable", and those with a resolution of 18 μm or more were rated as "unacceptable".

[0144] (4) High temperature storage test of the cured relief pattern on Cu and subsequent void area evaluation The wafer with the cured relief pattern formed on Cu was heated in air at 150 °C for 168 hours using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.). Subsequently, all the resin layers on Cu were removed by plasma etching using a plasma surface treatment apparatus (EXAM type, manufactured by Shinko Seiki Co., Ltd.). The plasma etching conditions are as follows. Output: 133 W Gas type · flow rate: O2: 40 mL / min + CF4: 1 mL / min Gas pressure: 50 Pa Mode: hard mode Etching time: 1800 seconds

[0145] The Cu surface with all the resin layers removed was observed by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and the area of the voids occupying the surface of the Cu layer was calculated using image analysis software (A Image-kun, manufactured by Asahi Kasei Corporation). When the total void area ratio was less than 50% with the total void area of the photosensitive resin composition described in Comparative Example 1 evaluated as 100%, it was rated as "excellent", when it was 50% or more and less than 75%, it was rated as "good", when it was 75% or more and less than 100%, it was rated as "acceptable", and when it was 100% or more, it was rated as "unacceptable".

[0146] (5) Chemical resistance evaluation of the cured relief pattern (polyimide coating film) The cured relief pattern formed on Cu was immersed for 5 minutes in a resist stripper solution {manufactured by ATMI, product name ST-44, main components: 2-(2-aminoethoxy)ethanol, and 1-cyclohexyl-2-pyrrolidone} heated to 50°C, washed with running water for 1 minute, and air-dried. Thereafter, the film surface was visually observed with an optical microscope, and the chemical resistance was evaluated based on the presence or absence of damage caused by the chemical solution such as cracks, and / or the change rate of the film thickness after the chemical solution treatment. As the evaluation criteria, those with no damage such as cracks and a film thickness change rate within 10% based on the film thickness before chemical immersion were rated "excellent", those exceeding 10% and within 15% were rated "good", those exceeding 15% and within 20% were rated "acceptable", and those with cracks generated or a film thickness change rate exceeding 20% were rated "unacceptable".

[0147] Production Example 1: Synthesis of Polymer A-1 as a Polyimide Precursor 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added, and the mixture was stirred at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After the exothermic reaction ended, the reaction mixture was allowed to cool to room temperature and left standing for 16 hours. Next, while stirring, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone under ice cooling was added to the reaction mixture over 40 minutes. Subsequently, a suspension prepared by suspending 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour. Then, 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 L of ethyl alcohol to form a precipitate composed of a crude polymer. The formed crude polymer was filtered off, dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer. After the obtained precipitate was filtered off, it was dried under vacuum to obtain a powdery polymer (Polymer A-1). When the molecular weight of Polymer (A-1) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.

[0148] Production Example 2: Synthesis of Polymer A-2 as a Polyimide Precursor The reaction was carried out in the same manner as the method described in Production Example 1 above, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1, to obtain Polymer (A-2). When the molecular weight of Polymer (A-2) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 22,000.

[0149] Production Example 3: Synthesis of Polymer A-3 as a Polyimide Precursor The reaction was carried out in the same manner as the method described in Production Example 1 above, except that 50.2 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1, to obtain Polymer (A-3). When the molecular weight of Polymer (A-3) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 19,000.

[0150] <Example 1-1> A negative photosensitive resin composition was prepared using Polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of Polymer A-1 as a polyimide precursor, (B1) 5 g of Compound B-11 as an active esterifying agent, (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the above-mentioned method. The results are shown in Table 1.

[0151] <Examples 1-2 to 1-10, Comparative Example 1> A negative photosensitive resin composition similar to that of Example 1-1 was prepared and evaluated in the same manner as in Example 1-1, except that it was prepared with the components and mixing ratios as shown in Table 1. The results are shown in Table 1. The compounds (B-11 to B-15) and photosensitizer (C-1) described in Table 1 are as follows.

[0152] B-11: 1-Hydroxy-7-azabenzotriazole B-12: Pentafluorophenol B-13: Bis(pentafluorophenyl) carbonate B-14: Bis(4-nitrophenyl) carbonate B-15: 4-Nitrophenyl trifluoroacetate C-1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

[0153]

Table 1

[0154] Hereinafter, the second aspect will be described. Among these, <Measurement and Evaluation Methods> and Production Examples 1 to 3 are the same as above.

[0155] <Example 2-1> Using Polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) 100 g of Polymer A-1 as a polyimide precursor, (B2) 8 g of Compound B-21 as a thermosetting agent, (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photoinitiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the above-mentioned method. The results are shown in Table 2.

[0156] <Examples 2-2 to 2-11, Comparative Example 1> A negative photosensitive resin composition similar to that of Example 2-1 was prepared and evaluated in the same manner as above, except that it was prepared with the components and blending ratios as shown in Table 2. The results are shown in Table 2. Compound (B-21 to B-26) and photosensitizer (C-1) described in Table 2 are as follows.

[0157] B-21: Benzoxazine represented by the following general formula (10)

Chemical formula

Chemical formula

Chemical formula

[0158]

Table 2

[0159] Next, the third aspect will be described. Among these, <Measurement and Evaluation Method> and Production Examples 1 to 3 are the same as above.

[0160] <Example 3-1> Using Polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) 100 g of Polymer A-1 as a polyimide precursor, (B3) 8 g of Compound B-31 as a tertiary amine compound and / or guanidine compound, (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 3.

[0161] <Examples 3-2 to 3-8, Comparative Example 1> A negative photosensitive resin composition similar to that of Example 3-1 was prepared and evaluated in the same manner as above, except that it was prepared with the components and blending ratios as shown in Table 3. The results are shown in Table 3. Compounds (B-31 to B-34) and photosensitizer (C-1) described in Table 3 are as follows.

[0162] B-31: 4-Hydroxymethyl-N,N-dimethylaniline B-32: Bis[4-(dimethylamino)phenyl]methane B-33: Dicyandiamide B-34: D-(-)-Arginine C-1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

[0163]

Table 3

[0164] The following describes the fourth aspect. Among these, <Measurement and Evaluation Method> and Production Examples 1 to 3 are the same as above.

[0165] <Example 4-1> Using Polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) 100 g of Polymer A-1 as a polyimide precursor, (B4) 8 g of Compound B-41 as an acidic compound, and (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 4.

[0166] <Examples 4-2 to 4-10, Comparative Example 1> A negative photosensitive resin composition similar to Example 4-1 was prepared and evaluated in the same manner as above, except that it was prepared with the components and mixing ratios as shown in Table 4. The results are shown in Table 4. The compounds (B-41 to B-46) and photosensitizer (C-1) described in Table 4 are as follows.

[0167] B-41: Methyl gallate B-42: Methylene disalicylate B-43: o-Cumaric acid B-44: Phthalic acid B-45: 4-Acetamidobenzoic acid B-46: 3-Hydroxybenzamide C-1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

[0168]

Table 4

[0169] The following describes the fifth aspect. Among these, <Measurement and Evaluation Method> and Production Examples 1 to 3 are the same as above.

[0170] <Example 5-1> Using Polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) 100 g of Polymer A-1 as a polyimide precursor, (B5) 8 g of Compound B-51 as a nitrogen-containing compound, and (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 5.

[0171] <Examples 5-2 to 5-12, Comparative Example 1> A negative photosensitive resin composition similar to that of Example 5-1 was prepared and evaluated in the same manner as above, except that it was prepared with the components and mixing ratios as shown in Table 5. The results are shown in Table 5. The compounds (B-51 to B-57) and photosensitizer (C-1) described in Table 5 are as follows.

[0172] B-51: Biuret B-52: 3,6-Diaminocarbazole B-53: 5-Aminoindole B-54: Hydantoin B-55: Barbituric acid B-56: Violuric acid B-57: Uracil C-1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

[0173]

Table 5

Industrial Applicability

[0174] By using the photosensitive resin composition according to the present invention, a cured relief pattern having high chemical resistance and resolution can be obtained, and the generation of voids on the Cu surface can be suppressed. The present invention can be suitably used in the field of photosensitive materials useful for the production of electrical and electronic materials such as semiconductor devices and multilayer wiring boards, for example.

Claims

1. (A) A polyimide precursor; (B) An active esterifying agent; and (C) A photopolymerization initiator A negative photosensitive resin composition containing the same.

2. The negative photosensitive resin composition according to claim 1, wherein the (B) active esterifying agent is at least one selected from the group consisting of bis(pentafluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, di(N-succinimidyl) carbonate, pentafluorophenol, 1-hydroxy-7-azabenzotriazole, and 4-nitrophenyl trifluoroacetate.

3. The negative photosensitive resin composition according to claim 1 or 2, wherein the (A) polyimide precursor contains a polyimide precursor having a structural unit represented by the following general formula (2): 【Chemical 1】 {In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and at least one of R １ and R ２ is a monovalent organic group.}

4. In the general formula (2), R １ and R ２ at least one of which is represented by the following general formula (3): 【Chemical 2】 {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer of 2 to 10.}, The negative photosensitive resin composition according to claim 3, which is a monovalent organic group represented by.

5. In the general formula (2), X １ is the following general formula (20a): [Chemical Formula 3] The negative photosensitive resin composition according to claim 3 or 4, containing a structure represented by

6. In the general formula (2), X １ is the following general formula (20b): 【Chemical Formula 4】 The negative photosensitive resin composition according to claim 3 or 4, containing a structure represented by

7. In the general formula (2), Y １ is the following general formula (21b): [Chemical Formula 5] The negative photosensitive resin composition according to any one of claims 3 to 6, containing a structure represented by

8. The negative photosensitive resin composition according to claim 3 or 4, wherein the (A) polyimide precursor contains a polyimide precursor having a structural unit represented by the following general formula (4): [Chemical Formula 6] {wherein, R １ , R ２ , and n １ are as defined above.}{{END}}

9. The negative photosensitive resin composition according to claim 3 or 4, wherein the (A) polyimide precursor contains a polyimide precursor having a structural unit represented by the following general formula (5): [Chemical Formula 7] {Wherein, R １ , R ２ , and n １ are as defined above.}{{END]]

10. The negative photosensitive resin composition according to any one of claims 3 to 9, wherein the (A) polyimide precursor simultaneously contains structural units represented by the following general formulas (4) and (5): 【Chemical Formula 8】 {In the formula, R １ , R ２ , and n １ are each as defined above, and R １ , R ２ , and n １ in the general formula (5) may be the same as or different from them.}{{END]] 【Chemical Formula 9】 {In the formula, R １ , R ２ , and n １ are each as defined above, and R １ , R ２ , and n １ in the general formula (4) may be the same as or different from those.}

11. The negative photosensitive resin composition according to claim 10, wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5).

12. 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) active esterifying agent based on 100 parts by mass of the (A) polyimide precursor, and 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor A negative photosensitive resin composition according to any one of claims 1 to 11, containing the same.

13. A method for producing a polyimide, including a step of converting the negative photosensitive resin composition according to any one of claims 1 to 12 into a polyimide.

14. (1) Coating the negative photosensitive resin composition according to any one of claims 1 to 12 on a substrate to form a photosensitive resin layer on the substrate; (2) Exposing the photosensitive resin layer; (3) Developing the exposed photosensitive resin layer to form a relief pattern; (4) Heat-treating the relief pattern to form a cured relief pattern A method for manufacturing a cured relief pattern, comprising:

15. (A) A polyimide precursor; (B) A thermosetting agent; and (C) A photopolymerization initiator A negative photosensitive resin composition comprising:

16. The negative photosensitive resin composition according to claim 15, wherein the (B) thermosetting agent is at least one selected from the group consisting of benzoxazine, epoxy resin, and oxetane resin.

17. The negative photosensitive resin composition according to claim 15 or 16, wherein the (B) thermosetting agent is benzoxazine.

18. The negative photosensitive resin composition according to any one of claims 15 to 17, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (2): 【Chemical Formula 10】 {In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and at least one of R １ and R ２ is a monovalent organic group.}

19. In the general formula (2), R １ and R ２ at least one of which is represented by the following general formula (3): 【Chemical 11】 {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer of 2 to 10.}, which is a monovalent organic group represented by the formula, The negative photosensitive resin composition according to claim 18.

20. In the general formula (2), X １ is the following general formula (20a): 【Chemical Formula 12】 The negative photosensitive resin composition according to claim 18 or 19, comprising a structure represented by:

21. In the general formula (2), X １ is the following general formula (20b): 【Chemical 13】 The negative photosensitive resin composition according to claim 18 or 19, comprising a structure represented by:

22. In the general formula (2), Y １ is the following general formula (21b): 【Chemical 14】 The negative photosensitive resin composition according to any one of claims 18 to 21, comprising a structure represented by:

23. The negative photosensitive resin composition according to claim 18 or 19, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (4): 【Chemical Formula 15】 {Wherein, R １ , R ２ , and n １ are as defined above.}{{END}}

24. The negative photosensitive resin composition according to claim 18 or 19, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (5): 【Chemical 16】 {wherein R １ , R ２ , and n １ are as defined above.}{{END]]

25. The negative photosensitive resin composition according to any one of claims 18 to 24, wherein the (A) polyimide precursor simultaneously comprises structural units represented by the following general formulas (4) and (5): 【Chemical 17】 {In the formula, R １ , R ２ , and n １ are each as defined above, and R １ , R ２ , and n １ in General Formula (5) may be the same as or different from those.}{{END]] 【Chemical 18】 {In the formula, R １ , R ２ , and n １ are each as defined above, and R １ , R ２ , and n １ in the general formula (4) may be the same as or different from those.}{{END]]

26. The negative photosensitive resin composition according to claim 25, wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5).

27. 100 parts by mass of the (A) polyimide precursor; Based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) thermosetting agent; Based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photoinitiator and The negative photosensitive resin composition according to any one of claims 15 to 26, comprising

28. A method for producing a polyimide, comprising a step of converting the negative photosensitive resin composition according to any one of claims 15 to 27 into a polyimide.

29. (1) A step of applying the negative photosensitive resin composition according to any one of claims 15 to 27 onto a substrate to form a photosensitive resin layer on the substrate; (2) A step of exposing the photosensitive resin layer; (3) A step of developing the exposed photosensitive resin layer to form a relief pattern; (4) A step of heat-treating the relief pattern to form a cured relief pattern A method for producing a cured relief pattern, comprising

30. (A) A polyimide precursor; (B) The following general formula (B-1): 【Chemical 19】 {In the formula, Ra and Rb are each independently a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom, Rc is each independently a monovalent organic group which may contain a heteroatom, and m represents an integer of 0 to 5.} At least one selected from the group consisting of a tertiary amine compound and a guanidine compound represented by; and (C) A photoinitiator; A negative photosensitive resin composition comprising

31. In the general formula (B-1), the negative photosensitive resin composition according to claim 30, wherein Ra and Rb are at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

32. The negative photosensitive resin composition according to claim 30, wherein the guanidine compound is a compound represented by the following general formula (B-2): 【Chemical 20】 {In the formula, Rd represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom.}

33. The negative photosensitive resin composition according to any one of claims 30 to 32, wherein the (A) polyimide precursor contains a polyimide precursor having a structural unit represented by the following general formula (2):

34. 【Chemical 21】 {Wherein, X １ is a tetravalent organic group, Y １ is a divalent organic group, n １ is an integer of 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and at least one of R １ and R ２ is a monovalent organic group.} The negative photosensitive resin composition according to claim 33, which is a monovalent organic group represented by

35. In the general formula (2), R １ and R ２ at least one of which is represented by the following general formula (3): 【Chemical 22】 {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer of 2 to 10.} The negative photosensitive resin composition according to claim 33 or 34, comprising a structure represented by

36. In the general formula (2), X １ is the following general formula (20a): 【Chemical 23】 The negative photosensitive resin composition according to claim 33 or 34, comprising a structure represented by

37. In the general formula (2), X １ is the following general formula (20b): 【Chemical 24】 ​ ​ In the general formula (2), Y １ is the following general formula (21b): 【Chemical 25】 The negative photosensitive resin composition according to any one of claims 33 to 36, comprising a structure represented by

38. The negative photosensitive resin composition according to claim 33 or 34, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (4): 【Chemical 26】 {wherein R １ , R ２ , and n １ are as defined above.}{{END]]

39. The negative photosensitive resin composition according to claim 33 or 34, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (5):

40. 【Chemical 27】 {Wherein, R １ , R ２ , and n １ are as defined above.}{{END]] The negative photosensitive resin composition according to any one of claims 33 to 39, wherein the (A) polyimide precursor simultaneously comprises structural units represented by the following general formulas (4) and (5):

41. The negative photosensitive resin composition according to claim 40, wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5). 【Chemical 28】 {In the formula, R １ , R ２ , and n １ are each as defined above, and R １ , R ２ , and n １ in the general formula (5) may be the same as or different from those.}{{END]] 【Chemical 29】 {In the formula, R １ , R ２ , and n １ are each as defined above, and R １ , R ２ , and n １ in the general formula (4) may be the same as or different from those.}

42. 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) tertiary amine compound and / or guanidine compound based on 100 parts by mass of the (A) polyimide precursor, and 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor The negative photosensitive resin composition according to any one of claims 30 to 41, comprising

43. A method for producing a polyimide, comprising a step of converting the negative photosensitive resin composition according to any one of claims 30 to 42 into a polyimide.

44. (1) A step of applying the negative photosensitive resin composition according to any one of claims 30 to 42 onto a substrate to form a photosensitive resin layer on the substrate; (2) A step of exposing the photosensitive resin layer; (3) A step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) A step of heat-treating the relief pattern to form a cured relief pattern A method for producing a cured relief pattern, comprising

45. The following components: (A) A polyimide precursor; (B-1) An acidic compound having two or more phenolic hydroxyl groups or carboxyl groups in the structure; and (C) A photopolymerization initiator A negative photosensitive resin composition, comprising

46. The negative photosensitive resin composition according to claim 45, wherein the (B-1) acidic compound is at least one acidic compound selected from the group consisting of methyl gallate, methylene disalicylate, o-coumaric acid, and phthalic acid.

47. ​ ​ ​ The negative photosensitive resin composition according to claim 45 or 46, wherein the (B-1) acidic compound is methylenedisalicylic acid or o-coumaric acid.

48. The following components: (A) A polyimide precursor; having one group selected from phenolic hydroxyl group or carboxyl group in the (B-2) structure, and -NH-CO-A １ , or -CO-NH ２ an acidic compound having one or more groups selected from; (A １ is an organic group having 1 to 4 carbon atoms); and (C) A photopolymerization initiator The negative photosensitive resin composition containing these.

49. The (B-2) acidic compound is represented by the following general formula (1): 【Chemical Formula 30】 {In formula (1), A ２ is a hydroxyl group or a carboxyl group, and A ３ is a group selected from -NH-CO-A １ or -CO-NH ２ ; A １ is an organic group having 1 to 4 carbon atoms, and A ４ is a monovalent group; m ２ is 1 or 2, and m ３ is an integer of 0 to 4.} The negative photosensitive resin composition according to claim 48.

50. The (A) polyimide precursor is represented by the following general formula (2): 【Chemical 31】 {In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and at least one of R １ and R ２ is a monovalent organic group.} The negative photosensitive resin composition according to any one of claims 45 to 49, comprising a polyimide precursor having a structural unit represented by this.

51. In the general formula (2), R １ and R ２ at least one of which is represented by the following general formula (3): 【Chemical Formula 32】 {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer of 2 to 10.} The negative photosensitive resin composition according to claim 50, which is a monovalent organic group represented by this.

52. In the general formula (2), X １ is the following general formula (20a): 【Chemical 33】 The negative photosensitive resin composition according to claim 50 or 51, containing a structure represented by this.

53. In the general formula (2), X １ is the following general formula (20b): 【Chemical 34】 The negative photosensitive resin composition according to claim 50 or 51, containing a structure represented by this.

54. In the general formula (2), Y １ is the following general formula (21b): 【Chemical 35】 Or the general formula (7): 【Chemical 36】 (wherein, R ９ ~R １２ is a hydrogen atom or a monovalent aliphatic group having 1 to 4 carbon atoms, and they may be different from each other or the same.) The negative photosensitive resin composition according to any one of claims 50 to 53, containing a structure represented by this.

55. The (A) polyimide precursor is represented by the following general formula (4): 【Chemical 37】 {In the formula, R １ , R ２ , and n １ are as defined above.}{{END]] The negative photosensitive resin composition according to claim 50 or 51, comprising a polyimide precursor having a structural unit represented by this.

56. The (A) polyimide precursor is represented by the following general formula (5): 【Chemical 38】 {In the formula, R １ , R ２ , and n １ are as defined above.}{{END]] The negative photosensitive resin composition according to claim 50 or 51, comprising a polyimide precursor having a structural unit represented by this.

57. The (A) polyimide precursor is represented by the following general formula (4): 【Chemical 39】 {In the formula, R １ , R ２ , and n １ are each as defined above, and R １ , R ２ , and n １ in the general formula (5) may be the same as or different from those.} And the following general formula (5): 【Chemical 40】 {In the formula, R １ , R ２ , and n １ are each as defined above, and R １ , R ２ , and n １ in the general formula (4) may be the same as or different from those.}{{END]] The negative photosensitive resin composition according to any one of claims 50 to 56, simultaneously containing structural units represented by these.

58. The negative photosensitive resin composition according to claim 57, wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5).

59. 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B-1) acidic compound based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor, The negative photosensitive resin composition according to any one of claims 45 to 47, containing these.

60. 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B-2) acidic compound based on 100 parts by mass of the (A) polyimide precursor, Based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photopolymerization initiator, and The negative photosensitive resin composition according to claim 48 or 49, comprising

61. A method for producing a polyimide, comprising a step of converting the negative photosensitive resin composition according to any one of claims 45 to 60 into a polyimide.

62. (1) A step of applying the negative photosensitive resin composition according to any one of claims 45 to 60 on a substrate to form a photosensitive resin layer on the substrate; (2) A step of exposing the photosensitive resin layer; (3) A step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) A step of heat-treating the relief pattern to form a cured relief pattern A method for producing a cured relief pattern, comprising

63. (A) A polyimide precursor; (B) At least one nitrogen-containing compound selected from the group consisting of biuret compounds, carbazole compounds, indole compounds, hydantoin compounds, uracil derivatives, and barbituric acid compounds; and (C) A photopolymerization initiator A negative photosensitive resin composition, comprising

64. The negative photosensitive resin composition according to claim 63, wherein the (B) nitrogen-containing compound is at least one selected from the group consisting of biuret compounds, carbazole compounds, and indole compounds.

65. The negative photosensitive resin composition according to claim 63 or 64, wherein the (B) nitrogen-containing compound is a biuret compound.

66. The (A) polyimide precursor is a polyimide precursor having a structural unit represented by the following general formula (2): 【Chemical 41】 {In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and at least one of R １ and R ２ is a monovalent organic group.} The negative photosensitive resin composition according to any one of claims 63 to 65, comprising a polyimide precursor having a structural unit represented by

67. In the general formula (2), R １ and R ２ at least one of which is represented by the following general formula (3): 【Chemical Formula 42】 {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer of 2 to 10.} A monovalent organic group represented by

68. In the general formula (2), X １ is the following general formula (20a): 【Chemical 43】 The negative photosensitive resin composition according to claim 66 or 67, comprising a structure represented by

69. In the general formula (2), X １ is the following general formula (20b): 【Chemical 44】 The negative photosensitive resin composition according to claim 66 or 67, comprising a structure represented by

70. In the general formula (2), Y １ is the following general formula (21b): 【Chemical 45】 The negative photosensitive resin composition according to any one of claims 66 to 69, comprising a structure represented by

71. The (A) polyimide precursor is a polyimide precursor having a structural unit represented by the following general formula (4): 【Chemical Formula 46】 {Wherein, R １ , R ２ , and n １ are as defined above.}{{END]] The negative photosensitive resin composition according to claim 66 or 67, comprising a polyimide precursor having a structural unit represented by

72. The (A) polyimide precursor is a polyimide precursor having the following general formula (5): 【Chemical 47】 {wherein R １ , R ２ , and n １ are as defined above.}{{END}} The negative photosensitive resin composition according to claim 66 or 67, comprising a polyimide precursor having a structural unit represented by

73. The negative photosensitive resin composition according to any one of claims 66 to 72, wherein the (A) polyimide precursor simultaneously contains structural units represented by the following general formulas (4) and (5): 【Chemical 48】 {In the formula, R １ , R ２ , and n １ are as defined above, and R １ , R ２ , and n １ in the general formula (5) may be the same as or different from those.}{{END]] 【Chemical 49】 {In the formula, R １ , R ２ , and n １ are each as defined above, and R １ , R ２ , and n １ in the general formula (4) may be the same as or different from those.}{{END]] The negative photosensitive resin composition according to any one of claims 66 to 72, comprising a polyimide precursor having a structural unit represented by

74. The negative photosensitive resin composition according to claim 73, wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5).

75. 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) nitrogen-containing compound based on 100 parts by mass of the (A) polyimide precursor, 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor, The negative photosensitive resin composition according to any one of claims 63 to 74, comprising

76. A method for producing a polyimide, comprising a step of converting the negative photosensitive resin composition according to any one of claims 63 to 75 into a polyimide.

77. (1) A step of applying the negative photosensitive resin composition according to any one of claims 63 to 75 onto a substrate to form a photosensitive resin layer on the substrate; (2) A step of exposing the photosensitive resin layer; (3) A step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) a step of heat-treating the relief pattern to form a cured relief pattern A method for producing a cured relief pattern, comprising

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