Negative photosensitive resin composition and method for manufacturing cured relief pattern

Abstract

To provide: a negative photosensitive resin composition with which high resolution properties are exhibited when a relief pattern is formed on copper wiring, imidization adequately progresses even when the curing temperature is low, and a cured relief pattern having good adhesion to copper wiring can be manufactured; and a method for manufacturing a cured relief pattern using the negative photosensitive resin composition.SOLUTION: The negative photosensitive resin composition contains (A) a polyimide precursor including specific structural units which are represented by the general formula (1), and (B) a photopolymerization initiator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a negative-type photosensitive resin composition and a method for producing a cured relief pattern. [Background technology]

[0002] Polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have traditionally been used as insulating materials for electronic components, and as passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursor compositions can easily form heat-resistant relief pattern films by applying the composition, exposing it to light, developing it, and subjecting it to a thermal imidization treatment involving curing. Such photosensitive polyimide precursor compositions have the advantage of enabling significant process reduction compared to conventional non-photosensitive polyimide materials.

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

[0004] To address this issue, flip-chip packaging has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the rewiring layer, and then the chip is flipped over and directly mounted on a printed circuit board. Because flip-chip packaging allows for precise control of wiring distance, it is being adopted for high-end applications that handle high-speed signals, and because of its small packaging size, it is being used in mobile phones and other devices, and demand is rapidly expanding. More recently, a semiconductor chip packaging technology called fan-out wafer-level packaging (FOWLP) has been proposed, in which individual chips are manufactured by dicing a pre-processed wafer, reassembled on a support, encapsulated with molding resin, and then a rewiring layer is formed after the support is peeled off (see, for example, Patent Document 1). FOWLP offers the advantages of thinner packages, high-speed transmission, and low cost. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-167191 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in recent years, the diversification of package mounting technologies has led to an increase in the number of types of supports and the multi-layering of rewiring layers, which has led to problems such as deviations in focus depth when exposing a photosensitive resin composition, resulting in a significant deterioration in resolution. Furthermore, while adhesion between copper wiring and a polyimide layer is important, lowering the curing temperature has the problem of reducing the imidization rate and adhesion to copper.

[0007] Therefore, an object of the present disclosure is to provide a negative-type photosensitive resin composition that exhibits high resolution when forming a relief pattern on copper wiring, and that allows imidization to proceed sufficiently even at a low curing temperature, making it possible to produce a cured relief pattern that has good adhesion to copper wiring, and a method for producing a cured relief pattern using the negative-type photosensitive resin composition. [Means for solving the problem]

[0008] The present inventors have found that the above-mentioned problems can be solved by combining a polyimide precursor having a side chain containing a urea structure with a photopolymerization initiator. Examples of embodiments of the present disclosure are listed below. [1] (A) a polyimide precursor containing a structural unit represented by the following general formula (1), and (B) Photopolymerization initiator A negative photosensitive resin composition comprising: [ka] In formula (1), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and R1 and R2 are each independently selected from the group consisting of a hydroxyl group, a monovalent organic group having 1 to 40 carbon atoms that does not have a urea structure, and a monovalent organic group having a urea structure, provided that at least one of R1 and R2 is the monovalent organic group having a urea structure. [2] (A') The negative photosensitive resin composition according to item 1, further comprising a polyimide precursor containing a structural unit represented by the following general formula (1'): [ka] In formula (1'), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and R1' and R2' are each independently selected from the group consisting of a hydroxyl group and a monovalent organic group having 1 to 40 carbon atoms that does not have a urea structure. [3] Item 3. The negative photosensitive resin composition according to item 1 or 2, wherein the polyimide precursor (A) is a copolymer containing a structural unit represented by the above general formula (1) and a structural unit represented by the following general formula (1'): [ka] In formula (1'), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and R1' and R2' are each independently selected from the group consisting of a hydroxyl group and a monovalent organic group having 1 to 40 carbon atoms that does not have a urea structure. [4] 4. The negative photosensitive resin composition according to any one of items 1 to 3, comprising 0.1 parts by mass to 20 parts by mass of the (B) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor, or, when the (A') polyimide precursor is contained, based on a total of 100 parts by mass of the (A) polyimide precursor and the (A') polyimide precursor. [5] 5. The negative photosensitive resin composition according to any one of items 1 to 4, wherein in the polyimide precursor (A), one of R1 and R2 is a monovalent organic group having a urea structure, and the other is a monovalent organic group having 1 to 40 carbon atoms and not having a urea structure. [6] 6. The negative photosensitive resin composition according to any one of items 1 to 5, wherein the proportion of the monovalent organic group having a urea structure in the polyimide precursor (A) is 0.1 mol % to 95 mol % relative to the total amount of R1 and R2. [7] 7. The negative photosensitive resin composition according to any one of items 1 to 6, wherein the monovalent organic group having 1 to 40 carbon atoms and no urea structure is represented by the following general formula (2): [ka] {In the formula, R3, R4, and R5 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.} [8] 8. The negative photosensitive resin composition according to any one of items 1 to 7, wherein the monovalent organic group having a urea structure further has a (meth)acrylic group. [9] 9. The negative photosensitive resin composition according to any one of items 1 to 8, wherein the monovalent organic group having a urea structure is represented by the following general formula (3): [ka] In the formula, R6 and R9 each independently represent a divalent organic group having 1 to 10 carbon atoms; R7, R8, and R 10 each independently represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.}

[10] 10. The negative photosensitive resin composition according to any one of items 1 to 9, wherein the monovalent organic group having a urea structure is at least one selected from the group consisting of the following general formulas (4) to (7): [ka] [ka] [ka] [ka] {In the formula, R6 is a divalent organic group having 1 to 10 carbon atoms, and R7 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.}

[11] 11. The negative photosensitive resin composition according to any one of items 1 to 10, wherein the proportion of the monovalent organic group having a urea structure relative to the total amount of R1 and R2 in the (A) polyimide precursor is 5 mol % or more and 75 mol % or less.

[12] 12. The negative photosensitive resin composition according to any one of items 1 to 11, wherein the (B) photopolymerization initiator is an oxime compound.

[13] 13. The negative photosensitive resin composition according to any one of items 1 to 12, wherein the photopolymerization initiator (B) is represented by the following general formula (19) or (20): [ka] {In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents a monovalent organic group having 1 to 20 carbon atoms, Rc represents a monovalent organic group having 1 to 10 carbon atoms, and Rd represents a monovalent organic group having 1 to 10 carbon atoms.)} [ka] {In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents a monovalent organic group having 1 to 10 carbon atoms.}

[14] 14. The negative photosensitive resin composition according to any one of items 1 to 13, further comprising (C) a photopolymerizable unsaturated monomer.

[15] 15. The negative photosensitive resin composition according to any one of items 1 to 14, wherein X1 is at least one selected from the group consisting of the following general formulae (8) to (11): [ka] [ka] [ka] [ka]

[16] 16. The negative photosensitive resin composition according to any one of items 1 to 15, wherein Y1 is at least one selected from the group consisting of the following general formulae (12) to (15): [ka] [ka] [ka] [ka] {where, R 11 are each independently a monovalent organic group having 1 to 10 carbon atoms, and each a is independently an integer of 0 to 4.}

[17] 17. The negative photosensitive resin composition according to any one of items 1 to 16, further comprising 0.01 to 20 parts by mass of a (D) rust inhibitor, based on 100 parts by mass of the (A) polyimide precursor, or, when the (A') polyimide precursor is contained, based on a total of 100 parts by mass of the (A) polyimide precursor and the (A') polyimide precursor.

[18] 18. The negative photosensitive resin composition according to any one of items 1 to 17, further comprising 0.1 to 30 parts by mass of (E) a compound having a urethane bond or a urea bond, based on 100 parts by mass of the (A) polyimide precursor, or, when the (A′) polyimide precursor is contained, based on a total of 100 parts by mass of the (A) polyimide precursor and the (A′) polyimide precursor.

[19] 19. A method for producing a polyimide, comprising a step of curing the negative photosensitive resin composition according to any one of items 1 to 18 to form a polyimide.

[20] The following steps: (1) A step of applying the negative photosensitive resin composition according to any one of items 1 to 18 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising: [twenty one] Item 21. The method for producing a cured relief pattern according to Item 20, wherein the imidization rate is 60% or more when the heat treatment according to (4) is performed at 150°C to 250°C. [twenty two] A polyimide precursor comprising a structural unit represented by the following general formula (1): [ka] In formula (1), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and R1 and R2 are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms that does not have a urea structure, and a monovalent organic group having a urea structure, provided that at least one of R1 and R2 is the monovalent organic group having a urea structure. [twenty three] Item 23. The polyimide precursor according to item 22, wherein X1 is at least one selected from the group consisting of the following general formulae (8) to (11), and Y1 is at least one selected from the group consisting of the following general formulae (12) to (15): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] {where, R 11 are each independently a monovalent organic group having 1 to 10 carbon atoms, and each a is independently an integer of 0 to 4.} [twenty four] 24. The polyimide precursor according to item 22 or 23, wherein the monovalent organic group having a urea structure is represented by the following general formula (3): [ka] In the formula, R6 and R9 each independently represent a divalent organic group having 1 to 10 carbon atoms; R7, R8, and R 10 each independently represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.} [twenty five] (A) a polyimide precursor containing a structural unit represented by the following general formula (1), and (B) Photopolymerization initiator A negative photosensitive resin composition comprising: [ka] {In formula (1), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and at least one of R1 and R2 is a monovalent organic group derived from a compound having a volatilization rate of 14% to 40% when heated at 170°C for 2 hours.}

[26] Item 26. The negative photosensitive resin composition according to item 25, wherein the volatilization rate is 14% to 30%.

[27] A negative-type photosensitive resin composition containing a polyimide precursor and a photopolymerization initiator, which has an imidization rate of 40% to 100% after heat-curing at 170°C, and has a concavo-convex difference of 0.5 microns to 3.5 microns after being coated on a polyimide film having a film thickness of 15 microns and a via size of 25 microns and heat-curing at 170°C.

[28] Item 28. The negative photosensitive resin composition according to Item 27, wherein the difference in unevenness is 0.5 microns to 2.5 microns. [Effects of the Invention]

[0009] According to the present disclosure, there are provided a negative-type photosensitive resin composition that exhibits high resolution when forming a relief pattern on copper wiring, undergoes sufficient imidization even at a low curing temperature, and is capable of producing a cured relief pattern that has good adhesion to copper wiring; and a method for producing a cured relief pattern using the negative-type photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0010] <Negative-type photosensitive resin composition> The negative photosensitive resin composition of the present disclosure comprises: (A) a polyimide precursor containing a structural unit represented by the following general formula (1), and (B) Photopolymerization initiator The negative photosensitive resin composition comprises: [ka] {In formula (1), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and R1 and R2 are each independently selected from the group consisting of a hydroxyl group, a monovalent organic group having 1 to 40 carbon atoms without a urea structure, and a monovalent organic group having a urea structure. However, at least one of R1 and R2 is the monovalent organic group having the urea structure.} The organic group may be an organic group containing a heteroatom other than carbon and hydrogen, or may be an organic group consisting of carbon and hydrogen atoms. Examples of heteroatoms include a nitrogen atom, an oxygen atom, and a sulfur atom. Throughout this specification, when a plurality of structures represented by the same symbol in a general formula are present in a molecule, they may be the same or different.

[0011] The negative photosensitive resin composition may further contain (A') a polyimide precursor containing a structural unit represented by the following general formula (1'), in addition to (A) the polyimide precursor. [ka] {In formula (1'), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and R1' and R2' are each independently selected from the group consisting of a hydroxyl group and a monovalent organic group having 1 to 40 carbon atoms and not having a urea structure.} The organic group may be an organic group containing a heteroatom other than carbon and hydrogen, or may be an organic group consisting of carbon and hydrogen atoms. Examples of heteroatoms include a nitrogen atom, an oxygen atom, and a sulfur atom. When (A') polyimide precursor is further contained, the amount of the polyimide precursor is more than 0 but less than 100 mass%, preferably more than 0 but less than 50 mass%, more preferably more than 0 but less than 20 mass%, and even more preferably more than 0 but less than 10 mass%, based on 100 mass% of the total of (A) polyimide precursor and (A') polyimide precursor.

[0012] The (A) polyimide precursor may be a copolymer of structural units represented by the above general formula (1) and the above general formula (1'). The copolymer may be a random copolymer, a block copolymer, or a combination thereof. When the total amount of the above general formula (1) is mm moles and the above general formula (1') is nm moles, the copolymerization ratio (molar ratio) is m+n=100, where m represents a number greater than 0 and less than 100, and n represents a number greater than 0 and less than 100. m is preferably 50 or more and less than 100, more preferably 80 or more and less than 100, and even more preferably 90 or more and less than 100. n is preferably greater than 0 and less than 50, more preferably greater than 0 and less than 20, and even more preferably greater than 0 and less than 10.

[0013] That is, the polyimide precursor may be a polyimide precursor in which at least one of R1 and R2 contains a monovalent organic group having a urea structure, as in the above general formula (1), or a mixture of the above general formula (1) and the above general formula (1'), i.e., a mixture (blend) of a polyimide precursor in which at least one of R1 and R2 contains a monovalent organic group having a urea structure, and a polyimide precursor in which R1' and R2' are monovalent organic groups having 1 to 40 carbon atoms and not having a hydroxyl group or a urea structure. Alternatively, the polyimide precursor may be a copolymer of the above general formula (1) and the above general formula (1'), i.e., a copolymer containing a polyimide structure in which at least one of R1 and R2 contains a monovalent organic group having a urea structure, and a polyimide structure in which R1' and R2' are monovalent organic groups having 1 to 40 carbon atoms and not having a hydroxyl group or a urea structure. Alternatively, the polyimide precursor may be a mixture of a polyimide precursor of the above copolymer and the above general formula (1').

[0014] The negative photosensitive resin composition of the present disclosure comprises: (A) a polyimide precursor containing a structural unit represented by the following general formula (1), and (B) Photopolymerization initiator The composition may be a negative photosensitive resin composition comprising: [ka] {In formula (1), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and at least one of R1 and R2 represents a monovalent organic group derived from a compound having a volatilization amount (hereinafter simply referred to as "volatilization amount") of 14% to 40% when heated at 170°C for 2 hours.} The volatilization amount can be measured by the method described in the Examples below. When at least one of R1 and R2 is derived from a compound having a volatilization amount of 14% to 40%, the film after heat curing has excellent chemical resistance and exhibits excellent elongation after a reliability test. From the viewpoint of chemical resistance, the volatilization amount is preferably 38% or less, more preferably 35% or less, and particularly preferably 32% or less. From the viewpoint of elongation after a reliability test, the volatilization amount is preferably 14% or more, more preferably 15% or more, and particularly preferably 16% or more. The compound having a volatilization amount of 14% to 40% is preferably a urea compound used in the synthesis of a polyimide precursor.

[0015] Although it is unclear whether the heat-cured film exhibits excellent chemical resistance and excellent elongation after a reliability test when at least one of R1 and R2 is derived from a compound with a volatilization amount of 14% to 40%. The present inventors believe as follows. Specifically, when at least one of R1 and R2 is derived from a compound with a volatilization amount of 40% or less, the organic groups of R1 and / or R2 tend to remain in the film even after heat curing. The remaining organic groups interact with the polyimide film, improving chemical resistance. When R1 and / or R2 contain a functional group with strong interaction, such as a urea structure or a urethane structure, chemical resistance tends to be further improved. When at least one of R1 and R2 is derived from a compound with a volatilization amount of 14% or more, excessive interaction of the organic groups that may remain after heat curing is suppressed, thereby improving elongation after a reliability test.

[0016] The negative photosensitive resin composition of the present disclosure may be a negative photosensitive resin composition containing a polyimide precursor and a photopolymerization initiator, which has an imidization rate of 40% to 100% after heat curing at 170° C., and has a concavo-convex difference of 0.5 microns to 3.5 microns after being coated on a polyimide film having a film thickness of 15 microns and a via size of 25 microns and heat curing at 170° C. The polyimide precursor is preferably the polyimide precursor (A) of the present disclosure, a copolymer polyimide precursor (A), or a mixture of these with the polyimide precursor (A').

[0017] The imidization rate can be calculated by the method described in the Examples below. By setting the imidization rate to 40% to 100%, peeling between the copper wiring and the polyimide film tends to be suppressed, for example, during a reflow process in the manufacturing process of a fan-out wafer-level package, which is preferable. From the viewpoint of suppressing peeling, the imidization rate is preferably 50% or more, more preferably 60% or more. From the viewpoint of elongation after heat curing, the imidization rate is preferably 98% or less, more preferably 95% or less.

[0018] The unevenness difference can be calculated by the method described in the Examples below. By keeping the unevenness difference at 3.5 microns or less, it is possible to ensure a sufficient yield when forming copper wiring during the manufacturing process, for example, when manufacturing a fan-out wafer-level package having multiple polyimide layers, which is preferable. It is preferably 3.0 microns or less, and more preferably 2.5 microns or less. By keeping it at 0.5 microns or more, it tends to suppress the occurrence of cracks in the polyimide layer when it is made into a multilayer structure. It is preferably 0.7 microns or more, and more preferably 0.9 microns or more.

[0019] (A) Polyimide precursor (A) Polyimide precursor is a resin component contained in the negative photosensitive resin composition and represented by the above general formula (1), and is converted into polyimide by heat cyclization treatment.

[0020] In general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, in order to achieve both heat resistance and photosensitive properties. X1 is more preferably an aromatic group in which the -COR1 and -COR2 groups and the -CONH- group are ortho-positioned relative to each other, or an alicyclic aliphatic group. Examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, and specific examples thereof include organic groups represented by the following general formulae (X1-1) and (X1-2): [ka] [ka] In formulae (X1-1) and (X1-2), R6 represents a hydrogen atom, a fluorine atom, or a C1 to C 10 and hydrocarbon groups of C1 to C 10 where 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.}, but is not limited to these. The structure of X1 may be one type or a combination of two or more types. X1 groups having structures represented by the above formulas (X1-1) and (X1-2) are particularly preferred in that they achieve both heat resistance and photosensitive properties, and structures represented by the above formulas (X1-1) are more preferred.

[0021] As the X1 group, among the structures represented by the above formulae (X1-1) and (X1-2), particularly, those represented by the following formula: [ka] {In the above formula, R6 and m have the same meanings as R6 and m in the above formulas (X1-1) and (X1-2), respectively.} are preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0022] More specifically, from the viewpoints of imidization rate, degassing property, copper adhesion, and chemical resistance, X1 is more preferably at least one selected from the group consisting of the following general formulae (8) to (11). [ka] [ka] [ka] [ka]

[0023] In the general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, in order to achieve both heat resistance and photosensitive properties. Y1 is, for example, a group represented by the following formulae (Y1-1) and (Y1-2): [ka] [ka] wherein R6 is a hydrogen atom, a fluorine atom, or a C1 to C 10 and hydrocarbon groups of C1 to C 10 and n is an integer selected from 0 to 4.}, but is not limited to these. The structure of Y1 may be one type or a combination of two or more types. Y1 groups having structures represented by the above formulas (Y1-1) and (Y1-2) are particularly preferred in that they achieve both heat resistance and photosensitive properties, and structures represented by the above formulas (Y1-1) are more preferred.

[0024] As the Y1 group, among the structures represented by the above formula (Y1-1), particularly, those represented by the following formula: [ka] {In the above formula, R6 and n have the same meanings as R6 and n in the above formula (Y1-1), respectively.} are preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0025] More specifically, from the viewpoints of imidization rate, degassing property, copper adhesion, and chemical resistance, Y1 is more preferably at least one selected from the group consisting of the following general formulae (12) to (15). [ka] [ka] [ka] [ka] {where, R 11 are each independently a monovalent organic group having 1 to 10 carbon atoms, and each a is independently an integer of 0 to 4. 11 may or may not contain a halogen atom.

[0026] At least one of R1 and R2 in the general formula (1) is preferably a group further containing a polymerizable group selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group, where the acid-polymerizable group, the base-polymerizable group, and the radical-polymerizable group respectively refer to groups that can be polymerized by the action of an acid, a base, or a radical.

[0027] From the viewpoint of resolution, it is preferred that R1 and R2 in the polyimide precursor (A) are each independently selected from monovalent organic groups having a urea structure and monovalent organic groups having 1 to 40 carbon atoms and not having a urea structure. Both R1 and R2 may be monovalent organic groups having a urea structure, and it is preferred that one of R1 and R2 is a monovalent organic group having a urea structure and the other is a monovalent organic group having 1 to 40 carbon atoms and not having a urea structure.

[0028] From the viewpoints of imidization rate, degassing property, copper adhesion, and chemical resistance, the monovalent organic group having 1 to 40 carbon atoms and not having a urea structure is more preferably a group represented by the following general formula (2). [ka] {In the formula, R3, R4, and R5 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.}

[0029] The monovalent organic group having a urea structure preferably has 1 to 40 carbon atoms. From the viewpoint of resolution, the monovalent organic group having a urea structure preferably further has, in addition to the urea structure, a polymerizable group selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group. From the viewpoint of resolution, the polymerizable group is more preferably a (meth)acrylic group. The monovalent organic group having a urea structure is more preferably represented by the following general formula (3): [ka] In the formula, R6 and R9 are each independently a divalent organic group having 1 to 10 carbon atoms, and R7, R8, and R 10 each independently represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.}

[0030] From the viewpoints of imidization rate, copper adhesion, and chemical resistance, it is also preferable that the monovalent organic group having a urea structure is at least one selected from the group consisting of the following general formulas (4) to (7). [ka] [ka] [ka] [ka] {In the formula, R6 is a divalent organic group having 1 to 10 carbon atoms, and R7 is a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or a monovalent organic group having 1 to 6 carbon atoms.}

[0031] From the viewpoint of the imidization rate during low-temperature heating and resolution, the ratio of monovalent organic groups having a urea structure to the total amount of R1 and R2 is preferably 0.1 mol% or more and 95 mol% or less. At 0.1 mol% or more, the imidization process is promoted, and at 95 mol% or less, the resolution is further improved. From the viewpoint of chemical resistance, 1 mol% or more is more preferable, and from the viewpoint of promoting the imidization process, 5 mol% or more is even more preferable, and from the viewpoint of reducing unevenness, 10 mol% or more is particularly preferable. From the viewpoint of resolution, 90 mol% or less is more preferable, and from the viewpoint of storage stability, 75 mol% or less is even more preferable, and 70 mol% or less is particularly preferable.

[0032] In one embodiment, the structural unit represented by the general formula (1) in the polyimide precursor (A) is represented by the following general formula (1-1): [ka] It is preferable that the compound contains a structural unit represented by the following formula: {In formula (1-1), R1 and R2 are defined as in general formula (1) above.}

[0033] The structural unit represented by the general formula (1) in the polyimide precursor (A) containing the structural unit represented by the general formula (1-1) particularly enhances the chemical resistance of the resulting polyimide film, and is also preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, and copper adhesion.

[0034] In one embodiment, the structural unit represented by the general formula (1) in the polyimide precursor (A) is represented by the following general formula (1-2): [ka] It is preferable that the compound contains a structural unit represented by the following formula: {wherein R1 and R2 are as defined in the general formula (1) above.}

[0035] The structural unit represented by the general formula (1) in the polyimide precursor (A) containing the structural unit represented by the general formula (1-2) particularly enhances the chemical resistance of the resulting polyimide film, and is also preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, and copper adhesion.

[0036] In one embodiment, the structural unit represented by the general formula (1) in the polyimide precursor (A) is represented by the following general formula (1-3): [ka] It is preferable that the compound contains a structural unit represented by the following formula: {wherein R1 and R2 are as defined in the general formula (1) above.}

[0037] The structural unit represented by the general formula (1) in the polyimide precursor (A) containing the structural unit represented by the general formula (1-3) further enhances the effect of improving resolution, and is also preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0038] (A) Preparation of polyimide precursor (A) A method for preparing a polyimide precursor is, for example: the tetracarboxylic acid dianhydride containing the tetravalent organic group X1; a compound having a urea group; Optionally, an alcohol having a polymerizable group selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group, which does not have a urea group, and optionally, another alcohol having no urea group. to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as "acid / ester"); Next, a partially esterified tetracarboxylic acid (acid / ester form) and a diamine containing the divalent organic group Y1; and subjecting the above to amide polycondensation to obtain (A) a polyimide precursor.

[0039] (Preparation of Acid / Ester Forms) (A) The tetracarboxylic acid dianhydride containing a tetravalent organic group X1 that is preferably used to prepare the polyimide precursor includes a tetracarboxylic acid dianhydride represented by the following formula: [ka] A compound represented by the following formula is preferred: {wherein X1 is as defined in general formula (1) above.} X1 is more preferably selected from the structures represented by general formulas (X1-1) and (X1-2) above, and is even more preferably the structure represented by general formula (X1-1) above.

[0040] Preferred examples of the tetracarboxylic dianhydride include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride (also known as oxydiphthalic dianhydride, abbreviated as "ODPA"), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (abbreviated as "BPDA"), diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. More preferred examples of the tetracarboxylic dianhydride include, but are not limited to, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0041] (A) Examples of organic groups having a polymerizable group selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group, which do not have a urea group and are suitably used for preparing a polyimide precursor, include 2-hydroxyethyl methacrylate, 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-methacryloyloxypropyl acrylate, 2-hydroxy-3-methyl-2-propanol ... Examples of the hydroxypropyl acrylate include 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, glycerol dimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate.

[0042] The compound having a urea group that is suitably used for preparing the (A) polyimide precursor is preferably a compound that further has, in addition to the urea group, a polymerizable group selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group, and more preferably a compound that further has, in addition to the urea group, a (meth)acrylic group.

[0043] A compound having a urea group can be synthesized, for example, from an isocyanate compound and an amine compound containing a hydroxyl group. Examples of isocyanate compounds used in this synthesis include 2-isocyanatoethyl methacrylate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and n-hexyl isocyanate. Commercially available examples of these compounds include Karenz MOI (registered trademark; Showa Denko), Karenz BEI (registered trademark; Showa Denko), Karenz AOI (registered trademark; Showa Denko), and Karenz MOI-EG (registered trademark; Showa Denko). Examples of amine compounds containing a hydroxyl group include 2-aminoethoxyethanol, 1-aminoethanol, and amino PEG3.

[0044] A non-photosensitive polyimide precursor prepared by reacting only an alcohol having no polymerizable group with a tetracarboxylic dianhydride may be used in combination with the polyimide precursor (A). In this case, from the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor is preferably 200 parts by mass or less per 100 parts by mass of the photosensitive polyimide precursor.

[0045] The tetracarboxylic dianhydride and the alcohol are dissolved and mixed in the presence of a suitable basic catalyst such as pyridine, preferably in a solvent as described below, to cause an esterification reaction of the acid anhydride groups of the tetracarboxylic dianhydride, thereby obtaining the desired acid / ester. The reaction is preferably carried out at a temperature of 20 to 50°C, and is preferably carried out by stirring continuously for 4 to 10 hours.

[0046] (Preparation of Polyimide Precursor) The acid / ester compound (typically in the form of a solution dissolved in a solvent, as described below) is mixed with an appropriate dehydration condensation agent under ice cooling to convert the acid / ester compound into a polyanhydride. A diamine containing a divalent organic group Y1, dissolved or dispersed in a separate solvent, is then added dropwise to the resulting mixture to carry out amide polycondensation, thereby obtaining the desired polyimide precursor. Examples of dehydration condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. Alternatively, the acid moiety of the acid / ester compound can be converted into an acid chloride using thionyl chloride or the like, followed by reaction with a diamine in the presence of a base such as pyridine to obtain the desired polyimide precursor.

[0047] Diamines containing a divalent organic group Y1 include those represented by the formula: H2N-Y1-NH2 A compound represented by the following formula is preferred: {wherein Y1 is as defined in the above general formula (1)}. It is more preferred that Y1 is a structure represented by each of the above general formulas (Y1-1) and (Y1-2).

[0048] More preferred diamines include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (also known as 4,4'-oxydianiline, abbreviated as "ODA"), 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- 4,4-bis(4-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 some of the hydrogen atoms on the benzene ring are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,Examples of the diaminodiphenylmethane include, but are not limited to, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl. These may be used alone or in combination of two or more.

[0049] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution can be filtered off as needed, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof can be added to the resulting polymer component to precipitate the polymer component. Furthermore, the polymer can be purified by repeating redissolution and reprecipitation procedures, and then vacuum dried to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution can be passed through a column packed with an anion exchange resin, a cation exchange resin, or both, swollen with an appropriate organic solvent to remove ionic impurities.

[0050] The molecular weight of the polyimide precursor (A), as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. A weight average molecular weight of 8,000 or more provides good mechanical properties, while a weight average molecular weight of 150,000 or less provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrenes. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent standard sample "STANDARD SM-105" manufactured by Showa Denko K.K.

[0051] (B) Photopolymerization initiator The negative photosensitive resin composition contains (B) a photopolymerization initiator, which is preferably a photoradical polymerization initiator or a photoacid generator.

[0052] Examples of the photoradical polymerization initiator include benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone compounds such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl compounds such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin compounds such as benzoin and benzoin methyl ether; and 1-phenyl Examples of suitable oxime compounds include 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, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycine compounds such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazole compounds; and titanocene compounds.

[0053] A preferred example of the photoacid generator is α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide.

[0054] The (B) photopolymerization initiator is not limited to the above examples. Among the above photopolymerization initiators, photoradical polymerization initiators are more preferred, and oxime compounds are even more preferred, particularly in terms of photosensitivity.

[0055] From the viewpoint of resolution, the oxime compound is preferably at least one selected from the group consisting of the following general formulae (19), (20) and (21). [ka] {(In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents a monovalent organic group having 1 to 20 carbon atoms, Rc represents a monovalent organic group having 1 to 10 carbon atoms, and Rd represents a monovalent organic group having 1 to 10 carbon atoms.)} [ka] {In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents a monovalent organic group having 1 to 10 carbon atoms.} [ka] {In the formula, Rg represents a monovalent organic group having 1 to 20 carbon atoms, Rh represents a monovalent organic group having 1 to 10 carbon atoms, and Ri represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.}

[0056] In general formula (19), Ra is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms. From the viewpoint of heat resistance, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, an ethyl group, or a propyl group is more preferred. Rb is not limited as long as it is an organic group having 1 to 20 carbon atoms. From the viewpoint of resolution, a monovalent organic group derived from an aromatic group having 6 to 20 carbon atoms or a heterocyclic compound having 5 to 20 carbon atoms is preferred. Rc is not limited as long as it is an organic group having 1 to 10 carbon atoms. Of these, from the viewpoint of resolution, a monovalent organic group containing a saturated alicyclic structure having 3 to 10 carbon atoms is more preferred. Rd is not limited as long as it is an organic group having 1 to 10 carbon atoms. Of these, from the viewpoint of resolution, an organic group having 1 to 3 carbon atoms is preferred, and a methyl group, an ethyl group, or a propyl group is more preferred.

[0057] In general formula (20), Re is not limited as long as it is an organic group having 1 to 20 carbon atoms, and from the viewpoint of resolution, it is preferably an organic group having 5 to 20 carbon atoms, and more preferably an organic group having 6 to 15 carbon atoms. Rf is not limited as long as it is an organic group having 1 to 10 carbon atoms, and from the viewpoint of resolution, it is preferably an organic group having 1 to 3 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group.

[0058] In general formula (21), Rg is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of heat resistance, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, or propyl group. Rh is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of resolution, it is preferably a group having 2 to 9 carbon atoms, and more preferably a group having 2 to 8 carbon atoms. Ri is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of resolution, it is preferably a hydrogen atom or a monovalent organic group having 1 to 9 carbon atoms.

[0059] Among the general formulae (19) to (21), the structure represented by the general formula (19) or (20) is more preferable in terms of resolution.

[0060] The blending amount of the (B) photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 8 parts by mass, based on 100 parts by mass of the (A) polyimide precursor, or, when the (A') polyimide precursor is included, based on the total 100 parts by mass of the (A) polyimide precursor and the (A') polyimide precursor. The blending amount is preferably 0.1 part by mass or more from the viewpoint of photosensitivity or patterning ability, and is preferably 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.

[0061] (C) Photopolymerizable monomer The negative photosensitive resin composition may contain a photopolymerizable monomer to improve the resolution of the relief pattern. The photopolymerizable monomer refers to a monomer having a photopolymerizable unsaturated bond. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator. Examples of such a monomer include, but are not limited to, monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of ethylene glycol; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of polyethylene glycol; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of propylene glycol; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of polypropylene glycol; monoacrylate, diacrylate, triacrylate, monomethacrylate, dimethacrylate, and trimethacrylate of glycerol; diacrylate and dimethacrylate of cyclohexane; and 1,4-butanediol. diacrylate and dimethacrylate of 1,6-hexanediol; diacrylate and dimethacrylate of neopentyl glycol; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of bisphenol A; benzene trimethacrylate; isobornyl acrylate and isobornyl methacrylate; acrylamide and derivatives thereof; methacrylamide and derivatives thereof; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; diacrylate, triacrylate, tetraacrylate, dimethacrylate, trimethacrylate, and tetramethacrylate of pentaerythritol; and ethylene oxide adducts or propylene oxide adducts of these compounds.

[0062] When the photosensitive resin composition contains the above-mentioned photopolymerizable unsaturated monomer for improving the resolution of the relief pattern, the amount of the photopolymerizable unsaturated monomer is preferably 1 to 50 parts by mass based on 100 parts by mass of the polyimide precursor (A), or, when the photosensitive resin composition contains the polyimide precursor (A'), based on the total amount of the polyimide precursor (A) and the polyimide precursor (A').

[0063] (D) Rust inhibitor When a cured film is formed on a substrate made of copper or a copper alloy using the photosensitive resin composition, the negative photosensitive resin composition may optionally contain a rust inhibitor to suppress discoloration of the copper. Examples of the rust inhibitor include an azole compound and a purine compound.

[0064] Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and 2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole. 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.

[0065] Particularly preferred azole compounds include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0066] Specific examples of purine compounds include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 2-hydroxy ... 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9 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-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and the like, and derivatives thereof.

[0067] When the photosensitive resin composition contains (D) a rust inhibitor, the amount of the rust inhibitor is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor, or when the (A') polyimide precursor is contained, based on 100 parts by mass of the combined total of the (A) polyimide precursor and the (A') polyimide precursor. From the viewpoint of photosensitivity, the amount of the rust inhibitor is more preferably 0.03 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, and may be, for example, 0.01 to 5 parts by mass. When the amount of the (D) rust inhibitor is 0.01 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or a copper alloy, while when the amount is 20 parts by mass or less, photosensitivity is excellent.

[0068] (E) Compounds having a urethane bond or a urea bond The photosensitive resin composition may further contain a compound having a urethane bond or a urea bond. The (E) compound contains at least one selected from the group consisting of a urethane bond and a urea bond in its molecular structure (hereinafter also referred to as a "urethane / urea compound"). When the photosensitive resin composition contains the (E) compound, it is possible to improve adhesion to the molding resin and / or in-plane uniformity when formed as a multilayer. However, such effects are achieved by using a solvent together with the urethane / urea compound.

[0069] The compound (E) may have a urethane bond and / or a urea bond in its molecular structure, and preferably has a urea bond from the viewpoint of suppressing voids on the Cu surface and improving chemical resistance.

[0070] Among the compounds having a urea bond, compounds represented by the following general formula (17) or (18) are more preferred from the viewpoint of developability. [ka] {where, R 12 and R 15 are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R 13 and R 14 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.} [ka] {where, R 16 and R 17 are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R 18 is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.}

[0071] Examples of heteroatoms include oxygen atoms, nitrogen atoms, phosphorus atoms, and sulfur atoms. 12 and R 15R are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and preferably contain an oxygen atom from the viewpoint of developability. 12 and R 15 The number of carbon atoms of may be 1 to 20, and from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10.

[0072] In formula (17), R 13 and R 14 R are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a hydrogen atom or a heteroatom, and more preferably contain a hydrogen atom or an oxygen atom from the viewpoint of developability. 13 and R 14 The number of carbon atoms may be 1 to 20, and from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10.

[0073] In formula (18), R 16 and R 17 R are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and preferably contain an oxygen atom from the viewpoint of developability. 16 and R 17 The number of carbon atoms in R may be 1 to 20, and from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10. 18 R may be a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and more preferably contains at least one oxygen atom from the viewpoint of suppressing cracking or improving elongation in reliability tests. 18 The carbon number of may be 1 to 20, preferably 2 or more from the viewpoint of containing a heteroatom, and preferably 1 to 18 from the viewpoint of heat resistance.

[0074] The compound (E) preferably further has at least one functional group selected from the group consisting of a (meth)acrylic group, a hydroxyl group, and an amino group, and more preferably has a (meth)acrylic group.

[0075] By including the (E) compound together with a solvent, the photosensitive resin composition improves adhesion to the molding resin or in-plane uniformity when formed into a multilayer. While the reasons for this are unclear, the present inventors believe the following: In one embodiment, negative-type photosensitive resin compositions are heat-cured at low temperatures of 180°C or less, which tends to result in insufficient conversion of the polyimide precursor to polyimide. On the other hand, by including the urethane / urea compound (E) in the photosensitive resin composition, a portion of the (E) compound is thermally decomposed to generate amines, etc., which are believed to promote the conversion of the polyimide precursor to polyimide. Furthermore, in a preferred embodiment, when the compound (E) further contains a (meth)acrylic group, the compound (E) reacts with the side chain portion of the polyimide precursor upon irradiation with light, crosslinking occurs, and the compound (E) is more likely to be present in the vicinity of the polyimide precursor, resulting in a dramatic increase in conversion efficiency. Therefore, in the production of polyimide or cured relief patterns, even though the heat curing is performed at a low temperature, the conversion to polyimide is almost complete, and therefore, the cyclization reaction does not proceed further, so that no shrinkage stress occurs and high adhesion can be maintained. Furthermore, since the conversion to polyimide is almost complete, when a photosensitive resin composition is coated and prebaked to form a second layer on the first polyimide film, the first layer is thought to have sufficient solvent resistance, resulting in sufficient in-plane uniformity.

[0076] When the (E) compound further has a (meth)acrylic group, the (meth)acrylic equivalent of the (E) compound is preferably 150 to 400 g / mol. When the (meth)acrylic equivalent of the (E) compound is 150 g / mol or more, the chemical resistance of the negative-type photosensitive resin composition tends to be good, and when it is 400 g / mol or less, the developability tends to be good. The lower limit of the (meth)acrylic equivalent of the (E) compound is more preferably 200 g / mol or more, 210 g / mol or more, 220 g / mol or more, or 230 g / mol or more, even more preferably 240 g / mol or more, or 250 g / mol or more, and the lower limit is more preferably 350 g / mol or less, or 330 g / mol or less, even more preferably 300 g / mol or less. The (meth)acrylic equivalent of the (E) compound is even more preferably 210 to 400 g / mol, particularly preferably 220 to 400 g / mol.

[0077] The urethane / urea compound (E) is preferably a urethane / urea compound having a (meth)acrylic group and a structure represented by the following general formula (e1). [ka] {In the formula, R3 is a hydrogen atom or a methyl group, A is a group selected from the group consisting of -O-, -NH-, and -NL4-, L4 is a monovalent organic group having 1 to 12 carbon atoms, Z1 is an m2-valent organic group having 2 to 24 carbon atoms, Z2 is a divalent organic group having 2 to 8 carbon atoms, and m2 is an integer of 1 to 3.}

[0078] In formula (e1), R3 may be a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of developability. Z1 may be an m-divalent organic group having 2 to 24 carbon atoms, and preferably has 2 to 20 carbon atoms. Here, Z1 may also contain a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or phosphorus atom. When Z1 has 2 or more carbon atoms, the negative photosensitive resin composition tends to have good chemical resistance, and when it has 20 or less carbon atoms, the developability tends to be good. Z1 preferably has 3 or more carbon atoms, even more preferably 4 or more carbon atoms, and more preferably 18 or less, and even more preferably 16 or less. Z2 may be a divalent organic group having 2 to 8 carbon atoms. Here, Z2 may also contain a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or phosphorus atom. When Z2 has 2 or more carbon atoms, the negative photosensitive resin composition tends to have good chemical resistance, and when it has 8 or less carbon atoms, the heat resistance tends to be good. Z2 preferably has 6 or less carbon atoms, more preferably 4 or less. A is a group selected from the group consisting of -O-, -NH-, and -NL4- {wherein L4 is a monovalent organic group having 1 to 12 carbon atoms.} From the viewpoint of chemical resistance, A is preferably -NH- or NL4-.

[0079] The (meth)acrylic group-containing urea / urethane compound of the above general formula (e1) can be produced, for example, by reacting an isocyanate compound represented by the following general formula with an amine and / or a hydroxyl group-containing compound. [ka]

[0080] Among the compounds (E) explained above, at least one compound selected from the group consisting of the following formulae (e2) to (e11) is particularly preferred from the viewpoints of chemical resistance, void suppression, and developability. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0081] In another embodiment, tetramethylurea can be used as the compound having an (E) urea bond.

[0082] The (E) compound may be used alone or in combination of two or more. The blending amount of the (E) compound is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the (A) polyimide precursor, or, when the (A') polyimide precursor is included, based on the total 100 parts by mass of the (A) polyimide precursor and the (A') polyimide precursor. The blending amount of the (E) compound is 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning ability, and is 30 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.

[0083] The negative photosensitive resin composition may further contain components other than the above components (A) to (E). The components other than the components (A) to (E) are not limited to, but include, for example, solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organotitanium compounds, adhesion aids, sensitizers, thermal polymerization inhibitors, and thermal base generators.

[0084] solvent Examples of the solvent include amides, sulfoxides, urea and derivatives thereof, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. Specific examples of the solvent that can be used include 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, and mesitylene. Among these, from the viewpoints of resin solubility, resin composition stability, and adhesion to substrates, one or more selected from the group consisting of 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.

[0085] Among these solvents, those that completely dissolve the polyimide precursor are particularly preferred, and suitable examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma-butyrolactone.

[0086] In the photosensitive resin composition, the amount of solvent used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, based on 100 parts by mass of the (A) polyimide precursor, or, when the (A') polyimide precursor is contained, based on 100 parts by mass of the (A) polyimide precursor and the (A') polyimide precursor combined.

[0087] Hindered phenol compounds To suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound, such as 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butyl) Phenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenyl)propionate ol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4, 6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) 1,3,5-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-tri Examples of suitable amines include, but are not limited to, azine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0088] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor, or, when the (A') polyimide precursor is included, based on 100 parts by mass of the combined total of the (A) polyimide precursor and the (A') polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity. When the amount of the hindered phenol compound is 0.1 part by mass or more, for example, when the photosensitive resin composition of the present disclosure is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0089] Organotitanium Compounds The negative photosensitive resin composition may contain an organotitanium compound. By containing the organotitanium compound in the negative photosensitive resin composition, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0090] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0091] Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the negative photosensitive resin composition and produce good cured 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), and titanium diisopropoxide bis(ethylacetoacetate). 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 tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -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(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0092] Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0093] When an organotitanium compound is added, the 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, or, when the (A') polyimide precursor is included, based on the total 100 parts by mass of the (A) polyimide precursor and the (A') polyimide precursor. When the amount is 0.05 part by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the storage stability of the photosensitive resin composition is excellent.

[0094] Adhesion aid To improve adhesion between a film formed using the negative photosensitive resin composition and a substrate, the negative photosensitive resin composition may optionally contain an adhesion promoter, such as an aluminum-based adhesion promoter or a silane coupling agent.

[0095] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0096] Examples of silane coupling agents include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3- (triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.: trade name) KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: 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-mercaptoethyltrippropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltrippropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: 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-trippropoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-trippropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2),2-(Trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: 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(methoxyethoxy) Silane), 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] [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 arylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol,In addition to n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like, the following formula (S-1): [ka] Examples of silane coupling agents include, but are not limited to, those represented by the following formula:

[0097] Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. As the silane coupling agent, among the above-mentioned silane coupling agents, it is preferable to use one or more selected from the group consisting of phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the silane coupling agents represented by the above formula (S1), from the viewpoint of storage stability.

[0098] When the photosensitive resin composition contains an adhesion promoter, the amount of the adhesion promoter is preferably 0.01 to 25 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the (A) polyimide precursor, or, when the (A') polyimide precursor is included, based on the total 100 parts by mass of the (A) polyimide precursor and the (A') polyimide precursor. When a silane coupling agent is used, the amount is preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the (A) polyimide precursor, or, when the (A') polyimide precursor is included, based on the total 100 parts by mass of the (A) polyimide precursor and the (A') polyimide precursor.

[0099] sensitizer The negative photosensitive resin composition may optionally contain a sensitizer 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, and p-dimethylaminocinnamylidene indole. Non, p-dimethylaminobenzylideneindanone, 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-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of, for example, 2 to 5 types.

[0100] When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount of the sensitizer is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the polyimide precursor (A), or, when the photosensitive resin composition contains the polyimide precursor (A'), based on the total of 100 parts by mass of the polyimide precursor (A) and the polyimide precursor (A').

[0101] Thermal polymerization inhibitor The negative photosensitive resin composition may optionally contain a thermal polymerization inhibitor to improve the stability of viscosity and photosensitivity, particularly when stored in a solvent-containing solution. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0102] Thermal base generator The negative photosensitive resin composition may contain a thermal base generator. A base generator is a compound that generates a base upon heating. By containing the thermal base generator, imidization of the photosensitive resin composition can be further promoted.

[0103] Examples of thermal base generators include, but are not limited to, amine compounds protected by a tert-butoxycarbonyl group, the thermal base generators disclosed in WO 2017 / 038598, etc. However, the thermal base generators are not limited to these, and other known thermal base generators can also be used.

[0104] Examples of amine compounds protected by a tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)-1-propanol, 4-amino-2-methyl-1-but ...4-amino-2-methyl-1-butanol, 4-amino-2-methyl-1-butanol, 4-amino-2-methyl-1-butanol, 4-amino-2-methyl-1-but (isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanol bis(3-aminopropyl)ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, diethylene glycol bis(3-aminopropyl) ether, and compounds in which the amino group of an amino acid or a derivative thereof is protected with a tert-butoxycarbonyl group, but are not limited to these.

[0105] The amount of the thermal base generator is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 20 parts by mass, based on 100 parts by mass of the (A) polyimide precursor, or, when the (A') polyimide precursor is included, based on the total 100 parts by mass of the (A) polyimide precursor and the (A') polyimide precursor. The amount is preferably 0.1 parts by mass or more from the viewpoint of the imidization-accelerating effect, and is preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative-type photosensitive resin composition.

[0106] <Method for producing cured relief pattern> The method of producing a cured relief pattern of the present disclosure includes: (1) a step of applying the above-described negative photosensitive resin composition of the present disclosure onto a substrate to form a photosensitive resin layer on the substrate (a resin layer forming step); (2) a step of exposing the photosensitive resin layer to light (exposure step); (3) a step of developing the exposed photosensitive resin layer to form a relief pattern (relief pattern formation step); (4) a step of heat-treating the relief pattern to form a cured relief pattern (a cured relief pattern forming step); Includes:

[0107] (1) Resin layer formation process In this step, a negative photosensitive resin composition is applied to a substrate and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0108] If necessary, the coating film containing the photosensitive resin composition can be dried. Drying methods include air drying, heat drying using an oven or a hot plate, and vacuum drying. Specifically, in the case of air drying or heat drying, drying can be carried out under conditions of 20°C to 150°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on a substrate.

[0109] (2) Exposure process In this step, the photosensitive resin layer formed above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a patterned photomask or reticle. This exposure causes the polymerizable groups of the polyimide precursor ((A) and / or (A')) contained in the negative photosensitive resin composition to crosslink due to the action of the photopolymerization initiator (B). This crosslinking makes the exposed areas insoluble in the developer described below, enabling the formation of a relief pattern.

[0110] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) or pre-development baking, or both, may be performed at any combination of temperature and time, as necessary. The baking conditions are preferably a temperature of 40°C to 120°C and a time of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition.

[0111] (3) Relief pattern formation process In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The developing method for developing the exposed (irradiated) photosensitive resin layer can be any method selected from conventionally known photoresist developing methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, as needed, for the purpose of adjusting the shape of the relief pattern, etc.

[0112] The developer used for development is preferably, for example, a good solvent for the negative-tone photosensitive resin composition, or a combination of the good solvent and a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative-tone photosensitive resin composition. Two or more solvents, for example, a combination of several solvents, can also be used.

[0113] (4) Hardened relief pattern formation process In this step, the relief pattern obtained by the development is heat-treated to dissolve the photosensitive component and imidize the polyimide precursor, thereby converting it into a cured relief pattern composed of polyimide. Heat treatment can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heat treatment can be performed, for example, at 150°C to 350°C for 30 minutes to 5 hours. The heat treatment temperature is 150°C to 250°C, preferably 150°C to 200°C, and more preferably 150°C to 180°C. Air or an inert gas such as nitrogen or argon can be used as the atmospheric gas during heat curing. Heat treatment at 150°C to 250°C from the negative-type photosensitive resin composition can provide a polyimide having an imidization rate of preferably 60% or more.

[0114] The photosensitive resin layer after exposure has a crosslinked structure formed by crosslinking of polymerizable groups of the polyimide precursor. However, this crosslinked structure is eliminated from the polymer during heating in the cured relief pattern formation step, and the amide acid structure generated by this elimination undergoes ring closure to form an imide ring structure, which is thought to result in the formation of a cured relief pattern made of polyimide.

[0115] <Polyimide> The negative-type photosensitive resin composition of the present disclosure can be cured to form a polyimide. The cured relief pattern formed from the photosensitive resin composition of the present disclosure is believed to contain a polyimide having a structure represented by the following general formula (16): [ka] {In general formula (16), X 1 and Y 1 respectively represent X in general formula (1). 1 and Y 1}Preferred X in general formula (1) is the same as 1 , Y 1 is also preferred in the polyimide of general formula (16) for the same reason.

[0116] <Semiconductor device> The present disclosure also provides a semiconductor device having a cured relief pattern obtained from the above-described photosensitive resin composition. More specifically, the present disclosure provides a semiconductor device having a substrate that is a semiconductor element and a cured relief pattern. The cured relief pattern may be produced by the above-described method for producing a cured relief pattern using the above-described photosensitive resin composition.

[0117] The present disclosure can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern of the present disclosure as part of the process. In this case, the cured relief pattern formed by the method for manufacturing a cured relief pattern of the present disclosure can be formed as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and can be manufactured by combining the cured relief pattern formed by the method for manufacturing a cured relief pattern of the present disclosure with a known method for manufacturing a semiconductor device.

[0118] <Display device> The present disclosure provides a display device including a display element and a cured film disposed on the display element, the cured film having the above-described cured relief pattern. The cured relief pattern may be laminated in direct contact with the display element, or may be laminated via another layer. The cured film can be used, for example, as a surface protection film, insulating film, or planarizing film for a TFT liquid crystal display element or a color filter element; a protrusion for an MVA-type liquid crystal display device; or a partition wall for a cathode of an organic EL element.

[0119] The negative photosensitive resin composition of the present disclosure is useful not only for application to the semiconductor devices described above, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. [Example]

[0120] <Measurement and evaluation methods> (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene equivalent) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Showa Denko Shodex KD-805 / KD-804 / KD-803 in series Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko K.K. Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min.

[0121] (2) Fabrication of hardened relief patterns on Cu A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti layer and a 400 nm thick Cu layer, in that order, using a sputtering device (Model L-440S-FHL, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto the wafer using a coater developer (Model D-Spin60A, manufactured by SOKUDO Co., Ltd.), and prebaked on a hot plate at 110°C for 180 seconds to form a coating film approximately 15 μm thick. A test pattern mask was used to apply 40 to 600 mJ / cm2 to this coating film using a Prisma GHI (manufactured by Ultratech Co., Ltd.). 2 The coating was then spray-developed using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) using cyclopentanone as the developer for a time equal to 1.4 times the time required for the unexposed areas to completely dissolve and disappear. The coating was then rinsed with propylene glycol methyl ether acetate by rotary spray for 10 seconds, yielding a relief pattern on the Cu. The wafer with the relief pattern formed on the Cu was then heat-treated in a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) for 2 hours in a nitrogen atmosphere at the curing temperature listed in Table 1, yielding a cured relief pattern of resin approximately 8 to 10 μm thick on the Cu.

[0122] (3) Resolution evaluation of hardened relief patterns 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. If the area of ​​the opening in the obtained pattern was at least half the area of ​​the corresponding pattern mask opening, it was considered to be resolved, and the length of the mask opening side corresponding to the smallest area among the resolved openings was taken as the resolution. The resolution was evaluated based on the following criteria. "Excellent": Resolution less than 10 μm "Good": Resolution is 10 μm or more and less than 12 μm "Acceptable": Resolution is 12 μm or more and less than 17 μm "Not acceptable": Resolution is 17 μm or more

[0123] (4) Imidization rate measurement The cured relief pattern resin portion was measured using an ATR-FTIR measurement device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) with a Si prism, and the peak intensity was measured at 1380 cm -1 The peak intensity at 1500cm -1 The imidization index is defined as the value obtained by dividing the imidization index of the film of each Example and Comparative Example cured at the curing temperature shown in Table 1 by the imidization index of the film obtained by curing the resin composition at 350°C. The imidization ratio was calculated as the value. The imidization ratio was evaluated based on the following criteria. "Excellent": Imidation rate is 90% or more "Good": Imidation rate is 75% or more but less than 90% "Acceptable": Imidation rate is 40% or more but less than 75% "Not acceptable": Imidation rate less than 40%

[0124] (5) Copper adhesion evaluation A photosensitive resin composition prepared by the method described below was applied to a 6-inch silicon wafer that had been pre-sputtered with Ti and Cu, similar to the preparation of the cured relief pattern described above, and the wafer was pre-baked. The wafer was then heat-treated for 2 hours in a nitrogen atmosphere at the temperature shown in Table 1 using a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg Co., Ltd.), yielding a cured resin film approximately 10 μm thick on the Cu. The heat-treated film was evaluated for adhesion properties between the copper substrate and the cured resin film using the cross-cut method of JIS K 5600-5-6, based on the following criteria: "Excellent": The lattice number of the cured resin coating adhered to the substrate is 80 to 100 "Acceptable": The lattice number of the cured resin coating adhered to the substrate is 40 or more but less than 80 "Not acceptable": The lattice number of the cured resin coating adhered to the substrate is less than 40

[0125] (6) Volatilization measurement The urea compounds synthesized in the examples were heated in a nitrogen atmosphere from 25°C to 170°C at a rate of 5°C / min using a DTG-60A apparatus manufactured by Shimadzu Corporation, and then held at 170°C for 2 hours to measure the weight loss rate.

[0126] (7)Irregularity difference measurement A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti layer and a 400 nm thick Cu layer, in that order, using a sputtering device (Model L-440S-FHL, manufactured by Canon Anelva Corporation). Subsequently, the resin composition of Comparative Example 1, described below, was spin-coated onto this wafer using a coater developer (Model D-Spin60A, manufactured by SOKUDO Co., Ltd.), and prebaked on a hot plate at 110°C for 180 seconds to form a coating film with a final film thickness of 15 microns. A test pattern mask was used to apply 400 mJ / cm to this coating film using a Prisma GHI (manufactured by Ultratech Co., Ltd.). 2The coating was then spray-developed using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) for a time equal to 1.4 times the time required for the unexposed areas to completely dissolve and disappear. A relief pattern was then obtained by rinsing with propylene glycol methyl ether acetate for 10 seconds using a rotary spray. The wafer with the relief pattern formed on Cu was then heat-treated in a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) at 230°C for 2 hours under a nitrogen atmosphere, resulting in a cured relief pattern of approximately 15 μm thick resin on Cu. The photosensitive resin compositions obtained in the examples and comparative examples were spin-coated onto the resulting relief pattern using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) in the same manner, and the resulting relief pattern was pre-baked on a hot plate at 110°C for 180 seconds to form a coating. The resulting coating film was heat-treated for 2 hours in a temperature-rising programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg) under a nitrogen atmosphere at the temperature shown in Table 1, thereby obtaining a cured film made of resin approximately 5 μm thick on the relief pattern of the cured product of Comparative Example 1. A 25 μm via in the resulting cured film was cut into a cross section using an FIB device (JIB-4000, manufactured by JEOL Ltd.), and the difference in unevenness from the surface was measured.

[0127] (8) Elongation measurement The photosensitive resin compositions obtained in the Examples and Comparative Examples were spin-coated onto a 6-inch silicon wafer substrate with an aluminum vapor-deposited layer on its surface to a film thickness of approximately 5 μm after curing, and then heated at 170°C for 2 hours in a nitrogen atmosphere to obtain a cured resin film. The resulting cured film was cut into 3 mm widths using a dicing saw and then peeled from the wafer using a dilute hydrochloric acid solution. 20 of the resulting samples were left to stand in an atmosphere of 23°C and 50% humidity for at least 24 hours, after which the elongation (%) was measured using a tensile tester (e.g., Tensilon). The measurement conditions for the tensile tester were as follows: Temperature: 23℃ Humidity: 50% Initial sample length: 50 mm Test speed: 40mm / min Load cell rating: 2kgf

[0128] (9) Chemical resistance evaluation of cured relief pattern (polyimide coating) The cured relief pattern formed on Cu was immersed in a resist stripper (product name ST-44, manufactured by ATMI, mainly consisting of 2-(2-aminoethoxy)ethanol and 1-cyclohexyl-2-pyrrolidone) heated to 50°C for 5 minutes, rinsed with running water for 1 minute, and air-dried. The film surface was then visually observed under an optical microscope to evaluate chemical resistance based on the presence or absence of damage caused by the chemical solution, such as cracks, and the rate of change in film thickness after chemical treatment. Chemical resistance was evaluated according to the following criteria. "Excellent": No cracks occur, and the film thickness change rate is 10% or less based on the film thickness before immersion in chemicals "Good": No cracks occur, and the rate of change in film thickness is more than 10% and less than 15% based on the film thickness before chemical immersion. "Acceptable": No cracks occur, and the film thickness change rate is more than 15% and less than 20% based on the film thickness before chemical immersion. "Unacceptable": Cracks have occurred or the change in film thickness exceeds 20%

[0129] (10) Reflow conditions The photosensitive resin compositions obtained in the examples and comparative examples were spin-coated onto a 6-inch silicon wafer substrate with a copper vapor deposition layer on its surface to a film thickness of approximately 5 μm after curing, and then heated at 170°C for 2 hours in a nitrogen atmosphere to obtain a cured resin film. The resulting cured film was heated to a peak temperature of 260°C in a nitrogen atmosphere under simulated solder reflow conditions using a mesh belt continuous firing furnace (manufactured by Koyo Thermo Systems Co., Ltd., model number 6841-20AMC-36). The simulated reflow conditions were standardized by assuming a high solder melting point of 220°C, in accordance with the solder reflow conditions described in Section 7.6 of IPC / JEDEC J-STD-020A, a standard established by the US semiconductor industry association regarding semiconductor device evaluation methods.

[0130] Example 1 (A) Synthesis of Polymer A-1 as a Polyimide Precursor 10.5 g (0.1 mol) of 1-aminoethoxyethanol (AEE) and 26.0 g of γ-butyrolactone were placed in a 100 mL three-neck flask and cooled to 0°C. 15.5 g (0.1 mol) of Karenz MOI (registered trademark, Showa Denko K.K.) as an isocyanate compound was added dropwise to obtain a γ-butyrolactone solution of urea compound U-1. The volatilization rate of urea compound U-1 after heating at 170°C for 2 hours was 15%.

[0131] 62.0 g (0.2 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 1 L separable flask and 74.9 g of γ-butyrolactone was added. Next, 41.6 g of a γ-butyrolactone solution of U-1 (U-1: 0.08 mol) and 41.6 g of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA, 0.32 mol) were added, and 31.6 g (0.4 mol) of pyridine was added while stirring. The mixture was then stirred at 40°C for 5 hours using an oil bath to obtain a reaction mixture. After the reaction was complete, the mixture was allowed to cool to room temperature and left for 16 hours.

[0132] Next, while stirring the resulting reaction mixture under ice cooling, a solution of 81.3 g (0.39 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 100 g of γ-butyrolactone was added over 40 minutes, followed by a suspension of 33.3 g (0.17 mol) of diaminodiphenyl ether (DADPE) suspended in 300 g of γ-butyrolactone over 60 minutes. After stirring at room temperature for 2 hours, 18 g of ethyl alcohol was added and the mixture was stirred for an additional hour, followed by the addition of 140 g of γ-butyrolactone. The reaction mixture was filtered to remove any precipitate that had formed in the reaction system, yielding a reaction solution.

[0133] The resulting reaction solution was added to 1.2 kg of ethyl alcohol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 600 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 7 kg of water to reprecipitate the polymer. The resulting reprecipitate was collected by filtration and then vacuum dried to obtain a powdered polymer (Polymer A-1). The molecular weight of Polymer A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 29,000.

[0134] <Example 2> (A) Synthesis of Polymer A-2 as a Polyimide Precursor Polymer B-2 was obtained by the same reaction as in Example 1, except that the amount of DADPE in Example 1 was changed to 35.6 g (0.18 mol). The molecular weight of Polymer A-2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 40,000.

[0135] Example 3 (A) Synthesis of Polymer A-3 as a Polyimide Precursor Polymer A-3 was obtained by carrying out a reaction in the same manner as in Example 1, except that 21.8 g (0.1 mol) of pyrrolimetic anhydride (hereinafter referred to as PMDA) and 31.0 g (0.1 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) were used instead of 62.0 g (0.2 mol) of ODPA in Example 1. The molecular weight of Polymer A-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 30,000.

[0136] Example 4 (A) Synthesis of Polymer A-4 as a Polyimide Precursor Polymer A-4 was obtained by carrying out a reaction in the same manner as in Example 1, except that 58.8 g (0.2 mol) of biphenyl-3,4,3',4'-tetracarboxylic dianhydride (hereinafter referred to as BPDA) was used instead of 62.0 g (0.2 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) in Example 1. The molecular weight of Polymer A-4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 29,000.

[0137] <Example 5> (A) Synthesis of Polymer A-5 as a Polyimide Precursor Polymer A-5 was obtained by carrying out a reaction in the same manner as in Example 1, except that 35.4 g (0.17 mol) of m-tolidine was used instead of 33.3 g (0.17 mol) of DADPE in Example 1. The molecular weight of Polymer A-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 29,000.

[0138] Example 6 (A) Synthesis of Polymer A-6 as a Polyimide Precursor 10.5 g (0.1 mol) of 1-aminoethoxyethanol (AEE) and 24.6 g of γ-butyrolactone were placed in a 100 mL three-neck flask and cooled to 0°C. 14.1 g (0.1 mol) of Karenz A01 (registered trademark, Showa Denko K.K.) was added dropwise to obtain a γ-butyrolactone solution of urea compound U-2. The volatilization rate of urea compound U-2 after heating at 170°C for 2 hours was 17%.

[0139] Polymer A-6 was obtained by carrying out a reaction in the same manner as in Example 1, except that 39.4 g of a γ-butyrolactone solution of urea compound U-2 (U-2: 0.08 mol) was used instead of 41.6 g of a γ-butyrolactone solution of urea compound U-1 in Example 1. The molecular weight of polymer A-6 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 28,000.

[0140] Example 7 (A) Synthesis of Polymer A-7 as a Polyimide Precursor 10.5 g (0.1 mol) of 1-aminoethoxyethanol (AEE) and 30.4 g of γ-butyrolactone were placed in a 100 mL three-neck flask and cooled to 0°C. 19.9 g (0.1 mol) of Karenz MOI-EG (registered trademark, Showa Denko K.K.) was added dropwise to obtain a γ-butyrolactone solution of urea compound U-3. The volatilization rate of urea compound U-3 after heating at 170°C for 2 hours was 14%.

[0141] Polymer A-7 was obtained by carrying out a reaction in the same manner as in Example 1, except that 48.7 g of a γ-butyrolactone solution of urea compound U-3 (U-3: 0.08 mol) was used instead of 41.6 g of a γ-butyrolactone solution of urea compound U-1 in Example 1. The molecular weight of polymer A-7 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 30,000.

[0142] Example 8 (A) Synthesis of Polymer A-8 as a Polyimide Precursor 10.5 g (0.1 mol) of 1-aminoethoxyethanol (AEE) and 34.4 g of γ-butyrolactone were placed in a 100 mL three-neck flask and cooled to 0° C. 23.9 g (0.1 mol) of Karenz BEI (registered trademark, Showa Denko K.K.) was added dropwise to obtain a γ-butyrolactone solution of urea compound U-4.

[0143] Polymer A-8 was obtained by carrying out a reaction in the same manner as in Example 1, except that 55.1 g of a γ-butyrolactone solution of urea compound U-4 (U-4: 0.08 mol) was used instead of 41.6 g of a γ-butyrolactone solution of urea compound U-1 in Example 1. The molecular weight of polymer A-8 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 29,000.

[0144] Example 9 (A) Synthesis of Polymer A-9 as a Polyimide Precursor Polymer A-9 was obtained by carrying out the reaction in the same manner as in Example 1, except that the amount of the γ-butyrolactone solution of urea compound U-1 in Example 1 was changed to 10.4 g (U-1: 0.02 mol) and the amount of HEMA was changed to 49.5 g (0.38 mol). The molecular weight of polymer A-9 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 29,000.

[0145] Example 10 (A) Synthesis of Polymer A-10 as a Polyimide Precursor Polymer A-10 was obtained by carrying out a reaction in the same manner as in Example 1, except that the amount of the γ-butyrolactone solution of urea compound U-1 in Example 1 was changed to 197.8 g (U-1: 0.38 mol) and the amount of HEMA was changed to 2.6 g (0.02 mol). The molecular weight of polymer A-10 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 30,000.

[0146] Example 11 (A) Synthesis of Polymer A-11 as a Polyimide Precursor Polymer A-11 was obtained by carrying out a reaction in the same manner as in Example 1, except that the amount of the γ-butyrolactone solution of urea compound U-1 in Example 1 was changed to 208.2 g (U-1: 0.4 mol) and HEMA was not added. The molecular weight of polymer A-11 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 30,000.

[0147] Example 12 (A) Synthesis of Polymer A-12 as a Polyimide Precursor 10.5 g (0.1 mol) of 1-aminoethoxyethanol (AEE) and 23.2 g of γ-butyrolactone were placed in a 100 mL three-neck flask and cooled to 0°C. 12.7 g (0.1 mol) of n-hexyl isocyanate was added dropwise to obtain a γ-butyrolactone solution of urea compound U-5. After heating at 170°C for 2 hours, the volatilization rate of urea compound U-5 was 40%.

[0148] Polymer A-12 was obtained by carrying out a reaction in the same manner as in Example 1, except that 37.2 g of a γ-butyrolactone solution of urea compound U-5 (U-5: 0.08 mol) was used instead of 41.6 g of the γ-butyrolactone solution of urea compound U-1 in Example 1. The molecular weight of polymer A-12 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 28,000.

[0149] Example 13 (A) Synthesis of Polymer A-13 as a Polyimide Precursor 5.78 g (0.077 mol) of N-methylethanolamine (MEA) and 41.0 g of γ-butyrolactone were placed in a 100 mL three-neck flask and cooled to 0°C. 11.95 g (0.077 mol) of Karenz MOI (registered trademark, Showa Denko K.K.) as an isocyanate compound was added dropwise to obtain a γ-butyrolactone solution of urea compound U-6. The volatilization rate of urea compound U-6 after heating at 170°C for 2 hours was 30%.

[0150] 31.0 g (0.1 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 1 L separable flask and 74.9 g of γ-butyrolactone was added. Next, 58.7 g of a γ-butyrolactone solution of U-6 (U-6: 0.077 mol) and 16.79 g of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA, 0.13 mol) were added, and 15.82 g of pyridine was added while stirring. The mixture was then stirred at 40°C for 5 hours using an oil bath to obtain a reaction mixture. After the reaction was complete, the mixture was allowed to cool to room temperature and left for 16 hours.

[0151] Next, while stirring the resulting reaction mixture under ice cooling, a solution of 40.44 g (0.196 mol) of dicyclohexylcarbodiimide (DCC) in 50 g of γ-butyrolactone was added over 40 minutes, followed by a solution of 8.85 g (0.042 mol) of m-tolidine in 30 g of γ-butyrolactone over 40 minutes, followed by a suspension of 8.34 g (0.042 mol) of DADPE in 30 g of γ-butyrolactone over 40 minutes. After stirring at room temperature for 2 hours, 9 g of ethyl alcohol was added and the mixture was stirred for an additional hour. 70 g of γ-butyrolactone was then added. The reaction mixture was filtered to remove any precipitate that had formed in the reaction system, yielding a reaction solution.

[0152] The resulting reaction solution was added to 600 g of ethyl alcohol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 300 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 3.5 kg of water to reprecipitate the polymer. The resulting reprecipitate was collected by filtration and then vacuum dried to obtain a powdered polymer (Polymer A-13). The molecular weight of Polymer A-13 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 23,000.

[0153] Example 14 (A) Synthesis of Polymer A-14 as a Polyimide Precursor A reaction was carried out in the same manner as in Example 13, except that 11.64 g (0.077 mol) of N-benzylethanolamine (NBEA) was used instead of 5.78 g (0.077 mol) of MEA used in Example 13, to obtain a γ-butyrolactone solution of urea compound U-7 and polymer A-14. The molecular weight of polymer A-14 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight-average molecular weight (Mw) of 23,000. The volatilization rate of urea compound U-7 after heating at 170°C for 2 hours was 30%.

[0154] Example 15 (A) Synthesis of Polymer A-15 as a Polyimide Precursor Polymer A-15 was obtained by carrying out a reaction in the same manner as in Example 1, except that 68.3 g (0.17 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter referred to as BAPP) was used instead of 33.3 g (0.17 mol) of DADPE in Example 1. The molecular weight of Polymer A-15 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 25,000.

[0155] Example 16 (A) Synthesis of Polymer A-16 as a Polyimide Precursor Polymer A-16 was obtained by carrying out a reaction in the same manner as in Example 1, except that 104.0 g (0.2 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was used instead of 62.0 g (0.2 mol) of ODPA in Example 1. The molecular weight of Polymer A-16 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

[0156] Example 17 (A) Synthesis of Polymer A-17 as a Polyimide Precursor 10.5 g (0.1 mol) of 1-aminoethoxyethanol (AEE) and 26.0 g of γ-butyrolactone were placed in a 100 mL three-neck flask and cooled to 0°C. 15.5 g (0.1 mol) of Karenz MOI (registered trademark, Showa Denko K.K.) as an isocyanate compound was added dropwise to obtain a γ-butyrolactone solution of urea compound U-1. The volatilization rate of urea compound U-1 after heating at 170°C for 2 hours was 15%.

[0157] 49.6 g (0.16 mol) of ODPA was placed in a 1 L separable flask and 50.0 g of γ-butyrolactone was added. Next, 41.7 g (0.32 mol) of HEMA was added, and 25.3 g (0.32 mol) of pyridine was added while stirring, and then the mixture was stirred at 40°C in an oil bath for 5 hours to obtain reaction mixture A. After the reaction was completed, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0158] 11.8 g (0.04 mol) of BPDA was placed in a 1 L separable flask and 15.0 g of γ-butyrolactone was added. Next, 41.6 g of a γ-butyrolactone solution of U-1 (U-1: 0.08 mol) was added, and 6.32 g (0.08 mol) of pyridine was added while stirring. After that, the mixture was stirred at 40°C for 5 hours using an oil bath to obtain reaction mixture B. After the reaction was completed, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0159] The resulting reaction mixtures A and B were combined and, while stirring under ice cooling, a solution of 81.3 g (0.39 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 100 g of γ-butyrolactone was added over 40 minutes, followed by a suspension of 33.3 g (0.17 mol) of diaminodiphenyl ether (DADPE) suspended in 300 g of γ-butyrolactone over 60 minutes. After stirring at room temperature for 2 hours, 18 g of ethyl alcohol was added and the mixture was stirred for an additional hour. Next, 140 g of γ-butyrolactone was added. The reaction mixture was filtered to remove any precipitate that had formed in the reaction system, yielding a reaction solution.

[0160] The resulting reaction solution was added to 1.2 kg of ethyl alcohol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 600 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 7 kg of water to reprecipitate the polymer. The resulting reprecipitate was collected by filtration and then vacuum dried to obtain a powdered polymer (Polymer A-17). The molecular weight of Polymer A-17 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 26,000.

[0161] <Production Example 1> (A) Synthesis of Polymer A-18 as a Polyimide Precursor 62.0 g (0.2 mol) of ODPA was placed in a 1 L separable flask and 74.9 g of γ-butyrolactone was added. Next, 52.1 g (0.4 mol) of HEMA was added, and 31.6 g (0.4 mol) of pyridine was added while stirring. After stirring for 5 hours at 40°C using an oil bath, a reaction mixture was obtained. After the reaction was completed, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0162] Next, while stirring the resulting reaction mixture under ice cooling, a solution of 81.3 g (0.39 mol) of DCC in 100 g of γ-butyrolactone was added over 40 minutes, followed by a suspension of 33.3 g (0.17 mol) of DADPE in 300 g of γ-butyrolactone over 60 minutes. After stirring at room temperature for 2 hours, 18 g of ethyl alcohol was added and the mixture was stirred for an additional hour, after which 140 g of γ-butyrolactone was added. The reaction mixture was filtered to remove any precipitate that had formed in the reaction system, yielding a reaction solution.

[0163] The resulting reaction solution was added to 1.2 kg of ethyl alcohol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 600 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 7 kg of water to reprecipitate the polymer. The resulting reprecipitate was collected by filtration and then vacuum dried to obtain a powdery polymer (Polymer A-17). The molecular weight of Polymer A-18 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 29,000.

[0164] Example 18 A negative-tone photosensitive resin composition was prepared and evaluated using the following method. (A) 100 g of A-1 (polyimide precursor), (B) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (hereinafter referred to as PDO, B-1) (photopolymerization initiator), (C) 8 g of polyethylene glycol dimethacrylate (C-1) (photopolymerizable monomer), and (D) 0.5 g of adenine (D-1) (corrosion inhibitor) were dissolved in 100 g of γ-butyl lactone (hereinafter referred to as GBL). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding a small amount of GBL, and a negative-tone photosensitive resin composition was prepared. The composition was evaluated according to the aforementioned method. The results are shown in Table 1.

[0165] <Examples 19 to 35, Comparative Example 1> Negative photosensitive resin compositions were prepared in the same manner as in Example 18, except that polymers shown in Table 1 were used, and evaluations were carried out in the same manner as in Example 18. The results are shown in Table 1. In Table 1, urea compound E-1 is a compound represented by the following chemical formula. [ka]

[0166] Example 36 A negative-tone photosensitive resin composition was prepared and evaluated using the following method. (A) 100 g of A-1 (polyimide precursor), (B) 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]propanone-1-(O-acetyloxime) (trade name: PBG-304, Changzhou Strong Electronics Co., Ltd.) (hereinafter referred to as PBG-304, B-2) (photopolymerization initiator), (C) 8 g of polyethylene glycol dimethacrylate (C-1) (photopolymerizable monomer), and (D) 0.5 g of adenine (D-1) (corrosion inhibitor) were dissolved in 100 g of γ-butyl lactone (hereinafter referred to as GBL). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding a small amount of GBL, and a negative-tone photosensitive resin composition was prepared. The composition was evaluated according to the aforementioned method. The results are shown in Table 2.

[0167] Example 37 Evaluation was carried out in the same manner as in Example 35, except that the photopolymerization initiator (B) in Example 36 was changed to 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (trade name: PBG-305, manufactured by Changzhou Strong Electronics Co., Ltd.). The results are shown in Table 2.

[0168] <Examples 38 to 41, Comparative Example 2> Negative photosensitive resin compositions were prepared in the same manner as in Example 36 except for the compositions shown in Table 2, and were evaluated in the same manner as in Example 36. The results are shown in Table 2.

[0169] <Example 42> (A) 100 g of A-13 (polyimide precursor), (B) 3 g of B-2 (photopolymerization initiator), (C) 8 g of polyethylene glycol dimethacrylate (C-1) (photopolymerizable monomer), and (D) 0.5 g of adenine (D-1) (corrosion inhibitor) were dissolved in 100 g of γ-butyl lactone (hereinafter referred to as GBL). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding a small amount of GBL to prepare a negative-tone photosensitive resin composition. The composition was evaluated using the aforementioned unevenness measurement, and the imidization rate after heat curing at 170°C to a thickness of 2.0 microns was 100%. Observation of the polyimide film after reflow using this cured product revealed no cracking or peeling. Furthermore, a fanout-type wafer-level chip size package semiconductor device was fabricated and functioned without any problems.

[0170] <Comparative Example 3> A resin composition was prepared and evaluated in the same manner as in Example 42, except that A-18 was used as the polyimide precursor. The unevenness difference was 0.4 microns, and the imidization rate was 20%. When the polyimide film obtained by this cured product was observed after reflow, cracks and peeling were observed.

[0171] <Comparative Example 4> A resin composition was prepared in the same manner as in Comparative Example 3, except that 20 g of 1-(tert-butoxycarbonyl)-4-piperidinemethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added as an imidization accelerator to the composition of Comparative Example 3. Evaluation revealed that the unevenness difference was 4.1 microns and the imidization rate was 100%. When the polyimide film after reflow was observed using this cured product, no cracks or peeling were observed. However, when a fan-out type wafer-level chip size package type semiconductor device was fabricated, it did not function.

[0172] [Table 1]

[0173] [Table 2] [Industrial Applicability]

[0174] By using the negative-tone photosensitive resin composition according to the present disclosure, it is possible to obtain a cured relief pattern that has a high imidization rate, chemical resistance, and copper adhesion, and that exhibits little outgassing during a heating step after thermal curing. The negative-tone photosensitive resin composition according to the present disclosure can be suitably used in the field of photosensitive materials that are useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) a polyimide precursor containing a structural unit represented by the following general formula (1), and (B) Photopolymerization initiator which is an oxime compound and satisfying the following (i): 【Chemistry 1】 {In formula (1), X １ is a tetravalent organic group having 4 to 40 carbon atoms, and Y １ is a divalent organic group having 6 to 40 carbon atoms, and R １ and R ２ At least one of represents a monovalent organic group directly derived from a urea compound that has a volatilization rate of 14% to 40% when heated at 170°C for 2 hours.} (i) R １ and R ２ One of these represents a monovalent organic group directly derived from a urea compound having a volatilization rate of 14% to 40% when heated at 170°C for 2 hours, and the other represents a group represented by the following general formula (2): 【Chemistry 2】 {In the formula, R ３ , R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer from 2 to 10.

2. 2. The negative photosensitive resin composition according to claim 1, wherein the volatilization rate is 14% to 30%.

3. A method for producing a polyimide, comprising the step of curing the negative photosensitive resin composition according to claim 1 to form a polyimide.

4. The following steps: (1) applying the negative photosensitive resin composition according to claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising:

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