Negative photosensitive resin composition, manufacturing method of polyimide, and manufacturing method of cured relief pattern

Abstract

To provide a negative photosensitive resin composition that realizes high chemical resistance and resolution and can inhibit generation of voids at an interface of a Cu layer in contact with a resin layer after a high-temperature storage test.SOLUTION: The negative photosensitive resin composition comprises (A) a polyimide precursor, (B) a photopolymerization initiator, (C) a silane coupling agent represented by the general formula (1), and (D) an organic solvent containing at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate and ε-caprolactone. In the formula, R22 is a hydroxyl group or a C1-4 alkyl group, and R20 is at least one selected from the group consisting of substituents including epoxy groups, phenylamino groups, ureido groups and isocyanate groups.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a negative photosensitive resin composition, a method for producing a polyimide, and a method for producing a cured relief pattern. [Background technology]

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

[0003] Incidentally, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards by various methods according to the purpose. Conventional elements were generally fabricated by a wire bonding method in which thin wires connect the external terminals (pads) of the element to a lead frame. However, today, as elements have become faster and the operating frequency has 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 precisely control the length of the mounting wiring, and it has become difficult to meet this requirement using wire bonding.

[0004] Therefore, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped over and directly mounted on a printed circuit board (see, for example, Patent Document 1). This flip-chip mounting allows accurate control of wiring distance, and is therefore adopted for high-end devices that handle high-speed signals, and for mobile phones and the like due to its small mounting size, and demand is rapidly expanding. When materials such as polyimide, polybenzoxazole, and phenolic resin are used for flip-chip mounting, a metal wiring layer formation process is performed after the resin layer pattern is formed. The metal wiring layer is usually formed by roughening the surface of the resin layer by plasma etching, forming a metal layer to be a plating seed layer by sputtering to a thickness of 1 μm or less, and then using the metal layer as an electrode, by electrolytic plating. In this case, titanium (Ti) is generally used as the metal that becomes the seed layer, and copper (Cu) is generally used as the metal for the rewiring layer formed by electrolytic plating.

[0005] In recent years, fan-out type semiconductor packages have also been attracting attention. In fan-out type semiconductor packages, a chip sealing body larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with an encapsulant (resin layer). Furthermore, a redistribution layer is formed that extends to the area of ​​the semiconductor chip and the encapsulant. The redistribution layer is formed with a thin film thickness. Furthermore, since the redistribution layer can be formed up to the area of ​​the encapsulant, the number of external connection terminals can be increased.

[0006] For such a metal rewiring layer, it is required that the adhesion between the rewired metal layer and the resin layer is high after the reliability test. In particular, in recent years, it is required that the temperature for heat curing the rewiring layer is lower. Examples of the reliability test include a high-temperature storage test in which the rewiring layer is stored in air at a high temperature of 125°C or higher for 100 hours or more; a high-temperature operation test in which the rewiring layer is stored in air at a temperature of about 125°C for 100 hours or more while wiring is assembled and a voltage is applied; a temperature cycle test in which the rewiring layer is cycled between a low-temperature state of about -65°C to -40°C and a high-temperature state of about 125°C to 150°C in air; a high-temperature and high-humidity storage test in which the rewiring layer is stored in a water vapor atmosphere at a temperature of 85°C or higher and a humidity of 85% or higher; a high-temperature and high-humidity bias test in which the same test as the high-temperature and high-humidity storage test is performed while wiring is assembled and a voltage is applied; and a solder reflow test in which the reflow oven is passed through a solder reflow furnace at 260°C multiple times in air or nitrogen. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2001-338947 A Summary of the Invention [Problem to be solved by the invention]

[0008] However, in the past, in the case of the high-temperature storage test among the above reliability tests, there was a problem that voids were generated at the interface of the rewired Cu layer and the resin layer after the test. In particular, when the heat curing temperature is low, this tends to be more pronounced. When voids are generated at the interface between the Cu layer and the resin layer, the adhesion between the two layers is reduced.

[0009] In addition to the problem of voids, the metal redistribution layer is required to have chemical resistance, and the demand for finer patterning is also increasing. For this reason, photosensitive resin compositions used in particular for forming the redistribution layer of semiconductors are required to suppress the generation of voids and to exhibit high chemical resistance and resolution.

[0010] The present invention has been devised in view of such conventional circumstances, and has as its object to provide a negative-type photosensitive resin composition (hereinafter, also simply referred to as "photosensitive resin composition" in this specification) that can obtain high chemical resistance and resolution and can suppress the generation of voids at the interface where the Cu layer contacts the resin layer after a high temperature storage test. Another object is to provide a method for forming a cured relief pattern using the negative-type photosensitive resin composition of the present invention. [Means for solving the problem]

[0011] The present inventors have found that the above-mentioned problems can be solved by combining a specific polyimide precursor, a silane coupling agent having a specific structure, and a specific organic solvent, and have thus completed the present invention. That is, the present invention is as follows. [1] Ingredients include: (A) polyimide precursor; (B) a photoinitiator; (C) the following general formula (1): [ka] In the formula, a is an integer of 1 to 3, n is an integer of 1 to 6, and R 21 are each independently an alkyl group having 1 to 4 carbon atoms, R 22 is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R 20 is at least one selected from the group consisting of substituents containing an epoxy group, a phenylamino group, a ureido group, and an isocyanate group.} A silane coupling agent represented by the formula: (D) an organic solvent containing at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone; A negative type photosensitive resin composition comprising: [2] In the general formula (1), R 20 is at least one selected from the group consisting of a phenylamino group and a substituent containing a ureido group. [3] In the general formula (1), R 20 is a substituent containing a phenylamino group. [4] The negative photosensitive resin composition according to any one of [1] to [3], further comprising (E) a thermal base generator. [5] The negative type photosensitive resin composition according to any one of [1] to [4], wherein the (D) organic solvent contains at least two selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone. [6] The polyimide precursor (A) is represented by the following general formula (2): [ka] {where, X 1 is a tetravalent organic group, and Y 1 is a divalent organic group, n 1 is an integer between 2 and 150, and R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and R 1 and R 2 At least one of is a monovalent organic group. The negative type photosensitive resin composition according to any one of [1] to [5], having a structural unit represented by the following formula: [7] In the general formula (2), R 1 and R 2 At least one of the following general formula (3): [ka] {In formula, L 1 , L2 and L 3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 1 is an integer between 2 and 10. The negative type photosensitive resin composition according to [6], wherein the monovalent organic group is represented by the following formula: [8] In the general formula (2), X 1 is represented by the following general formula (20a): [ka] The negative type photosensitive resin composition according to [6] or [7], having a structure represented by the following formula: [9] In the general formula (2), X 1 is represented by the following general formula (20b): [ka] The negative type photosensitive resin composition according to [6] or [7], having a structure represented by the following formula:

[10] In the general formula (2), X 1 is represented by the following general formula (20c): [ka] The negative type photosensitive resin composition according to [6] or [7], having a structure represented by the following formula:

[11] In the general formula (2), Y 1 is represented by the following general formula (21b): [ka] The negative type photosensitive resin composition according to any one of [6] to

[10] , comprising a structure represented by the following formula:

[12] In the general formula (2), Y 1 is represented by the following general formula (21c): [ka] {where, R 6is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.} The negative type photosensitive resin composition according to any one of [6] to

[10] , comprising a structure represented by the following formula:

[13] The polyimide precursor (A) is represented by the following general formula (4): [ka] {where, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of is a monovalent organic group, and n 1 is an integer between 2 and 150. The negative type photosensitive resin composition according to [6] or [7], having a structural unit represented by the following formula:

[14] The (A) polyimide precursor is represented by the following general formula (5): [ka] {where, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of is a monovalent organic group, and n 1 is an integer between 2 and 150. The negative type photosensitive resin composition according to [6] or [7], having a structural unit represented by the following formula:

[15] The polyimide precursor (A) is represented by the following general formula (4): [ka] {where, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, R 1 and R 2At least one of is a monovalent organic group, and n 1 is an integer of 2 to 150.}, The following general formula (5): [ka] {where, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of is a monovalent organic group, and n 1 is an integer of 2 to 150. These are R 1 , R 2 , and n 1 may be the same as or different from. The negative type photosensitive resin composition according to [6] or [7], further comprising a structural unit represented by the following formula:

[16] The negative photosensitive resin composition according to

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

[17] The (A) polyimide precursor is represented by the following general formula (6): [ka] {where, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of is a monovalent organic group, and n 1 is an integer between 2 and 150. The negative type photosensitive resin composition according to [6] or [7], having a structural unit represented by the following formula:

[18] 100 parts by mass of the (A) polyimide precursor; 0.1 to 20 parts by mass of the (B) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor; 0.1 to 20 parts by mass of the silane coupling agent (C) based on 100 parts by mass of the polyimide precursor (A); The negative type photosensitive resin composition according to any one of [1] to

[17] ,

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

[18] into a polyimide.

[20] The process is as follows: (1) A step of applying a negative type 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; and (4) heat treating the relief pattern to form a hardened relief pattern; 2. A method for producing a cured relief pattern comprising: Effect of the Invention

[0012] According to the present invention, it is possible to provide a negative-type photosensitive resin composition and a method for producing a polyimide which provide high chemical resistance and resolution and suppress the generation of voids at the interface where the Cu layer contacts the resin layer after a high temperature storage test, and also to provide a method for forming a cured relief pattern using the negative-type photosensitive resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, a detailed description will be given of an embodiment of the present invention (hereinafter, abbreviated as "embodiment"). Note that the present invention is not limited to the following embodiment, and can be modified in various ways within the scope of the present invention. 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.

[0014] <Negative-type photosensitive resin composition> The negative type photosensitive resin composition according to the present embodiment comprises the following components: (A) polyimide precursor; (B) a photoinitiator; (C) a silane coupling agent having a specific structure; and (D) certain organic solvents; Includes.

[0015] From the viewpoint of obtaining high resolution, the negative type photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor, 0.1 to 20 parts by mass of (B) photopolymerization initiator based on 100 parts by mass of (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) silane coupling agent having a specific structure based on 100 parts by mass of (A) polyimide precursor.

[0016] (A) Polyimide precursor The polyimide precursor (A) in this embodiment is a resin component contained in the negative photosensitive resin composition, and is converted into a polyimide by subjecting it to a heat cyclization treatment. The polyimide precursor is represented by the following general formula (2): [ka] {where, X 1 is a tetravalent organic group, and Y 1 is a divalent organic group, n 1 is an integer between 2 and 150, and R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group. It is preferable that the polyamide has a structural unit represented by the following formula:

[0017] R 1 and R 2 At least one of the above is preferably represented by the following general formula (3): [ka] {In formula, L 1 , L 2 and L3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 1 is an integer between 2 and 10. It is a monovalent organic group represented by the formula:

[0018] n in general formula (2) 1 is not limited as long as it is an integer from 2 to 150, but is preferably an integer from 3 to 100, and more preferably an integer from 5 to 70, from the viewpoint of the photosensitive properties and mechanical properties of the negative photosensitive resin composition.

[0019] In general formula (2), X 1 From the viewpoint of achieving both heat resistance and photosensitive properties, the tetravalent organic group represented by the formula (I) is preferably an organic group having 6 to 40 carbon atoms, and more preferably, -COOR 1 Group and -COOR 2 The X group and the -CONH- group are in the ortho position relative to each other, or the X group is an alicyclic aliphatic group. 1 Specific examples of the tetravalent organic group represented by the formula (20) include organic groups having 6 to 40 carbon atoms containing an aromatic ring, such as those represented by the formula (20): [ka] {where, R 6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4. Examples of the group having a structure represented by the formula {, but are not limited to these. In addition, X 1 The structure represented by the above formula (20) may be one type or a combination of two or more types. 1 The group is preferable from the viewpoint of achieving both heat resistance and photosensitive properties.

[0020] X 1 As the group, among the structures represented by the above formula (20), those represented by the following formula (20A), (20B), or (20C): [ka] [ka] [ka] The structure represented by the following formula (20a), (20b) or (20c) is more preferable from the viewpoints of chemical resistance, resolution and suppression of voids after a high-temperature storage test: [ka] [ka] [ka] The structure represented by the following formula is particularly preferred.

[0021] In the above general formula (2), Y 1 From the viewpoint of achieving both heat resistance and photosensitive properties, the divalent organic group represented by the following formula (21): [ka] {where, R 6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.} Examples of the structure include, but are not limited to, those represented by the following formula: 1 The structure represented by the above formula (21) may be one type or a combination of two or more types. 1 The group is preferable from the viewpoint of achieving both heat resistance and photosensitive properties.

[0022] Y 1 As the group, among the structures represented by the above formula (21), those represented by the following formula (21A), (21B) or (21C): [ka] [ka] [ka] The structure represented by the following formula (21b) or (21c): [ka] [ka] The structure represented by the following formula is particularly preferred.

[0023] L in the above general formula (3) 1 is preferably a hydrogen atom or a methyl group, and L 2 and L 3 From the viewpoint of photosensitive properties, it is preferable that m is a hydrogen atom. 1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitive characteristics.

[0024] In one embodiment, the polyimide precursor (A) is represented by the following general formula (4): [ka] {where, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of is a monovalent organic group, and n 1 is an integer between 2 and 150. It is preferable that the polyimide precursor has a structural unit represented by the following formula: In the general formula (4), R 1 and R 2It is more preferable that at least one of the above is a monovalent organic group represented by the above general formula (3). When the polyimide precursor (A) contains a polyimide precursor represented by the general formula (4), the effect of particularly improving the resolution is enhanced.

[0025] In one embodiment, the polyimide precursor (A) is represented by the following general formula (5): [ka] {where, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of is a monovalent organic group, and n 1 is an integer between 2 and 150. It is preferable that the polyimide precursor has a structural unit represented by the following formula: In the general formula (5), R 1 and R 2 It is more preferable that at least one of the above is a monovalent organic group represented by the general formula (3). When the polyimide precursor (A) contains a polyimide precursor represented by the general formula (5) in addition to the polyimide precursor represented by the general formula (4), the effect of particularly improving the resolution is further improved.

[0026] Among these, it is particularly preferable that (A) polyimide precursor simultaneously contains structural units represented by the above general formulas (4) and (5) or is a copolymer of structural units represented by the above general formulas (4) and (5) from the viewpoints of chemical resistance, resolution, and suppression of voids after high-temperature storage test. When (A) polyimide precursor is a copolymer of structural units represented by general formulas (4) and (5), R 1 , R 2 , and n 1 Each of R in the other formula 1 , R 2 , and n 1 may be the same as or different from.

[0027] In one embodiment, the polyimide precursor (A) is represented by the following general formula (6): [ka] {where, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of is a monovalent organic group, and n 1 is an integer between 2 and 150. It is preferable that the polyimide precursor has a structural unit represented by the following formula: In the general formula (6), R 1 and R 2 It is more preferable that at least one of the above is a monovalent organic group represented by the above general formula (3). When the (A) polyimide precursor contains a polyimide precursor represented by the general formula (6), the effect of chemical resistance is particularly enhanced.

[0028] (A) Method for preparing polyimide precursor (A) The polyimide precursor is first prepared by reacting a tetravalent organic group X 1 A tetracarboxylic acid dianhydride containing the compound represented by the formula (2) is reacted with an alcohol having a photopolymerizable unsaturated double bond and, optionally, an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester body). Then, the partially esterified tetracarboxylic acid is reacted with a divalent organic group Y 1 and diamines containing the same.

[0029] (Preparation of Acid / Ester Forms) In this embodiment, (A) a tetravalent organic group X that is suitably used for preparing a polyimide precursor is 1Examples of the tetracarboxylic dianhydride containing the formula (20) include tetracarboxylic dianhydrides having the structure represented by the above general formula (20), as well as, for example, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, Examples of the dianhydride include tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and preferably pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited thereto. These may be used alone or in combination of two or more.

[0030] In the present embodiment, examples of alcohols having a photopolymerizable unsaturated double bond that are suitably used for preparing the polyimide precursor (A) include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. 1-(2-tert-butoxypropyl)-2-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.

[0031] The above-mentioned photopolymerizable alcohols having an unsaturated double bond may be partially mixed with alcohols not having an unsaturated double bond, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

[0032] In addition, a non-photosensitive polyimide precursor prepared only from the alcohols not having an unsaturated double bond may be used as the polyimide precursor by mixing it with the photosensitive polyimide precursor. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

[0033] The above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohol are stirred, dissolved, and mixed in a solvent as described below at a temperature of 20 to 50° C. for 4 to 10 hours in the presence of a basic catalyst such as pyridine, whereby the esterification reaction of the acid anhydride proceeds, and the desired acid / ester can be obtained.

[0034] (Preparation of polyimide precursor) A suitable dehydration condensation agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, or the like is added to and mixed with the above acid / ester body (typically a solution in a solvent described below) under ice cooling to convert the acid / ester body into a polyacid anhydride, and then a divalent organic group Y 1 The desired polyimide precursor can be obtained by adding dropwise a diamine containing the compound dissolved or dispersed in a separate solvent and carrying out amide polycondensation. Alternatively, the desired polyimide precursor can be obtained by converting the acid moiety of the acid / ester product into an acid chloride using thionyl chloride or the like, and then reacting the acid with a diamine compound in the presence of a base such as pyridine.

[0035] Divalent organic group Y preferably used in this embodiment 1Examples of diamines containing the formula (21) include diamines having the structure represented by the above general formula (21), as well as, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'- Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3 -aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis [4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidinesulfone, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., 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, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

[0036] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation operations, and then vacuum drying is performed to isolate the desired polyimide precursor. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0037] The molecular weight of the polyimide precursor (A) is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, when measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

[0038] (B) Photopolymerization initiator The photopolymerization initiator (B) used in this embodiment will be described. The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples of the photopolymerization initiator include benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives, benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives, benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(o-methoxy Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as 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-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are more preferred, particularly from the viewpoint of photosensitivity.

[0039] The amount of the photopolymerization initiator (B) in the negative photosensitive resin composition is preferably 0.1 to 20 parts by mass, more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the polyimide precursor (A). The amount is 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning property, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

[0040] (C) Silane coupling agent having a specific structure The silane coupling agent having a specific structure (C) used in this embodiment will be described. The silane coupling agent having a specific structure (C) according to this embodiment has a structure represented by the following general formula (1). [ka] In the formula, a is an integer of 1 to 3, n is an integer of 1 to 6, and R 21 are each independently an alkyl group having 1 to 4 carbon atoms, R 22 is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R 20 is at least one selected from the group consisting of a substituent containing an epoxy group, a phenylamino group, and a ureido group.} In the general formula (1), a is not limited as long as it is an integer of 1 to 3, but is preferably 2 or 3, and more preferably 3, from the viewpoint of adhesion to the metal redistribution layer. Although n is not limited as long as it is an integer of 1 to 6, from the viewpoint of adhesion to the metal redistribution layer, it is preferably from 1 to 4. From the viewpoint of developability, it is preferably from 2 to 5. R 21 is not limited as long as it is an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. R 22 is not limited as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include R 21 The alkyl groups shown in the above are exemplified. R 20 is not limited as long as it is a substituent containing an epoxy group, a phenylamino group, a ureido group, or an isocyanate group. Among these, from the viewpoint of developability and adhesion of the metal redistribution layer, it is preferable that it is at least one selected from the group consisting of a substituent containing a phenylamino group and a substituent containing a ureido group, and a substituent containing a phenylamino group is more preferable. Examples of silane coupling agents containing an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. An example of a silane coupling agent containing a phenylamino group is N-phenyl-3-aminopropyltrimethoxysilane. An example of a silane coupling agent containing a ureido group is 3-ureidopropyltrialkoxysilane. An example of a silane coupling agent containing an isocyanate group is 3-isocyanatepropyltriethoxysilane.

[0041] (D) Organic solvent with a specific structure The organic solvent according to the present embodiment is not limited as long as it contains at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone. By containing the above organic solvent, sufficient adhesion to the sealing material can be exhibited. Among them, from the viewpoint of the solubility of the (A) polyimide precursor, γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, and ε-caprolactone are preferred, and from the viewpoint of suppressing voids on the copper surface, it is more preferred to contain at least two organic solvents selected from the above group.

[0042] Although it is not clear why the organic solvent having the specific structure according to the present embodiment has good adhesion to the sealing material, the present inventors presume it as follows. Conventionally, amide-based solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide have been used as organic solvents for dissolving photosensitive resin compositions containing polyimide precursors. Although these solvents have a very high dissolving ability for polyimide precursors, when the heat curing temperature required in recent years is low (for example, less than 200°C), they tend to remain in large amounts in the film due to their high affinity with the polyimide produced. Therefore, the performance is reduced due to interactions with the silane coupling agent having the above-mentioned (C) specific structure. On the other hand, by including the above-mentioned solvents, even if the heat curing temperature is low, the solvent remaining in the film after heat curing can be sufficiently reduced, so that the adhesion to the sealing material tends to be good.

[0043] In the negative type photosensitive resin composition of the present embodiment, the amount of the organic solvent used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and further preferably 125 to 500 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor.

[0044] (E) Thermal base generator The negative type photosensitive resin composition of the present embodiment may further contain components other than the above components (A) to (D). In particular, in order to accommodate lowering of the heat curing temperature, it is more preferable to contain a thermal base generator (E). The base generator refers to a compound that generates a base when heated. By including the thermal base generator, the imidization of the photosensitive resin composition can be further promoted.

[0045] The thermal base generator is not particularly limited in type, but examples thereof include amine compounds protected by a tert-butoxycarbonyl group, thermal base generators disclosed in International Publication No. 2017 / 038598, etc. However, the thermal base generator is not limited thereto, and other known thermal base generators can be used.

[0046] 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-(isopropyl ... propylamino)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, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a tert-butoxycarbonyl group, but these are not limited thereto.

[0047] The blending amount of the (E) thermal base generator is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. The blending amount is preferably 0.1 parts by mass or more from the viewpoint of the imidization promotion effect, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

[0048] The negative photosensitive resin composition of the present embodiment may further contain components other than the above components (A) to (E). Examples of components other than the components (A) to (E) include, but are not limited to, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors.

[0049] <Nitrogen-containing heterocyclic compounds> When the negative photosensitive resin composition of the present embodiment is used to form a cured film on a substrate made of copper or a copper alloy, the negative photosensitive resin composition may optionally contain a nitrogen-containing heterocyclic compound in order to suppress discoloration on the copper. Specific examples of such compounds include azole compounds and purine derivatives.

[0050] Examples of the azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, triazole, 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.

[0051] Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0052] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminopurine, and the like. 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.

[0053] When the negative photosensitive resin composition contains the azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound relative to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, when the negative photosensitive resin composition of this embodiment is formed on copper or a copper alloy, discoloration of the copper or copper alloy surface is suppressed, while when the blending amount is 20 parts by mass or less, the photosensitivity is excellent.

[0054] <Hindered phenol compounds> In order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenon), and 4,4'-butylidene-bis(3-methyl-6-t-butylphenon). ol), 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-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol) 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 the amine include azine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, but are not limited thereto. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0055] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and from the viewpoint of photosensitivity characteristics, is more preferably 0.5 to 10 parts by mass. When the amount of the hindered phenol compound is 0.1 part by mass or more relative to 100 parts by mass of the polyimide precursor (A), for example, when the negative type photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, whereas when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0056] <Organotitanium compounds> The negative photosensitive resin composition of the present embodiment may contain an organotitanium compound. By containing an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0057] Organotitanium compounds that can be used include those in which an organic chemical is bonded to a titanium atom via a covalent or ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability and a good pattern for the negative photosensitive resin composition. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.

[0058] 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}], and the like.

[0059] III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-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.

[0060] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate.

[0061] Among these, 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, and titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

[0062] When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the polyimide precursor (A). When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is obtained.

[0063] <Sensitizer> The negative photosensitive resin composition of the present embodiment 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, p-dimethylaminocinnamylidene indane, and the like. Non, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone ethyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-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.

[0064] When the negative photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of the polyimide precursor (A).

[0065] <Photopolymerizable unsaturated monomer> The negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and examples thereof include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates and dimethacrylates of 1,4-butanediol, and 1,6-hexane diacrylate and dimethacrylate. Examples of such compounds include diacrylates and dimethacrylates of diols, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylates and methacrylates of glycerol, di-, tri-, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0066] When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0067] <Thermal polymerization inhibitor> In addition, the negative photosensitive resin composition of the present embodiment may optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition during storage, particularly in the form of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether 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.

[0068] <Method for Producing Cured Relief Pattern and Semiconductor Device> The present invention also provides a method for producing a cured relief pattern, comprising the steps of: (1) applying the negative type photosensitive resin composition of the present embodiment described above 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; and (4) heat-treating the relief pattern to form a cured relief pattern.

[0069] (1) Photosensitive resin layer formation process In this step, the negative photosensitive resin composition of the present invention is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method that has been conventionally used for applying a photosensitive resin composition, such as a method of applying with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray application with a spray coater, etc., can be used.

[0070] If necessary, the coating film containing the negative photosensitive resin composition can be dried. As a drying method, air drying, heat drying using an oven or a hot plate, vacuum drying, etc. can be used. Specifically, when air drying or heat drying is performed, drying can be performed under conditions of 20°C to 140°C for 1 minute to 1 hour. As described above, a photosensitive resin layer (negative photosensitive resin layer) can be formed on a substrate.

[0071] (2) Exposure process In this step, the negative photosensitive resin layer formed above is exposed to an ultraviolet light source or the like through a photomask or reticle having a pattern, or directly, using an exposure device such as a contact aligner, mirror projection, or stepper.

[0072] Thereafter, for the purpose of improving the photosensitivity, etc., a post-exposure bake (PEB) and / or a pre-development bake may be performed at any combination of temperature and time, as necessary. The range of baking conditions is preferably a temperature of 40° C. to 120° C. and a time of 10 seconds to 240 seconds, but is not limited to this range as long as it does not impair the various properties of the negative-type photosensitive resin composition of the present invention.

[0073] (3) Relief pattern formation process In this process, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a development method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.

[0074] The developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferable. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more types of each solvent, for example, several types, can be used in combination.

[0075] (4) Hardened relief pattern formation process In this step, the relief pattern obtained by the above development is heated to disperse the photosensitive component and imidize the polyimide precursor (A), thereby converting it into a cured relief pattern made of polyimide. As a method for heat curing, various methods can be selected, such as a method using a hot plate, a method using an oven, or a method using a temperature-elevating oven that can set a temperature program. Heating can be performed, for example, under conditions of 170°C to 400°C for 30 minutes to 5 hours. As the atmospheric gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may also be used.

[0076] <Polyimide> The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (8). [ka] {where, X 1 and Y 1 is X in general formula (2). 1 and Y 1 where m is a positive integer. Preferred X in formula (2)1 and Y 1 For the same reason, is also preferred in the polyimide of general formula (8). The number m of repeating units in general formula (8) is not particularly limited as long as it is a positive integer, but may be an integer of 2 to 150, or an integer of 3 to 140.

[0077] Another aspect of the present invention is a method for producing a polyimide, which includes a step of converting the above-described negative photosensitive resin composition into a polyimide.

[0078] <Semiconductor device> In this embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. Thus, a semiconductor device can be provided having a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-mentioned method for producing a cured relief pattern. The present invention can also be applied to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-mentioned method for producing a cured relief pattern as part of the process. The semiconductor device of the present invention can be produced by forming the cured relief pattern formed by the above-mentioned method for producing a cured relief pattern 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 combining the method with a known method for producing a semiconductor device.

[0079] <Display device> In this embodiment, a display device is provided that includes a display element and a cured film provided on the upper portion of the display element, and the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. For example, the cured film may be a surface protection film, an insulating film, and a planarizing film for a thin film transistor (TFT) liquid crystal display element and a color filter element, a protrusion for a multi-domain vertical alignment (MVA) type liquid crystal display device, and a partition wall for a cathode of an organic electroluminescence (EL) element.

[0080] The negative photosensitive resin composition of the present invention is useful not only for application to the semiconductor device 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. EXAMPLES

[0081] The present embodiment will be described in detail below with reference to examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the polymer or the negative photosensitive resin composition were measured and evaluated according to the following methods.

[0082] <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-806M, 2 in series, or Showa Denko Shodex 805M / 806M series Standard monodisperse polystyrene: Showa Denko Co., Ltd. Shodex STANDARD SM-105 Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min.

[0083] (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 200 nm of Ti and 400 nm of Cu, in that order, using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation). Next, a negative-type photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Co., Ltd.), and prebaked on a hot plate at 110°C for 180 seconds to form a coating film with a thickness of approximately 7 μm. Using a test pattern mask, this coating film was then sprayed with 500 mJ / cm using Prisma GHI (manufactured by Ultratech Co., Ltd.). 2 The coating was then spray-developed with a coater developer (D-Spin60A, manufactured by SOKUDO Co., Ltd.) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The wafer with the relief pattern formed on Cu was heat-treated in a temperature-ramp programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg) in a nitrogen atmosphere at the curing temperature shown in Table 1 for 2 hours to obtain a cured relief pattern made of resin approximately 4 to 5 μm thick on Cu.

[0084] (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. At this time, if the area of ​​the opening of the obtained pattern was 1 / 2 or more of the corresponding pattern mask opening area, it was considered to be resolved, and the length of the mask opening side corresponding to the resolved opening having the smallest area was taken as the resolution. Resolutions less than 10 μm were rated "excellent," those between 10 μm and 14 μm were rated "good," those between 14 μm and 18 μm were rated "passable," and those over 18 μm were rated "poor."

[0085] (4) High temperature storage test of hardened relief patterns on Cu and subsequent void area evaluation The wafer with the cured relief pattern formed on Cu was heated in air at 150°C for 168 hours using a temperature-programmable curing furnace (VF-2000, manufactured by Koyo Lindberg). Then, the resin layer on Cu was entirely removed by plasma etching using a plasma surface treatment device (EXAM, manufactured by Shinko Seiki Co., Ltd.). The plasma etching conditions were as follows: Output: 133W Gas type / flow rate: O 2 :40mL / min + CF 4 :1mL / min Gas pressure: 50Pa Mode: Hard Mode Etching time: 1800 seconds

[0086] The Cu surface from which the resin layer had been completely removed was observed with an FE-SEM (S-4800 model, manufactured by Hitachi High-Technologies Corporation), and the area of ​​voids on the surface of the Cu layer was calculated using image analysis software (Azo-kun, manufactured by Asahi Kasei Corporation). When the total area of ​​voids in the evaluation of the photosensitive resin composition described in Comparative Example 1 was taken as 100%, those with a total void area ratio of less than 50% were judged as "excellent", those with a void area ratio of 50% or more and less than 75% were judged as "good", those with a void area ratio of 75% or more and less than 100% were judged as "passable", and those with a void area ratio of 100% or more were judged as "unacceptable".

[0087] (5) Chemical resistance evaluation of cured relief pattern (polyimide coating) The cured relief pattern formed on Cu was immersed in a resist stripper {manufactured by ATMI, product name ST-44, main components: 2-(2-aminoethoxy)ethanol and 1-cyclohexyl-2-pyrrolidone} heated to 50°C for 5 minutes, washed with running water for 1 minute, and air-dried. Thereafter, the film surface was visually observed with an optical microscope, and the chemical resistance was evaluated based on the presence or absence of damage caused by the chemical solution, such as cracks, and / or the change in film thickness after chemical treatment. As evaluation criteria, those without damage such as cracks and with a film thickness change rate of 10% or less based on the film thickness before chemical immersion were rated as "excellent", those with a film thickness change rate of 10-15% were rated as "good", those with a film thickness change rate of 15-20% were rated as "passable", and those with cracks or a film thickness change rate of more than 20% were rated as "unacceptable".

[0088] (6) Adhesion test with sealing material The R4000 series manufactured by Nagase Chemtex Corporation was used as the epoxy-based sealing material. Next, the sealing material was spin-coated onto an aluminum-sputtered silicon wafer to a thickness of about 150 microns, and the epoxy-based sealing material was cured by thermal curing at 130°C. The photosensitive resin composition prepared in the Examples and Comparative Examples was applied onto the above-mentioned epoxy-based cured film to a final film thickness of 10 microns. The applied photosensitive resin composition was applied at 500 mJ / cm 2 After exposing the entire surface under the above exposure conditions, the film was thermally cured at 180° C. for 2 hours to produce a first cured film having a thickness of 10 microns. The photosensitive resin composition used in forming the first cured film was applied onto the first cured film, and the entire surface was exposed to light under the same conditions as when the first cured film was prepared. The entire surface was then thermally cured to form a second cured film having a thickness of 10 microns. An epoxy resin was applied onto the photosensitive resin cured film of the above sample, and then a pin was inserted and an adhesion test was performed using a pull tester (Quad Group, Sebastian 5). Evaluation was performed according to the following criteria. Evaluation: Adhesive strength 70MPa or more: Excellent adhesion 50MPa or more - less than 70MPa: Good adhesion 30MPa or more - less than 50MPa: Adhesion is good Less than 30MPa: Adhesion not possible

[0089] Production Example 1: (A) Synthesis of Polymer A-1 as a Polyimide Precursor 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the reaction mixture was allowed to cool to room temperature and left to stand for 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, followed by the addition of 93.0 g of 4,4'-oxydianiline (ODA) suspended in 350 mL of γ-butyrolactone over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0090] The reaction solution obtained was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The crude polymer solution obtained was dropped into 28 L of water to precipitate the polymer, and the resulting precipitate was filtered off 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) to find that the weight average molecular weight (Mw) was 20,000.

[0091] Production Example 2: (A) Synthesis of Polymer A-2 as a Polyimide Precursor Polymer (A-2) was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. 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 22,000.

[0092] Production 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 the above-mentioned Production Example 1, except that 50.2 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. The molecular weight of polymer (A-3) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 19,000.

[0093] Production 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 the above-mentioned Production Example 1, except that 4,4'-oxydiphthalic dianhydride was replaced with fluorene dianhydride (229.2 g) and 4,4'-oxydianiline was replaced with 2,2'-bis(trifluoromethyl)benzidine (TFMB) (148.5 g) in Production Example 1. The molecular weight of polymer (A-4) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 12,000.

[0094] Production 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 the above-mentioned Production Example 1, except that 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production 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 21,000.

[0095] Production Example 6: (E) Synthesis of Thermal Base Generator E-1 In a 1L eggplant-shaped flask, 100g of diethylene glycol bis(3-aminopropyl)ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100g of ethanol were added and mixed with a stirrer to obtain a homogeneous solution, which was then cooled to 5°C or less with ice water. A solution of 215g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 120g of ethanol was added dropwise using a dropping funnel. At this time, the dropping speed was adjusted so that the reaction liquid temperature was kept below 50°C. Two hours after the end of the dropping, the reaction liquid was concentrated under reduced pressure at 50°C for 3 hours to obtain the target compound E-1.

[0096] <Example 1> A negative photosensitive resin composition was prepared using polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1 as a polyimide precursor, (B) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photopolymerization initiator B-1) as a photopolymerization initiator, (C) 1.5 g of KBM-403, and (D) 150 g of an organic solvent γ-butyrolactone (hereinafter referred to as GBL). The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the above-mentioned method. The results are shown in Table 1.

[0097] <Examples 2 to 13 and Comparative Examples 1 to 3> A negative type photosensitive resin composition similar to that in Example 1 was prepared, except that it was prepared with the components and the compounding ratios shown in Table 1, and was evaluated in the same manner as in Example 1. The results are shown in Table 1. The compounds listed in Table 1 are as follows.

[0098] B-1: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime C-1: 3-Glycidoxypropyltrimethoxysilane (KBM-403) C-2: N-phenyl-3-aminopropyltrimethoxysilane (KBM-573) C-3: 3-Ureidopropyltriethoxysilane (KBE-585) C-4: 3-Isocyanatepropyltriethoxysilane (KBE-9007) C-5: 3-aminopropyltrimethoxysilane (KBM-903) D-1: γ-Butyl lactone (hereinafter referred to as GBL) D-2: Dimethyl sulfoxide (DMSO) E-1: Compound represented by Production Example 5 E-2: 1-(tert-butoxycarbonyl)-4-hydroxypiperidine (Tokyo Chemical Industry Co., Ltd.)

[0099] [Table 1]

[0100] As is clear from Table 1, in Examples 1 to 13 containing the silane coupling agent (C) having the specific structure represented by the general formula (1), higher chemical resistance and resolution were obtained compared to Comparative Examples 1 to 3 not containing the silane coupling agent (C) having the specific structure represented by the general formula (1). Furthermore, after the high-temperature storage test, the generation of voids at the interface where the Cu layer contacts the resin layer could be suppressed, and the adhesion to the sealing material was also good. [Industrial Applicability]

[0101] By using the negative photosensitive resin composition according to the present invention, a cured relief pattern having high chemical resistance and resolution can be obtained, and the generation of voids on the Cu surface can be suppressed. The present invention can be suitably used in the field of photosensitive materials useful for manufacturing electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. A negative-type photosensitive resin composition used to produce a cured relief pattern at a heat curing temperature of less than 200°C, Ingredients below: (A) a polyimide precursor; (B) a photopolymerization initiator; (C) a compound represented by the following general formula (1): 【Chemistry 1】 In the formula, a is an integer from 1 to 3, n is an integer from 1 to 6, and R ２１ are each independently an alkyl group having 1 to 4 carbon atoms; R ２２ is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R ２０ is at least one selected from the group consisting of substituents containing an epoxy group, a phenylamino group, a ureido group, and an isocyanate group. A silane coupling agent represented by the formula: (D) an organic solvent containing at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone; A negative type photosensitive resin composition comprising:

2. In the general formula (1), R ２０ The negative type photosensitive resin composition according to claim 1 , wherein is at least one selected from the group consisting of a phenylamino group and a substituent containing a ureido group.

3. In the general formula (1), R ２０ The negative type photosensitive resin composition according to claim 1 or 2, wherein is a substituent containing a phenylamino group.

4. The negative type photosensitive resin composition according to any one of claims 1 to 3, further comprising (E) a thermal base generator.

5. The negative type photosensitive resin composition according to any one of claims 1 to 4, wherein the (D) organic solvent contains at least two selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone.

6. The polyimide precursor (A) is represented by the following general formula (2): 【Chemistry 2】 {In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of is a monovalent organic group. The negative type photosensitive resin composition according to any one of claims 1 to 5, having a structural unit represented by the following formula:

7. In the general formula (2), R １ and R ２ At least one of the following general formula (3): 【Chemistry 3】 {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer from 2 to 10. The negative type photosensitive resin composition according to claim 6, wherein the aryl group is a monovalent organic group represented by the following formula:

8. In the general formula (2), X １ is represented by the following general formula (20a): 【Chemistry 4】 The negative type photosensitive resin composition according to claim 6 or 7, having a structure represented by the following formula:

9. In the general formula (2), X １ is represented by the following general formula (20b): 【Chemistry 5】 The negative type photosensitive resin composition according to claim 6 or 7, having a structure represented by the following formula:

10. In the general formula (2), X １ is represented by the following general formula (20c): 【Chemistry 6】 The negative type photosensitive resin composition according to claim 6 or 7, having a structure represented by the following formula:

11. In the general formula (2), Y １ is represented by the following general formula (21b): 【Chemistry 7】 The negative type photosensitive resin composition according to any one of claims 6 to 10, comprising a structure represented by:

12. In the general formula (2), Y １ is represented by the following general formula (21c): 【Chemistry 8】 {In the formula, R ６ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4. The negative type photosensitive resin composition according to any one of claims 6 to 10, comprising a structure represented by:

13. The polyimide precursor (A) is represented by the following general formula (4): 【Chemistry 9】 {In the formula, R １ and R ２ are each independently a hydrogen atom or a monovalent organic group; R １ and R ２ At least one of is a monovalent organic group, and n １ is an integer from 2 to 150. The negative type photosensitive resin composition according to claim 6 or 7, which has a structural unit represented by the following formula:

14. The polyimide precursor (A) is represented by the following general formula (5): 【Chemistry 10】 {In the formula, R １ and R ２ are each independently a hydrogen atom or a monovalent organic group; R １ and R ２ At least one of is a monovalent organic group, and n １ is an integer from 2 to 150. The negative type photosensitive resin composition according to claim 6 or 7, which has a structural unit represented by the following formula:

15. The polyimide precursor (A) is represented by the following general formula (4): 【Chemistry 11】 {In the formula, R １ and R ２ are each independently a hydrogen atom or a monovalent organic group; R １ and R ２ At least one of is a monovalent organic group, and n １ is an integer from 2 to 150. The following general formula (5): 【Chemistry 12】 {In the formula, R １ and R ２ are each independently a hydrogen atom or a monovalent organic group; R １ and R ２ At least one of is a monovalent organic group, and n １ is an integer from 2 to 150. These are R １ , R ２ , and n １ may be the same as or different from. The negative type photosensitive resin composition according to claim 6 or 7, further comprising a structural unit represented by the following formula:

16. 16. The negative type photosensitive resin composition according to claim 15, wherein the polyimide precursor (A) is a copolymer of structural units represented by the general formulas (4) and (5).

17. The polyimide precursor (A) is represented by the following general formula (6): 【Chemistry 13】 {In the formula, R １ and R ２ are each independently a hydrogen atom or a monovalent organic group; R １ and R ２ At least one of is a monovalent organic group, and n １ is an integer from 2 to 150. The negative type photosensitive resin composition according to claim 6 or 7, which has a structural unit represented by the following formula:

18. 100 parts by mass of the polyimide precursor (A); 0.1 to 20 parts by mass of the photopolymerization initiator (B) based on 100 parts by mass of the polyimide precursor (A); 0.1 to 20 parts by mass of the silane coupling agent (C) based on 100 parts by mass of the polyimide precursor (A); The negative type photosensitive resin composition according to any one of claims 1 to 17, comprising:

19. A method for producing a polyimide, comprising a step of converting the negative type photosensitive resin composition according to any one of claims 1 to 18 into a polyimide.

20. The following steps: (1) A step of applying the negative type photosensitive resin composition according to any one of claims 1 to 18 onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heat treating the relief pattern to form a hardened relief pattern; 2. A method for producing a cured relief pattern comprising:

21. A negative type photosensitive resin composition described in any one of claims 1 to 18, which is used for producing a fan-out type semiconductor package.

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