Photosensitive resin composition, method for manufacturing cured relief pattern, and semiconductor device

Abstract

To provide: a photosensitive resin composition which has high adhesion even onto copper or copper alloys and can form a cured film reduced in migration; and a method for manufacturing a cured relief pattern and a semiconductor device which employ the composition.SOLUTION: A negative photosensitive resin composition comprises (A) a resin containing a polyimide precursor, a polyimide, or both, (B) a photoinitiator, and (C) a nitrogen-containing heterocyclic compound. The (C) nitrogen-containing heterocyclic compound is at least one selected from compounds of general formulas (4) and (5).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition, a method for producing a cured relief pattern, and a semiconductor device. [Background technology]

[0002] Polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used in insulating materials for electronic components, 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 precursors can easily form heat-resistant relief pattern coatings by applying the precursor, exposing it to light, developing it, and subjecting it to a thermal imidization treatment involving curing. Such photosensitive polyimide precursors have the advantage of enabling significant process reduction compared to conventional non-photosensitive polyimides.

[0003] Meanwhile, in recent years, methods for mounting semiconductor devices on printed wiring boards have been changing in light of improvements in integration density and functionality, as well as chip size miniaturization. Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures in which a polyimide coating directly contacts solder bumps, such as those used in BGA (ball-gripped array) and CSP (chip-size packaging), which enable higher-density mounting. When forming such bump structures, the coating must have high heat resistance and chemical resistance. Patent Document 1 discloses a method for improving the heat resistance of a polyimide coating or polybenzoxazole coating by adding a thermal crosslinking agent to a composition containing a polyimide precursor or polybenzoxazole precursor.

[0004] As semiconductor devices become increasingly miniaturized, the wiring resistance of semiconductor devices is becoming non-negligible. Therefore, the gold or aluminum wiring that has been used until now has been replaced with copper or copper alloy wiring, which has lower resistance. However, conventional photosensitive resin compositions have poor adhesion to copper, resulting in the problem of peeling between the resin and the copper wiring.

[0005] Such a metal redistribution layer is required to maintain its insulating properties even after a reliability test. Examples of the reliability test include a high-temperature storage test in which the layer is stored in air at 5% humidity and 150°C for 168 hours. However, with conventional photosensitive resin compositions, copper migration occurs during the reliability test, increasing the likelihood of short circuits or disconnections in the redistribution layer.

[0006] Patent Documents 2 and 3 disclose a method for improving adhesion to copper or copper alloys and preventing corrosion by adding tetrazole or a derivative thereof to a composition containing a polyimide precursor. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-287889 [Patent Document 2] Japanese Patent Publication No. 2020-2281 [Patent Document 3] Patent No. 3170174 Summary of the Invention [Problem to be solved by the invention]

[0008] However, the compositions described in Patent Documents 2 and 3 do not have sufficient migration-inhibiting effects or adhesion-improving effects, making it difficult to achieve both of these performance properties. Therefore, an object of the present disclosure is to provide a photosensitive resin composition that provides a cured film that has high adhesion even on copper or copper alloys and inhibits migration, a method for producing a cured relief pattern using the same, and a semiconductor device. [Means for solving the problem]

[0009] Examples of embodiments of the present disclosure are listed in the following items [1] to

[17] . [1] Ingredients: (A) a resin containing a polyimide precursor, a polyimide, or both; (B) a photoinitiator, and (C) Nitrogen-containing heterocyclic compound A negative photosensitive resin composition comprising: The polyimide precursor (A) is a polyimide precursor represented by the following general formula (1): [ka] In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n is an integer of 2 to 50, and R1 and R2 are each independently a hydrogen atom or a group represented by the following general formula (2a) or (2b): [ka] (wherein R3 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R4 and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms. However, R1 and R2 cannot both be hydrogen atoms at the same time.) is a polyamic acid ester or polyamic acid salt represented by The polyimide (A) is represented by the following general formula (3): [ka] {In the formula, X2 is a tetravalent organic group having 6 to 40 carbon atoms, Y2 is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50.} It is a polyimide resin represented by The nitrogen-containing heterocyclic compound (C) is represented by the following general formula (4): [ka] In the formula, R6 is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 25 carbon atoms, an alkoxyalkyl group, an aromatic group, a group having a nitrogen-containing heterocycle, and combinations thereof; and R7 to R 10 are each independently a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyalkyl group or an aromatic group having 1 to 10 carbon atoms, and a combination thereof. The following general formula (5): [ka] {where, R 31 ~R 33 are each independently a monovalent organic group selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group, an azo bond-containing group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, an aromatic group, a group having a nitrogen-containing heterocycle, and combinations thereof, with the proviso that R 31 ~R 33 At least one of the groups is a group having a nitrogen-containing heterocycle.} The photosensitive resin composition is at least one selected from the group consisting of compounds represented by the following formula: [2] The nitrogen-containing heterocyclic compound (C) is represented by the following general formula (4a): [ka] {where, R 11 is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a silicon atom-containing group, a hydroxyl group, an amino group, and an alkyl group or aromatic group having 1 to 10 carbon atoms.} Item 2. The photosensitive resin composition according to item 1, comprising a compound represented by the formula: [3] The nitrogen-containing heterocyclic compound (C) is represented by the following general formula (4b): [ka] {where, R12 is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 15 carbon atoms, an aromatic group or a group having a nitrogen-containing heterocycle, and combinations thereof, and m is an integer of 1 to 10. 3. The photosensitive resin composition according to item 1 or 2, comprising a compound represented by the formula: [4] In the above general formula (4b), R 12 is the group having a nitrogen-containing heterocycle or the silicon atom-containing group. [5] In the above general formula (4b), R 12 is a group having an imidazole skeleton. [6] In the above general formula (4b), R 12 6. The photosensitive resin composition according to any one of items 3 to 5, wherein is a group having an alkoxysilyl group. [7] In the nitrogen-containing heterocyclic compound represented by the general formula (5), R 31 ~R 33 7. The photosensitive resin composition according to any one of items 1 to 6, wherein at least two of the above are groups having a nitrogen-containing heterocycle. [8] 8. The photosensitive resin composition according to any one of items 1 to 7, further comprising (D) a tetrazole compound. [9] 9. The photosensitive resin composition according to item 8, wherein the (D) tetrazole compound is 5-amino-1H-tetrazole.

[10] The nitrogen-containing heterocyclic compound (C) is represented by the following general formulas (5a) and (5b): [ka] {In formulas (5a) and (5b), R 34is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a silicon atom-containing group, a phosphorus atom-containing group, a hydroxyl group, a carboxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, an aromatic group, or a group having a nitrogen-containing heterocycle, and in formula (5a), two R 35 are each independently CH or a nitrogen atom. 10. The photosensitive resin composition according to any one of items 1 to 9, comprising at least one compound selected from the group consisting of compounds represented by the following formula:

[11] X1 in the general formula (1) and / or X2 in the general formula (3) are each a compound represented by the following general formulae (6) to (8): [ka] [ka] [ka] {In general formula (8), R 13 is an oxygen atom, a sulfur atom, or a divalent organic group. 11. The photosensitive resin composition according to any one of items 1 to 10, wherein the organic group is at least one selected from the group consisting of:

[12] Y1 in the general formula (1) and / or Y2 in the general formula (3) are represented by the following general formulae (9) to (12): [ka] {R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different.} [ka] [ka] {R 26 is a divalent group, and R 18~R 25 are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different.} [ka] {R 27 and R 28 is a divalent group, and R 29 and R 30 are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different.} 12. The photosensitive resin composition according to any one of items 1 to 11, wherein the organic group is at least one selected from the group consisting of:

[13] 13. The photosensitive resin composition according to any one of items 1 to 12, comprising at least two or more types of (A) polyimide precursors represented by the general formula (1) above, and / or at least two or more types of (A) polyimides represented by the general formula (3) above.

[14] 14. The photosensitive resin composition according to any one of items 1 to 13, wherein the general formula (1) has at least two types of X1, and / or the general formula (3) has at least two types of X2.

[15] (1) A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of items 1 to 14 onto the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) forming a hardened relief pattern by heat treating the relief pattern; 1. A method for producing a cured relief pattern, comprising:

[16] Item 16. The method for producing a cured relief pattern according to Item 15, wherein the substrate is formed from copper or a copper alloy.

[17] 17. A semiconductor device comprising a cured relief pattern obtained by the method for producing a cured relief pattern according to Item 15 or 16. [Effects of the Invention]

[0010] According to the present disclosure, it is possible to provide a photosensitive resin composition that has excellent adhesion even on copper or a copper alloy and is capable of suppressing migration, a method for forming a cured relief pattern using the same, and a semiconductor device. DETAILED DESCRIPTION OF THE INVENTION

[0011] <Photosensitive resin composition> The photosensitive resin composition of the present disclosure includes, as the (A) resin component, a polyimide precursor, a polyimide, or both (collectively referred to simply as "(A) resin" in the present disclosure). The photosensitive resin composition further includes a (B) photopolymerization initiator and a (C) nitrogen-containing heterocyclic compound. The (A) polyimide precursor is a polyamic acid ester or a polyamic acid salt represented by the general formula (1) described below, and the (A) polyimide is a polyimide resin represented by the general formula (3) described below. The (C) nitrogen-containing heterocyclic compound is at least one selected from the compounds represented by the general formulas (4) and (5) described below. The photosensitive resin composition of the present disclosure, having the above-described configuration, can provide a photosensitive resin composition that has excellent adhesion even on copper or copper alloys and is capable of suppressing migration.

[0012] Each component will be described in detail below. Throughout this specification, when a structure represented by the same symbol in a general formula is present in a molecule, the structures may be the same or different from each other.

[0013] (A) Polyimide precursor The polyimide precursor (A) is a polyamic acid ester or polyamic acid salt having a structural unit represented by the following general formula (1): The polyimide precursor (A) is converted into a polyimide by heating (for example, at 200°C or higher) for cyclization. [ka] In formula (1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n is an integer of 2 to 50, and R1 and R2 are each independently a hydrogen atom, a monovalent organic group represented by general formula (2a) or (2b) described below, or a saturated aliphatic group having 1 to 4 carbon atoms. However, R1 and R2 cannot both be hydrogen atoms.

[0014] R1 and R2 in formula (1) may each independently be a monovalent organic group represented by the following general formula (2a) or (2b). [ka] {In formulas (2a) and (2b), R3 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R4 and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.} When R1 and / or R2 are general formula (2b), the corresponding moiety in general formula (1) is a carboxylate ion (-COO - ) and serves as a counter ion. More specific examples of R3 include a hydrogen atom, a methyl group, an ethyl group, and a propyl group, and a methyl group is preferred. More specific examples of R4 and R5 include a hydrogen atom, a methyl group, an ethyl group, and a propyl group, and a hydrogen atom is preferred. m is more preferably an integer of 2 to 5, and even more preferably 2 or 3. R3 to R5 and m, which are common to formulae (2a) and (2b), may be the same or different from each other.

[0015] In the above general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and even more preferably 6 to 20 carbon atoms. The tetravalent organic group represented by X1 is more preferably an aromatic group or an alicyclic aliphatic group in which a -COOR1 group or a -COOR2 group and a -CONH- group are mutually ortho-positioned.

[0016] In the general formula (1), X1 is represented by the following general formulas (6) to (8): [ka] [ka] [ka] {In general formula (8), R 13 is an oxygen atom, a sulfur atom, or a divalent organic group. It is preferable that the organic group is at least one selected from the following:

[0017] More specifically, X1 is represented by the following formula (13): [ka] It is more preferable that the structure is represented by the following formula: Furthermore, the structure of X1 may be one type or a combination of two or more types.

[0018] In the above general formula (1), the tetravalent organic group represented by X1 is particularly preferably selected from at least one of 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic dianhydride (PMDA), and biphenyltetracarboxylic dianhydride (BPDA) in order to achieve both heat resistance and photosensitive properties.

[0019] The structure of X1 may be one type or a combination of two or more types, but from the viewpoint of improving resolution, a combination of two or more types is more preferable.

[0020] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and even more preferably 6 to 20 carbon atoms, in order to achieve both heat resistance and photosensitive properties.

[0021] In the general formula (1), Y1 is preferably at least one organic group selected from the following general formulae (9) to (12). [ka] {R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different.} [ka] [ka] {R 26 is a divalent group, and R 18 ~R 25 are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different.} [ka] {R 27 and R 28 is a divalent group, and R 29 and R 30 are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different.}

[0022] More specifically, the divalent organic group represented by Y1 is represented by the following formula (14): [ka] Examples of the structure include, but are not limited to, the structure represented by the following formula: In addition, the structure of Y1 may be one type or a combination of two or more types.

[0023] In the above general formula (1), the divalent organic group represented by Y1 is particularly preferably selected from at least one of diaminodiphenyl ether (DADPE), p-phenylenediamine (pPD), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 4,4'-diamino-2,2'-dimethylbiphenyl (mTB), in that it achieves both heat resistance and photosensitive properties.

[0024] The polyimide precursor (A) preferably has a double bond at the terminal of R1 and R2, which contain a group represented by general formula (2a) or (2b), in general formula (1), in which at least one of R1 and R2 has a group represented by general formula (2a) or (2b).

[0025] (A) The polyimide precursor is converted into a polyimide by heating (for example, at 200° C. or higher) for cyclization.

[0026] (A) Polyimide The polyimide is a polyimide resin having a structural unit represented by the following general formula (3). [ka] {In the formula, X2 is a tetravalent organic group having 6 to 40 carbon atoms, Y2 is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50.} It is particularly preferable that the photosensitive resin composition contains a resin represented by general formula (3) in that sufficient film properties can be exhibited without requiring chemical changes in the heat treatment step, and therefore the composition is suitable for heat treatment at lower temperatures.

[0027] From the viewpoint of heat resistance, the divalent organic group of X2 and / or the tetravalent organic group of Y2 preferably contains an aromatic ring structure, more preferably a benzene ring structure. From the viewpoint of solubility in organic solvents, it is preferable that at least one of X2 and Y2 is a fluorine atom-containing group, and it is preferable that both X2 and Y2 are fluorine atom-containing groups. The tetravalent organic group of X2 and / or the divalent organic group of Y2 preferably has a structure in which 2 to 6 benzene rings are bonded via single bonds or divalent linking groups. Examples of the divalent linking group include an alkylene group, a fluorinated alkylene group, and an ether group. The alkylene group and the fluorinated alkylene group may be linear or branched.

[0028] X2 may be the same as or different from the structure of X1 described above in the description of general formula (1) of the polyimide precursor. X2 is preferably an organic group having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and even more preferably 6 to 20 carbon atoms. X2 is more preferably an aromatic group in which the -COOR1 group or -COOR2 group and the -CONH- group are located at the ortho positions relative to each other, or an alicyclic aliphatic group. X2 is preferably at least one organic group selected from general formulas (6) to (8) described above in the description of general formula (1) of the polyimide precursor, and more preferably a structure represented by formula (13) described above.

[0029] Y2 may be the same as or different from the structure of Y1 described above in the description of general formula (1) of the polyimide precursor. Y2 is preferably an aromatic group having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and even more preferably 6 to 20 carbon atoms. Y2 is preferably at least one organic group selected from general formulas (9) to (12) described above in the description of general formula (1) of the polyimide precursor, and more preferably a structure represented by formula (14) described above.

[0030] The (A) resin is preferably at least one resin selected from the group consisting of polyimide precursors and polyimides. As the (A) resin, only the polyimide precursor may be used, or only the polyimide may be used. When the (A) resin is a mixture of the polyimide precursor and the polyimide, the total mass of these may be 100 parts by mass, and the polyimide may be, for example, 50 to 90 parts by mass of the polyimide precursor and 10 to 50 parts by mass of the polyimide. It is preferable that the (A) resin contains a polyimide precursor from the viewpoint of better photosensitivity.

[0031] (A) Preparation of polyimide precursor The polyimide precursor represented by the general formula (1) can be obtained, for example, by reacting the above-mentioned tetracarboxylic acid dianhydride containing the tetravalent organic group X1 having 6 to 40 carbon atoms with (a) an alcohol formed by bonding a monovalent organic group represented by the general formula (2a) and a hydroxyl group to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester), and then polycondensing the resulting tetracarboxylic acid with a diamine compound containing a divalent organic group Y1.

[0032] (Preparation of Acid / Ester Forms) Examples of tetracarboxylic dianhydrides containing a tetravalent organic group X1 having 6 to 40 carbon atoms include 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, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 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. These may be used alone or in combination of two or more.

[0033] (a) Examples of aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms, which are formed by bonding a monovalent organic group represented by the above general formula (2a) to a hydroxyl group, include 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.

[0034] The content of the component (a) in the negative photosensitive resin composition is preferably more than 80 mol% relative to the total content of R1 and R2. When the content of the component (a) exceeds 80 mol%, the desired photosensitive characteristics can be obtained, which is preferable. The content of the component (a) in the negative photosensitive resin composition is more preferably 85 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, relative to the total content of R1 and R2.

[0035] The above tetracarboxylic acid dianhydride and the above alcohol are stirred, dissolved, and mixed in a reaction solvent in the presence of a basic catalyst such as pyridine at a reaction temperature of 20 to 50°C for 4 to 10 hours, whereby the half-esterification reaction of the acid dianhydride proceeds, and the desired acid / ester form can be obtained.

[0036] The reaction solvent is preferably one that dissolves the acid / ester compound and the polyimide precursor, which is a polycondensation product of the acid / ester compound and a diamine compound. Examples of reaction solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These solvents may be used alone or in combination as needed.

[0037] (Preparation of Polyimide Precursor) The acid / ester compound (typically a solution in the reaction solvent) can be converted into a polyanhydride by adding a known dehydration condensation agent to the acid / ester compound under ice cooling. A diamine compound containing a divalent organic group Y1, dissolved or dispersed in a separate solvent, is then added dropwise to the acid / ester compound to polycondense the resulting mixture, resulting in a 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.

[0038] Examples of diamines containing a divalent organic group Y1 that are preferably used in the present disclosure include 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)phen nyl) 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] )phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, and 9,9-bis(4-aminophenyl)fluorene, as well as 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, 3,3'-dimethyl-4,4'-Diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof can be used. Among these, 4,4'-diaminodiphenyl ether, p-phenylenediamine, 4,4-dimethyl-2,2'-diaminobiphenyl, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane are preferred, and 4,4'-diaminodiphenyl ether, p-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane are more preferred.

[0039] For the purpose of improving adhesion to various substrates, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized.

[0040] After the reaction is complete, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution can be filtered off, if necessary, and then a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof can be added to the resulting polymer component to precipitate the polymer component. The polymer can then be purified by repeated redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution can be passed through a column packed with an anion-cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0041] The molecular weight of the (A) polyimide precursor, 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, and particularly preferably 20,000 to 40,000. A weight average molecular weight of 8,000 or more is preferred because of good mechanical properties, while a weight average molecular weight of 150,000 or less is preferred because of good dispersibility in a developer and resolution performance of a relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK. The photosensitive resin composition may contain at least two types of (A) polyimide precursor represented by general formula (1).

[0042] (A) Preparation method of polyimide (A) Polyimide can be obtained by reacting a tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, a tetracarboxylic diester dichloride, or the like with a diamine, the corresponding diisocyanate compound, or a trimethylsilylated diamine. Polyimide can be obtained by dehydrating and cyclizing a polyamic acid, which is a polyimide precursor generally obtained by reacting a tetracarboxylic dianhydride with a diamine, through heating or a chemical treatment with an acid or a base.

[0043] Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenoxy)-2,2-dicarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-bis(3,4-dicarboxyphenoxy)-2,2-di ... 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl) Examples of the tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.

[0044] Among these, pyromellitic anhydride (PMDA), diphenylether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA) are preferred. These may be used alone or in combination of two or more.

[0045] Suitable diamines include 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diaminodiphenyl sulfone, 3,3'dimethylbenzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis(p-aminophenyl)hexafluoropropane, and the like. Pan, bis(trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydianiline (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2,2'-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DF POB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5-diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminobenzotrifluoride (3,5-DABTF), 3,5-diamino- Examples of the compound include 5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethylbenzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)xanthene (6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenylxanthene (3FCDAM), and compounds represented by 3,6-diamino-9,9-diphenylxanthene.

[0046] The molar ratio of the diamine to the acid dianhydride may basically be 1:1. However, to obtain a desired terminal structure, one of them may be used in excess. Specifically, by using an excess of diamine, the terminals (both terminals) of the polyimide (A) tend to become amino groups. On the other hand, by using an excess of acid dianhydride, the terminals (both terminals) of the polyimide (A) tend to become acid anhydride groups. As described above, in the present disclosure, it is preferable that the polyimide (A) has acid anhydride groups at its terminals. Therefore, in the present disclosure, it is preferable to use an excess of acid dianhydride when synthesizing the polyimide (A).

[0047] The amino group and / or acid anhydride group at the end of the polyimide obtained by condensation polymerization may be reacted with some kind of reagent so that the polyimide end has a desired functional group.

[0048] The molecular weight of the (A) polyimide, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, and particularly preferably 10,000 to 50,000. A weight average molecular weight of 5,000 or more is preferred because it provides good mechanical properties, while a weight average molecular weight of 150,000 or less is preferred because it provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. 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.

[0049] (B) Photopolymerization initiator The (B) photopolymerization initiator can be selected from any of the compounds conventionally used as photopolymerization initiators for UV curing. Examples of the (B) photopolymerization initiator include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone; thioxanthone derivatives such as 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; and 2,6-di(4'-diazidobenzal)-4-methylcyclohexyl. Examples of suitable compounds include azides such as cyclohexanone and 2,6'-di(4'-diazidobenzal)cyclohexanone, oximes such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl peroxide, aromatic biimidazoles, and titanocenes. Among these, the oximes are preferred in terms of photosensitivity.

[0050] The amount of the (B) photopolymerization initiator blended is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity characteristics, more preferably 2 to 15 parts by mass. The photosensitive resin composition has excellent photosensitivity when it contains 0.1 part by mass or more of the (B) photopolymerization initiator relative to 100 parts by mass of the (A) resin, while it has excellent thick-film curing properties when it contains 20 parts by mass or less.

[0051] (C) Nitrogen-containing heterocyclic compound The nitrogen-containing heterocyclic compound is at least one selected from the group consisting of 2,4,6-substituted-1,3,5-triazine derivatives represented by the general formula (4) described below and 2,4,6-substituted-pyridine derivatives represented by the general formula (5) described below. The use of these nitrogen-containing heterocyclic compounds (C) allows for the provision of photosensitive resin compositions with excellent adhesion and migration suppression on copper or copper alloys. While the chemical mechanism behind these excellent adhesion and migration suppression on copper or copper alloys is unclear, it is believed that the use of specific nitrogen-containing heterocyclic compounds results in a surface free energy that is relatively closer to that of copper compared to the resin and additives, allowing the compound to exist more stably near the copper interface than the surrounding resin and additives. It is believed that the π-conjugated heterocycles interact with the electrons in the d orbital of copper, thereby enhancing copper adhesion and preventing copper ion diffusion, thereby suppressing copper migration.

[0052] The 2,4,6-substituted-1,3,5-triazine derivative can be represented by the following general formula (4). [ka] In the formula, R6 is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 25 carbon atoms, an alkoxyalkyl group, an aromatic group, a group having a nitrogen-containing heterocycle, and combinations thereof; and R7 to R 10 are each independently a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyalkyl group or an aromatic group having 1 to 10 carbon atoms, and a combination thereof.}

[0053] In general formula (4), the number of carbon atoms in the alkyl group, alkoxyalkyl group, aromatic group, or group having a nitrogen-containing heterocycle represented by R6 is 1 to 25, and may be, for example, 1 to 20, 1 to 15, or 1 to 10. More preferred examples of R6 in general formula (4) include a group having a nitrogen-containing heterocycle with a total of 1 to 25 carbon atoms; an alkyl group having an alkoxysilyl group with a total of 4 to 25, 4 to 20, 4 to 15, or 4 to 10 carbon atoms; an alkyl group having a (meth)acryloyloxy group with a total of 5 to 25, 5 to 20, 5 to 15, or 5 to 10 carbon atoms; and an amino group having one or two alkoxyalkyl groups with a total of 4 to 25, 4 to 20, 4 to 15, or 4 to 10 carbon atoms. Examples of the group having a nitrogen-containing heterocycle include a substituted or unsubstituted pyrrolyl group, imidazolyl group, triazole group, pyridinyl group, triazinyl group, thiazolyl group, pyrazinyl group, and combinations thereof. Examples of the substituent that the nitrogen-containing heterocycle may have include an alkyl group having 1 to 12 carbon atoms, a halogen atom, an alkoxy group, an alkoxysilyl group, a hydroxyl group, an amino group, etc. Examples of the alkoxyalkyl group include an alkoxyalkyl group having a total of 2 to 10 carbon atoms, such as a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group.

[0054] R to R in general formula (4) 10 More preferably, the alkyl group is a hydrogen atom or an alkoxyalkyl group. Examples of the alkoxyalkyl group include alkoxyalkyl groups having a total of 2 to 10 carbon atoms, such as a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group.

[0055] Specific examples of the 2,4,6-substituted-1,3,5-triazine derivative represented by general formula (4) include 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-chloro-1,3,5-triazine, and 2,4-diamino-6-dimethylamino-1,3, 5-triazine, 2,4-diamino-6-(cyclopropylamino)-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-butylamino-1,3,5-triazine, 2,4-diamino-6-diethylamino-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-diallylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2,4-diamino-6-[2-( 2-undecyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-ethyl-4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-(triethoxysilyl)ethyl-1,3,5-triazine, 2,4-diamino-6-methacryloyloxyethyl-1,3,5-triazine, 2,4,6-tris(chloroamino)-1,3,5-triazine, N,N'-diisopropyl N,N',N''-tri(m-tolyl)-1,3,5-triazine-2,4,6-triamine, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,Examples include 10-tetraoxaspiro[5.5]undecane, 2,4,6-tri(9H-carbazol-9-yl)-1,3,5-triazine, and 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoate tris(2-ethylhexyl).

[0056] The 2,4,6-substituted-1,3,5-triazine derivative is represented by the following general formula (4a): [ka] {where, R 11 is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a silicon atom-containing group, a hydroxyl group, an amino group, and an alkyl group or aromatic group having 1 to 10 carbon atoms.}, or a compound represented by the following general formula (5): [ka] {where, R 12 is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 15 carbon atoms, an aromatic group or a group having a nitrogen-containing heterocycle, and combinations thereof, and m is an integer of 1 to 10. From the viewpoint of adhesion to copper or a copper alloy, it is preferable that the triazine derivative be at least one selected from the group consisting of compounds represented by the following formula:

[0057] In general formula (4b), R 12 The number of carbon atoms in the alkyl group, aromatic group, or group having a nitrogen-containing heterocycle is 1 to 15, and may be, for example, 1 to 10. 12More preferred examples of the heterocyclic group include a group having a nitrogen-containing heterocycle and having a total of 1 to 15 or 1 to 10 carbon atoms; an alkoxysilyl group having a total of 3 to 15 or 3 to 10 carbon atoms; and a (meth)acryloyloxy group. Examples of the group having a nitrogen-containing heterocycle include a substituted or unsubstituted pyrrolyl group, imidazolyl group, triazole group, pyridinyl group, triazinyl group, thiazolyl group, pyrazinyl group, and combinations thereof. Examples of the substituents for these groups include an alkyl group having 1 to 12 carbon atoms, a halogen atom, an alkoxy group, an alkoxysilyl group, a hydroxyl group, and an amino group.

[0058] In general formula (4b), R 12 More preferably, R is a group having a nitrogen-containing heterocycle or a group having a silicon atom-containing group. 12 By having a nitrogen-containing heterocyclic structure or a silicon atom-containing group, stronger copper adhesion can be achieved and good elongation at break can be maintained even after a wet heat durability test.

[0059] In general formula (4b), R 12 More preferably, R is a group having an imidazole skeleton. 12 The imidazole skeleton increases the number of nitrogen atoms, enhancing the coordination force with copper, resulting in stronger copper adhesion. Furthermore, the basicity of the imidazole group allows the imidization reaction to proceed efficiently at high temperatures, forming a stronger film, which allows good elongation at break to be maintained even after a humidity and heat durability test. The group having an imidazole skeleton is, for example, a substituted or unsubstituted imidazolyl group, and the substituent is preferably, for example, an alkyl group having 1 to 12 carbon atoms.

[0060] In general formula (4b), R 12 More preferably, R is a group having an alkoxysilyl group. 12 By having an alkoxysilyl group, the alkoxysilyl group forms a covalent bond with other components such as polymers through a polymerization reaction, thereby achieving even stronger adhesion to the copper substrate and maintaining good breaking elongation even after a wet heat durability test.

[0061] Specific examples of the compound represented by the general formula (4a) or (4b) include 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-ethyl-4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-(triethoxysilyl)ethyl-1,3,5-triazine, and 2,4-diamino-6-methacryloyloxyethyl-1,3,5-triazine.

[0062] The 2,4,6-substituted pyridine derivative can be represented by the following general formula (5). [ka] {where, R 31 ~R 33 are each independently a monovalent organic group selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group, an azo bond-containing group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, an aromatic group, a group having a nitrogen-containing heterocycle, and combinations thereof, with the proviso that R 31 ~R 33 At least one of the groups is a group having a nitrogen-containing heterocycle.}

[0063] In general formula (5), R 31 ~R 33Preferably, at least one of the groups is a group having a nitrogen-containing heterocycle, preferably having a total of 1 to 25 carbon atoms, for example 1 to 20. Examples of the group having a nitrogen-containing heterocycle include substituted or unsubstituted pyrrolyl groups, imidazolyl groups, triazole groups, pyridinyl groups, triazinyl groups, thiazolyl groups, pyrazinyl groups, and combinations thereof. Examples of combinations of nitrogen-containing heterocycles include a pyrazinyl group having a pyridinyl group, and a triazinyl group having one or two pyridinyl groups. Examples of substituents that the nitrogen-containing heterocycle may have include an alkyl group, a halogen atom, an alkoxy group, an alkoxysilyl group, a hydroxyl group, and an amino group.

[0064] In general formula (5), R 31 ~R 33 It is more preferable that at least two of the groups have a nitrogen-containing heterocycle. As described above, the nitrogen-containing heterocycle is preferably a group having a nitrogen-containing heterocycle with a total carbon number of preferably 1 to 25, for example 1 to 20. Examples of the group having a nitrogen-containing heterocycle include substituted or unsubstituted pyrrolyl groups, imidazolyl groups, triazole groups, pyridinyl groups, triazinyl groups, thiazolyl groups, pyrazinyl groups, and combinations thereof. Examples of the substituent that the nitrogen-containing heterocycle may have include alkyl groups, halogen atoms, alkoxy groups, alkoxysilyl groups, hydroxyl groups, and amino groups.

[0065] As the 2,4,6-substituted pyridine derivative, compounds represented by the following general formulae (5a) and (5b) are more preferred because they have a high migration suppressing effect. [ka] [ka] {In formulas (5a) and (5b), R 34is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a silicon atom-containing group, a phosphorus atom-containing group, a hydroxyl group, a carboxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, an aromatic group, or a group having a nitrogen-containing heterocycle, and in formula (5a), two R 35 are each independently CH or a nitrogen atom.

[0066] R in formulas (5a) and (5b) 34 is more preferably a hydrogen atom or a group having a nitrogen-containing heterocycle having 1 to 20 carbon atoms. Examples of the group having a nitrogen-containing heterocycle include a substituted or unsubstituted pyrrolyl group, imidazolyl group, triazole group, pyridinyl group, triazinyl group, thiazolyl group, pyrazinyl group, and combinations thereof. 35 and are more preferably both nitrogen atoms.

[0067] Examples of the 2,4,6-substituted pyridine derivative represented by the general formula (5) include the following compounds. [ka]

[0068] The blending amount of the nitrogen-containing heterocyclic compound (C) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the resin (A). When the blending amount is 0.01 part by mass or more, the adhesion to copper or copper alloys is excellent, while when the blending amount is 10 parts by mass or less, the storage stability is excellent.

[0069] (D) Tetrazole compounds The photosensitive resin composition may optionally contain (D) a tetrazole compound. In the present disclosure, the "tetrazole compound" has a structure that is not included in the above-mentioned (C) nitrogen-containing heterocyclic compound.

[0070] Examples of tetrazole compounds include 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, 5,5'-bis-1H-tetrazole, 1-methyl-5-ethyl-tetrazole, 1-methyl-5-mercapto-tetrazole, 1-carboxymethyl-5-mercapto-tetrazole, etc. From the viewpoint of improving copper adhesion, 5-amino-1H-1-tetrazole is particularly preferred.

[0071] The blending amount of the (D) tetrazole compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity characteristics, more preferably 0.5 to 10 parts by mass. When the blending amount of the tetrazole compound relative to 100 parts by mass of the (A) resin is 0.1 part by mass or more, the photosensitive resin composition has excellent adhesion to copper or copper alloys even when formed on copper or copper alloys and exposed to a high-temperature environment. On the other hand, when the blending amount is 20 parts by mass or less, the storage stability is excellent.

[0072] (Other ingredients) The negative photosensitive resin composition may further contain components other than the above components (A) to (D), such as resin components other than the (A) resin, sensitizers, monomers having a photopolymerizable unsaturated bond, adhesion aids, thermal polymerization inhibitors, hindered phenol compounds, organotitanium compounds, and solvents.

[0073] The negative photosensitive resin composition may further contain a resin component other than the resin (A). Examples of the resin component that can be contained in the negative photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, and acrylic resin.

[0074] The blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the (A) resin.

[0075] The negative photosensitive resin composition may further 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 can be used alone or in combination of two or more (for example, two to five types).

[0076] The amount of the sensitizer to be added is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the (A) resin.

[0077] The negative photosensitive resin composition may further contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, and examples thereof include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, including 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, diacrylate and dimethacrylate of 1,4-butanediol, and 1,6-hexamethylcyclohexane diacrylate and dimethacrylate. Examples of suitable compounds include diacrylates and dimethacrylates of Sandiol, 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.

[0078] The amount of the monomer having a photopolymerizable unsaturated bond to be blended is preferably 1 to 50 parts by mass relative to 100 parts by mass of the (A) resin.

[0079] The negative photosensitive resin composition may further contain an adhesion promoter to improve the adhesion between the film formed therefrom and the substrate. Examples of the adhesion promoter include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, and N-[3-(triethoxysilyl)propyl]phthalate. Examples of suitable adhesives include silane coupling agents such as amide acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane, as well as aluminum-based adhesive aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate. Among these adhesive aids, silane coupling agents are more preferred in terms of adhesive strength.

[0080] The amount of the adhesive aid to be added is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of the (A) resin.

[0081] The negative photosensitive resin composition may further 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, pt-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.

[0082] The amount of the thermal polymerization inhibitor to be added is preferably in the range of 0.005 to 12 parts by mass relative to 100 parts by mass of the (A) resin.

[0083] The negative photosensitive resin composition may further contain a hindered phenol compound to suppress discoloration on copper. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 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-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t -butylphenol), pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxybenzyl) 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-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3, 5-Tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2 ,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H, Examples of suitable hydroxybenzoates include, but are not limited to, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and the like. 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.

[0084] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, 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 relative to 100 parts by mass of the (A) resin, for example, when the negative photosensitive resin composition 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, which is preferable.

[0085] The negative photosensitive resin composition may further contain an organotitanium compound for the purpose of improving elongation after a wet heat durability test. The organotitanium compound that can be used is not particularly limited as long as an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

[0086] 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 a negative photosensitive resin composition with good storage stability and a good pattern. 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), and the like.

[0087] 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.

[0088] III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

[0089] IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0090] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

[0091] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0092] VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0093] Among the above I) to VII), the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. Titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

[0094] The amount of these organotitanium compounds added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the polyamic acid ester used as component (A). When the amount added is 0.01 part by mass or more, excellent adhesion is achieved, and when it is 10 parts by mass or less, excellent storage stability is achieved.

[0095] The photosensitive resin composition of the present disclosure is typically used as a varnish-like photosensitive resin composition prepared by dissolving the above-described components and any optional components used as needed in a solvent. Examples of other components include a solvent. From the viewpoint of solubility of the (A) resin, it is preferable to use a polar organic solvent as the solvent. Specific examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, and N-cyclohexyl-2-pyrrolidone, which can be used alone or in combination of two or more.

[0096] The solvent can be used in an amount of, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, per 100 parts by mass of the (A) resin, depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

[0097] Furthermore, from the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing an alcohol is preferred. Suitable usable alcohols are typically alcohols having an alcoholic hydroxyl group in the molecule and not having an olefinic double bond, and specific examples thereof include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol, lactic acid esters such as ethyl lactate, propylene glycol monoalkyl ethers such as propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, and propylene glycol-2-(n-propyl) ether, monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol-n-propyl ether, 2-hydroxyisobutyric acid esters, and dialcohols such as ethylene glycol and propylene glycol. Among these, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethyl alcohol are preferred, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether are particularly preferred.

[0098] When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50 mass %, more preferably 10 to 30 mass %. When the content of the alcohol having no olefinic double bond is 5 mass % or more, the storage stability of the photosensitive resin composition is improved, and when it is 50 mass % or less, the solubility of the (A) resin is improved.

[0099] <Method for producing cured relief pattern> The method for producing a cured relief pattern includes the following steps (1) to (4): (1) applying the above-mentioned negative photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) A step of heat-treating the relief pattern to form a hardened relief pattern. a method for producing a cured relief pattern, the method comprising:

[0100] Each step will be described below. (1) A step of applying a negative photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate. In this process, a negative photosensitive resin composition is applied to a substrate, and then dried as necessary to form a photosensitive resin layer. The substrate may have at least a surface (the surface on which the photosensitive resin layer is formed) made of copper or a copper alloy. In particular, the photosensitive resin composition of the present disclosure can provide a cured film and a cured relief pattern that have high adhesion even on copper or copper alloys and suppress migration.

[0101] As a method for applying the photosensitive resin composition onto a substrate, a method that has conventionally been used for applying photosensitive resin compositions, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or a method of spray application using a spray coater, can be used.

[0102] If necessary, the coating film made of the negative photosensitive resin composition can be dried. Examples of drying methods include air drying, heat drying using an oven or a hot plate, and vacuum drying. It is desirable to dry the coating film under conditions that do not cause imidization of the polyimide precursor (A) in the negative photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be performed at 20°C to 140°C for 1 minute to 1 hour. A photosensitive resin layer can be formed on the substrate in this manner.

[0103] (2) A step of exposing the photosensitive resin layer to light In this process, the photosensitive resin layer formed in the above process (1) 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 photomask or reticle having a pattern.

[0104] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as necessary for the purpose of improving photosensitivity, etc. The baking conditions are preferably in the range of a temperature of 40°C to 120°C and a time of 10 seconds to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the negative-type photosensitive resin composition.

[0105] (3) A step of developing the exposed photosensitive resin layer to form a relief pattern. In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The development method for developing the exposed (irradiated) photosensitive resin layer can be any of the conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment. Furthermore, after development, post-development baking may be performed at any temperature and time combination, as needed, for the purpose of adjusting the shape of the relief pattern. The developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of such a good solvent and a poor solvent. Examples of the good solvent include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the good solvent to the poor solvent depending on the solubility of the polymer in the negative photosensitive resin composition. Two or more types of each solvent, for example, several types, can also be used in combination.

[0106] (4) A step of heat-treating the relief pattern to form a hardened relief pattern. In this step, the relief pattern obtained by the development is heated to dissolve the photosensitive component and imidize the (A) polyimide precursor, thereby converting it into a cured relief pattern made of polyimide. Heat curing can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 200°C to 400°C for 30 minutes to 5 hours. The atmospheric gas used during heat curing may be air, or an inert gas such as nitrogen or argon.

[0107] <Semiconductor device> A semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern is also provided. Therefore, 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-described method for producing a cured relief pattern. The present disclosure is also applicable to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-described method for producing a cured relief pattern as part of its process. The semiconductor device of the present disclosure can be produced by forming the cured relief pattern formed by the above-described 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.

[0108] <Display device> A display device is provided that includes a display element and a cured film provided on the display element, the cured film having the above-described cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated via another layer. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA-type liquid crystal display devices, and partition walls for cathodes of organic EL elements.

[0109] In addition to being applied to the semiconductor devices described above, the negative photosensitive resin composition of the present disclosure is also useful 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]

[0110] Examples of the present disclosure will be specifically described below, but the present disclosure is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the polymer or negative-type photosensitive resin composition were measured and evaluated according to the following methods.

[0111] <<Measurement and Evaluation Methods>> (1) Copper migration evaluation A 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti film and a 400 nm thick copper film, in that order, using a sputtering system (L-440S-FHL, Canon Anelva Corporation). A photosensitive polyamic acid ester composition prepared by the method described below was then spin-coated onto the wafer using a coater developer (D-Spin 60A, SOKUDO Co., Ltd.) and dried to form a 10 μm thick coating. This coating was then irradiated with a test pattern mask using a parallel light mask aligner (PLA-501FA, Canon Inc.) at an energy of 300 mJ / cm2. The coating was then spray-developed using cyclopentanone as the developer using a coater developer (D-Spin 60A, SOKUDO Co., Ltd.). Then, a relief pattern on copper was obtained by rinsing with propylene glycol methyl ether acetate.

[0112] The wafer with the relief pattern formed on copper was heat-treated at 200°C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000, manufactured by Koyo Lindberg). In this way, a cured relief pattern of polyimide resin approximately 6 to 7 μm thick was obtained on copper. The resulting cured relief pattern was subjected to the following high-temperature storage test to check for the occurrence of copper migration. First, the wafer with the cured relief pattern formed on copper was heated at 150°C for 168 hours in air with a humidity of 5% using a temperature-programmed curing furnace (VF-2000, manufactured by Koyo Lindberg). Next, the polyimide resin layer on copper was cut using a focused ion beam processing and observation system JIB4000 (manufactured by JEOL Ltd.) to obtain a cross section of the polyimide resin / copper interface. The cross section of the resulting polyimide resin layer / copper interface was observed using a field emission scanning electron microscope (FE-SEM) (S-4800, manufactured by Hitachi High-Technologies Corporation). The thickness of the migration layer occurring at the interface was measured using a length measurement program on the FE-SEM. "A": Copper migration thickness is 0 nm or more and less than 25 nm "B": Copper migration thickness is 25nm or more and less than 50nm "C": Copper migration thickness is 50nm or more and less than 75nm "D": Copper migration thickness is 75nm or more

[0113] (2) 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 in a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg) at 200°C for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern of resin approximately 10 μm thick on the Cu. The heat-treated film was evaluated for adhesion properties between the copper substrate and the cured resin coating film according to the cross-cut method of JIS K 5600-5-6, based on the following criteria: "A": The lattice number of the cured resin coating adhered to the substrate is 100 "B": The lattice number of the cured resin coating adhered to the substrate is between 70 and less than 100. "C": The lattice number of the cured resin coating adhered to the substrate is 40 to less than 70. "D": The lattice number of the cured resin coating adhered to the substrate is less than 40

[0114] (3) Breaking elongation measurement after wet heat test A photosensitive resin composition was spin-coated onto a 6-inch silicon wafer to a cured film thickness of approximately 7 μm and dried. The entire surface was then exposed to light and heated at 200°C for 2 hours under a nitrogen atmosphere using a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg, Japan) to obtain a cured relief pattern (thermo-cured polyimide coating). The resulting polyimide coating was subjected to a high-temperature accelerated test (Hirayama Seisakusho PC-442R8D, 130°C, 85% RH, 168 hours) and then cut into 3 mm-wide strips using a dicing saw (DAD3350, manufactured by DISCO). The strips were then peeled from the silicon wafer using 46% hydrofluoric acid to produce polyimide tape. The elongation of the resulting polyimide tape was measured using a tensile tester (UTM-II-20, manufactured by Orientec Co., Ltd.) in accordance with ASTM D882-09. "A": Breaking elongation is 25% or more "B": Breaking elongation is 20% or more but less than 25% "C": Breaking elongation is 15% or more and less than 20% "D": Breaking elongation less than 15%

[0115] <(A) Resin Production Example> <Production Example 1> ((A) Synthesis of Polymer A-1 as Resin) 155 g (0.5 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, followed by 135 g (1.04 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone. The mixture was stirred at room temperature, and 79.1 g of pyridine was added while stirring, followed by stirring for 16 hours.

[0116] Next, under ice cooling, a solution of 203 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 89 g (0.44 mol) of diaminodiphenyl ether (DADPE) in 280 ml of γ-butyrolactone was added over 60 minutes with stirring. After stirring for another 4 hours at room temperature, 40 ml of ethyl alcohol was added and stirred for 1 hour, and then 1 L of γ-butyrolactone was added. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0117] The resulting reaction solution was added to 4 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 30 liters of water to precipitate the polymer, and the resulting precipitate was filtered 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 24,000.

[0118] <Production Example 2> ((A) Synthesis of Polymer A-2 as Resin) Polymer A-2 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 147 g (0.5 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155 g of ODPA in Production Example 1. The molecular weight of Polymer A-2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

[0119] <Production Example 3> ((A) Synthesis of Polymer A-3 as Resin) Polymer A-3 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 94 g (0.44 mol) of 2,2'-dimethyl-4,4-diaminobiphenyl (mTB) was used instead of 89 g of DADPE in Production Example 1. The molecular weight of Polymer A-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 26,000.

[0120] <Production Example 4> ((A) Synthesis of Polymer A-4 as Resin) Polymer A-4 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 46 g (0.44 mol) of p-phenylenediamine (pPD) was used instead of 89 g of DADPE in Production Example 1. The molecular weight of Polymer A-4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 19,000.

[0121] <Production Example 5> ((A) Synthesis of Polymer A-5 as Resin) Polymer A-5 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 176 g (0.44 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 89 g of DADPE in Production Example 1. The molecular weight of Polymer A-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 25,000.

[0122] <Production Example 6> ((A) Synthesis of Polymer A-6 as Resin) Polymer A-6 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 124 g (0.4 mol) of ODPA and 29 g (0.1 mol) of BPDA were used instead of the 155 g of ODPA used in Production Example 1. The molecular weight of Polymer A-6 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

[0123] <Production Example 7> ((A) Synthesis of Polymer A-7 as Resin) Polymer A-7 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 62 g (0.2 mol) of ODPA and 65 g (0.3 mol) of PMDA were used instead of 155 g of ODPA and 94 g (0.44 mol) of mTB were used instead of 89 g of DADPE. 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 20,000.

[0124] <Production Example 8> ((A) Synthesis of Polymer A-8 as Resin) A 3 L separable glass flask equipped with a stirrer and a stirring blade was charged with 64.1 g (0.20 mol) of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 97.7 g (0.22 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), and 500 g of dimethylacetamide (DMAc). The mixture was stirred to dissolve TFMB and 6FDA in the DMAc. The mixture was then stirred under a nitrogen stream at room temperature for 12 hours to polymerize the mixture, yielding a polyamic acid solution.

[0125] After adding 16 g of pyridine to the obtained polyamic acid solution, 82 g of acetic anhydride was added dropwise at room temperature, and then the liquid temperature was kept at 20 to 100°C and stirring was continued for 24 hours to carry out the imidization reaction, thereby obtaining a polyimide solution.

[0126] The resulting polyimide solution was poured into 1,000 g of methanol in a 5 L container while stirring to precipitate the polyimide resin. The solid polyimide resin was then filtered using a suction filter and washed with 1,000 g of methanol. The solid was then dried at 100°C for 24 hours using a vacuum dryer, and then further dried at 200°C for 3 hours. This yielded Polymer (A-8), a polyimide powder having terminal acid anhydride groups. The molecular weight of Polymer A-8 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight-average molecular weight (Mw) was 25,000.

[0127] Table 1 shows the compounds used in the synthesis of polymers A-1 to A-8.

[0128] [Table 1]

[0129] <<Production Example of Photosensitive Resin Composition>> Example 1 A negative-tone photosensitive resin composition was prepared using Polymer A by the following method, and the prepared composition was evaluated. 100 g of Polymer A ((A) polyimide precursor), 2.0 g of TR-PBG-3057 ((B) photopolymerization initiator), 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl]-1,3,5-triazine ((C) 2,4-substituted-1,3,5-triazine derivative, manufactured by Shikoku Kasei Co., Ltd.), and 8.0 g of tetraethylene glycol dimethacrylate (NK Ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.) were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL) and 40 g of dimethyl sulfoxide (hereinafter referred to as DMSO). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding a small amount of the solvent, resulting in a negative-tone photosensitive resin composition. The composition was evaluated according to the method described above.

[0130] <Examples 2 to 29 and Comparative Example 1> Negative photosensitive resin compositions similar to those in Example 1 were prepared except that the components were blended in the blending ratios shown in Table 2, and evaluations were carried out in the same manner as in Example 1. The evaluation results are shown in Table 2. The compounds indicated by abbreviations in Table 2 are shown in Tables 3 and 4.

[0131] [Table 2]

[0132] [Table 3]

[0133] [Table 4]

[0134] As is clear from Table 2, in Examples 1 to 29 containing (C) a nitrogen-containing heterocyclic compound represented by general formula (4) or (5), good results were obtained in copper adhesion, copper migration, and elongation at break after the wet heat test. However, in Comparative Examples not containing (C) a nitrogen-containing heterocyclic compound, insufficient results were obtained in copper adhesion, copper migration, and elongation at break after the wet heat test.

[0135] Although examples of embodiments of the present disclosure have been described above, the present disclosure is not limited to these and can be modified as appropriate within the scope of the invention. [Industrial Applicability]

[0136] Use of the photosensitive resin composition according to the present disclosure makes it possible to achieve excellent adhesion even on copper or copper alloys and suppress migration, and the composition can be widely used as a photosensitive composition used for forming a cured relief pattern, a method for forming a cured relief pattern, and a semiconductor device having a cured relief pattern.

Claims

1. Ingredients: (A) a resin containing a polyimide precursor, a polyimide, or both; (B) a photoinitiator, and (C) Nitrogen-containing heterocyclic compound A negative photosensitive resin composition comprising: The polyimide precursor (A) is a polyimide precursor represented by the following general formula (1): 【Chemical 1】 {In the formula, X １ is a tetravalent organic group having 6 to 40 carbon atoms, and Y １ is a divalent organic group having 6 to 40 carbon atoms, n is an integer of 2 to 50, and R １ and R ２ are each independently a hydrogen atom or a group represented by the following general formula (2a) or (2b): 【Chemistry 2】 (In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. １ and R ２ Both cannot be hydrogen atoms at the same time. is a polyamic acid ester or polyamic acid salt represented by The polyimide (A) is represented by the following general formula (3): 【Chemistry 3】 {In the formula, X ２ is a tetravalent organic group having 6 to 40 carbon atoms, and Y ２ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50. It is a polyimide resin represented by The nitrogen-containing heterocyclic compound (C) has the following general formula (4): 【Chemistry 4】 {In the formula, R ６ is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 25 carbon atoms, an alkoxyalkyl group, an aromatic group, a group having a nitrogen-containing heterocycle, and a combination thereof; R ７ ~R １０ are each independently a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyalkyl group or an aromatic group having 1 to 10 carbon atoms, and a combination thereof; The following general formula (5): 【Chemistry 5】 {In the formula, R ３１ ~R ３３ are each independently a monovalent organic group selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, an azo bond-containing group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, an aromatic group, a group having a nitrogen-containing heterocycle, and combinations thereof, with the proviso that R ３１ ~R ３３ At least one of the groups is a group having a nitrogen-containing heterocycle. The photosensitive resin composition is at least one selected from the group consisting of compounds represented by the following formula:

2. The nitrogen-containing heterocyclic compound (C) has the following general formula (4a): 【Chemistry 6】 {In the formula, R １１ is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a silicon atom-containing group, a hydroxyl group, an amino group, and an alkyl group or aromatic group having 1 to 10 carbon atoms.} The photosensitive resin composition according to claim 1, comprising a compound represented by the formula:

3. The nitrogen-containing heterocyclic compound (C) has the following general formula (4b): 【Chemistry 7】 {In the formula, R １２ is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 15 carbon atoms, an aromatic group or a group having a nitrogen-containing heterocycle, and a combination thereof, and m is an integer of 1 to 10. The photosensitive resin composition according to claim 1 or 2, comprising a compound represented by the formula:

4. In the general formula (4b), R １２ is the group having a nitrogen-containing heterocycle or the silicon atom-containing group.

5. In the general formula (4b), R １２ The photosensitive resin composition according to claim 3 , wherein is a group having an imidazole skeleton.

6. In the general formula (4b), R １２ The photosensitive resin composition according to claim 3 , wherein is a group having an alkoxysilyl group.

7. In the nitrogen-containing heterocyclic compound represented by the general formula (5), R ３１ ~R ３３ The photosensitive resin composition according to claim 1 or 2, wherein at least two of the above are groups having a nitrogen-containing heterocycle.

8. The photosensitive resin composition according to claim 5 , further comprising (D) a tetrazole compound.

9. 9. The photosensitive resin composition according to claim 8, wherein the tetrazole compound (D) is 5-amino-1H-tetrazole.

10. The nitrogen-containing heterocyclic compound (C) has the following general formulas (5a) and (5b): 【Chemistry 8】 {In formulas (5a) and (5b), R ３４ is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a silicon atom-containing group, a phosphorus atom-containing group, a hydroxyl group, a carboxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, an aromatic group, or a group having a nitrogen-containing heterocycle, and in formula (5a), two R ３５ are each independently CH or a nitrogen atom. The photosensitive resin composition according to claim 1 or 2, comprising at least one compound selected from the group consisting of compounds represented by the formula:

11. X in the general formula (1) １ and / or X in the general formula (3) ２ is represented by the following general formulas (6) to (8): 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 {In general formula (8), R １３ is an oxygen atom, a sulfur atom, or a divalent organic group. The photosensitive resin composition according to claim 1 or 2, wherein the organic group is at least one selected from the group consisting of:

12. Y in the general formula (1) １ and / or Y in the general formula (3) ２ is represented by the following general formulas (9) to (12): 【Chemistry 12】 {R １４ , R １５ , R １６ and R １７ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different. 【Chemistry 13】 【Chemistry 14】 {R ２６ is a divalent group, and R １８ ~R ２５ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different. 【Chemistry 15】 {R ２７ and R ２８ is a divalent group, and R ２９ and R ３０ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different. The photosensitive resin composition according to claim 1 or 2, wherein the organic group is at least one selected from the group consisting of:

13. 3. The photosensitive resin composition according to claim 1, comprising at least two or more types of polyimide precursors (A) represented by the general formula (1) and / or at least two or more types of polyimides (A) represented by the general formula (3).

14. In the general formula (1), X １ and / or, in the general formula (3), X ２ The photosensitive resin composition according to claim 1 or 2, comprising at least two or more of the following:

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

16. The method for producing a cured relief pattern of claim 15, wherein the substrate is formed from copper or a copper alloy.

17. A semiconductor device comprising a cured relief pattern obtained by the method for producing a cured relief pattern according to claim 15.

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