TWI852212B - Negative photosensitive resin composition, method for manufacturing hardened relief pattern, and semiconductor device - Google Patents

Abstract

The purpose of the present invention is to provide a photosensitive resin composition, a method for manufacturing a hardened relief pattern using the photosensitive resin composition, and a semiconductor device. The photosensitive resin composition will not precipitate due to low-temperature storage, and can form a hardened film with high adhesion and suppressed migration even on copper or copper alloy. The present invention provides a negative photosensitive resin composition, characterized in that it comprises: (A) at least one resin selected from (A1) polyimide precursor and (A2) polyimide; (B) photopolymerization initiator; (C) tetrazole compound as nitrogen-containing heterocyclic compound; and (D) solvent, wherein the photosensitive resin composition further comprises (E) precipitation inhibitor for preventing precipitation of the nitrogen-containing heterocyclic compound (C), and the Hansen solubility parameter (HSP) of the precipitation inhibitor (E) is in the following range: △D: 15.2-21.2 △P: 8.9-14.9 △H: 9.0-14.3.

Description

Negative photosensitive resin composition, method for manufacturing hardened relief pattern, and semiconductor device

The present invention relates to a photosensitive resin composition, a hardened relief pattern obtained by hardening the photosensitive resin composition, a semiconductor device, and the like.

Previously, polyimide resins with excellent heat resistance, electrical properties, and mechanical properties were used in insulating materials for electronic parts, passivation films for semiconductor devices, surface protection films, and interlayer insulation films. In the polyimide resin, a photosensitive polyimide precursor is provided to easily form a heat-resistant embossed pattern coating by coating, exposing, developing, and curing the precursor through thermal imidization. This photosensitive polyimide precursor has the characteristic of greatly shortening the steps compared to the previous non-photosensitive polyimide.

On the other hand, in recent years, the method of packaging semiconductor devices on printed wiring boards has also changed from the previous packaging method using metal pins and lead-tin eutectic soldering to a structure in which a polyimide film is directly in contact with the solder bumps, as shown in BGA (ball grid array) and CSP (chip size package) that can achieve higher density packaging. When forming such a bump structure, the film needs to have higher heat resistance and chemical resistance. A method for improving the heat resistance of a polyimide coating or a polybenzoxazole coating by adding a thermal crosslinking agent to a composition containing a polyimide precursor or a polybenzoxazole precursor is disclosed (see Patent Document 1).

Furthermore, as semiconductor devices become increasingly miniaturized, the wiring resistance of semiconductor devices has become a problem that cannot be ignored. Therefore, the industry is changing the gold or aluminum wiring used previously to copper or copper alloy wiring with lower resistance. However, the previous photosensitive resin composition has poor adhesion to copper, resulting in the problem of resin peeling off from copper wiring.

Furthermore, such a metal redistribution layer needs to exhibit insulation properties even after reliability testing. The reliability test performed here may be, for example, a high temperature storage test in which the device is stored at 150°C for 168 hours in an air with a humidity of 5%. However, the previous photosensitive resin composition is likely to cause copper migration during the reliability test, causing short circuits or disconnections in the redistribution layer.

As a method for solving the above-mentioned problem, a method for improving the adhesion with copper or copper alloy and preventing corrosion by adding tetrazole or its derivative to a composition containing a polyimide precursor is disclosed (see patent documents 2 and 3). [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 2003-287889 [Patent Document 2] Japanese Patent Publication No. 2020-2281 [Patent Document 3] Japanese Patent Publication No. 3170174

[The problem the invention is trying to solve]

However, the compositions described in Patent Documents 2 and 3 have the following problems: if the varnish is stored at a low temperature such as -20°C for a long time, precipitates will be generated. When precipitation occurs, the adhesion with copper decreases and migration deterioration is observed. Furthermore, as the amount of tetrazole or a compound similar to a derivative thereof increases, the generation of the precipitate becomes more significant.

Therefore, the purpose of the present invention is to provide a photosensitive resin composition, a method for manufacturing a hardened relief pattern using the photosensitive resin composition, and a semiconductor device, wherein the photosensitive resin composition will not precipitate due to low-temperature storage or frozen storage, and can form a hardened film having high adhesion and suppressed migration even on copper or copper alloy. [Technical means for solving the problem]

The above problems can be solved by the following technical means. That is, the present invention is as follows. <1> A negative photosensitive resin composition, characterized in that it comprises: (A) at least one resin selected from (A1) polyimide precursor and (A2) polyimide; (B) a photopolymerization initiator; (C) a nitrogen-containing heterocyclic compound; and (D) a solvent, wherein the above (A1) polyimide precursor is the following general formula (1): [Chemical 1] {wherein, _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 independently a hydrogen atom, the following general formula (2): [Chemical 2] (wherein, R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10) a monovalent organic group represented by the following general formula (25): [Chemical 3] (wherein, R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10) represented by a monovalent organic ammonium ion or a saturated aliphatic group having 1 to 4 carbon atoms; wherein R ₁ and R ₂ are not both hydrogen atoms} a polyamic acid ester or polyamic acid salt represented by, the above-mentioned (A2) polyimide is of the following general formula (24): [Chemical 4] (wherein, X ₂ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₂ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50), the above-mentioned photosensitive resin composition further contains the above-mentioned (C) nitrogen-containing heterocyclic compound and the (E) precipitation inhibitor, the above-mentioned (C) nitrogen-containing heterocyclic compound is a tetrazole compound, and the Hansen Solbility parameter (HSP) of the above-mentioned (E) precipitation inhibitor is in the following ranges: △D: 15.2 to 21.2 △P: 8.9 to 14.9 △H: 9.0 to 14.3. <2> The negative photosensitive resin composition as described in item 1, wherein the Hansen solubility parameter of the above-mentioned (E) anti-precipitation agent is in the following ranges: △D: 16.2-20.2 △P: 9.9-13.9 △H: 9.3-13.3. <3> The negative photosensitive resin composition as described in item 1 or 2, wherein the Hansen solubility parameter of the above-mentioned (E) anti-precipitation agent is in the following ranges: △D: 16.7-19.7 △P: 10.4-13.4 △H: 9.8-12.8. <4> A negative photosensitive resin composition as described in any one of items 1 to 3, wherein the Hansen solubility parameter of the above-mentioned (E) precipitation inhibitor is in the following range: △D: 17.2-19.2 △P: 10.9-12.9 △H: 10.3-12.3. <5> A negative photosensitive resin composition as described in any one of items 1 to 4, wherein the above-mentioned tetrazole compound is 5-amino-1H-tetrazole. <6> A negative photosensitive resin composition as described in any one of items 1 to 5, wherein in the above-mentioned general formula (1), _X1 is selected from the following general formulas (3) to (6): [Chemistry 5] [Chemistry 6] [Chemistry 7] [Chemistry 8] (wherein, R ₆ , R ₇ and R ₈ are independently an oxygen atom, a sulfur atom, or a divalent organic group; R ₉ and R ₁₀ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different) one or more organic groups. <7> A negative photosensitive resin composition as described in any one of items 1 to 6, wherein in the above general formula (1), Y ₁ is selected from the following general formulas (7) to (10): [Chemical 9] (In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different) [Chemical 10] (In the formula, R ₁₅ to R ₂₂ are hydrogen atoms, halogen atoms, monovalent organic groups with 1 to 5 carbon atoms, or hydroxyl groups, and they may be different or the same) [Chemical 11] (In the formula, R ₂₃ is a divalent group, R ₂₄ to R ₃₁ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and they may be the same or different) [Chemistry 12] (wherein, R ₃₂ and R ₃₃ are divalent groups, R ₃₄ and R ₃₅ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different) one or more organic groups. <8> A negative photosensitive resin composition as described in any one of items 1 to 7, wherein in the above general formula (1), Y ₁ is selected from the following general formulas (7), (9) and (10): [Chemical 13] (In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different) [Chemical 14] (In the formula, R ₂₃ is a divalent group, R ₂₄ to R ₃₁ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and they may be the same or different) [Chemistry 15] <9> A negative photosensitive resin composition as described in any one of items 1 to 8, wherein in the above general formula (1), _X1 is selected from the following general formulas (11) to (14): [Chemical 16] [Chemistry 17] [Chemistry 18] [Chemistry 19] <10> A negative photosensitive resin composition as described in any one of items 1 to 9, wherein in the above general formula (1), _X1 is selected from the following general formulas (11) to (14): [Chemical 20] [Chemistry 21] [Chemistry 22] [Chemistry 23] <11> A negative photosensitive resin composition as described in any one of items 1 to 10, wherein in the above general formula (1), _X1 is a compound comprising the following general formulas (12) and (13): [Chemical 24] [Chemistry 25] <12> A negative photosensitive resin composition as described in any one of items 1 to 11, wherein in the above general formula (1), _X1 is a general formula (11) and (13) as follows: [Chemistry 27] <13> A negative photosensitive resin composition as described in any one of items 1 to 11, wherein in the above general formula (1), _X1 is a general formula (14): [Chemical 28] <14> A negative photosensitive resin composition as described in any one of items 1 to 13, wherein in the above general formula (1), Y ₁ is selected from the following general formulas (21) to (23): [Chemical 29] [Chemistry 30] [Chemistry 31] <15> The negative photosensitive resin composition as described in any one of items 1 to 14, characterized in that: the above-mentioned (E) anti-precipitation agent is selected from acetaniline, acetic anhydride, acrylamide, ethylene dichloride, N,N-diethylformamide, diethylene glycol monoethyl ether, N,N-dimethylacetamide, dimethylethanolamine, ethyl carbamate, ethyl cyanoacrylate, ethyl isothiocyanate, ethyl methanesulfonate, ethyleneimide, 2-hydroxyethyl acrylate, isocyanic acid, isothiocyanate, methacrylamide, 3-methylisothiocyanate, propionamide, 2- - At least one selected from the group consisting of pyrrolidone, pyrrole, succinaldehyde, tetramethylene sulfone, thiocyanic acid, triethyl phosphate, trifluoroacetic acid, trimethyl phosphate, salicylic aldehyde, 1,3-bismethoxymethylurea, 2-acetylthiophene, benzoin, 2-methylpyrrolidone, 4-nitrophenol, 3,4-dinitrophenol, N-ethylformamide, maleic anhydride, pyrazole, ethyl cyanoacetate, benzamide, n-butylamide, vanillin, saccharin, cyclohexyl imide, caffeine, salicylic acid, spermidine, acetaminophen, diacetin and pyrimidine. <16> The negative photosensitive resin composition as described in any one of items 1 to 15, wherein the (E) precipitation inhibitor comprises a urea skeleton or an amide skeleton. <17> A negative photosensitive resin composition as described in any one of items 1 to 16, wherein the above-mentioned (E) anti-precipitation agent contains sulfur atoms. <18> A method for producing a hardened relief pattern, comprising the following steps: (1) applying the negative photosensitive resin composition as described in any one of items 1 to 17 on a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heating the relief pattern to form a hardened relief pattern. <19> The method as described in item 18, wherein the substrate is formed of copper or a copper alloy. <20> A semiconductor device comprising a hardened relief pattern obtained by the manufacturing method as described in item 18 or 19. [Effects of the invention]

According to the present invention, by adding a specific compound having a precipitation-preventing function to a photosensitive resin composition, precipitation can be suppressed during low-temperature storage or frozen storage, and a photosensitive resin composition having excellent adhesion and suppressed migration even on copper or copper alloy, a method for forming a hardened relief pattern using the photosensitive composition, and a semiconductor device having the polyimide pattern can be provided.

Hereinafter, the method for implementing the present invention (hereinafter, referred to as "implementation") is described in detail. In addition, the present invention is not limited to the following implementation, and can be implemented in various ways within the scope of the gist.

In the present embodiment, the photosensitive resin composition is a negative photosensitive resin composition comprising (A) at least one resin selected from the group consisting of polyimide precursor (A1) and polyimide (A2), (B) a photopolymerization initiator, (C) a nitrogen-containing heterocyclic compound, (D) a solvent, and (E) an anti-precipitation agent. The negative photosensitive resin composition may contain other components as required. Each component is described in order below.

Furthermore, in this specification, when a plurality of structures represented by the same symbol in a general formula exist in a molecule, the structures may be the same or different from each other.

(A) Resin (A1) Polyimide Precursor The (A1) polyimide precursor used in the present embodiment is described. The resin component in the photosensitive resin composition is a polyamic acid ester or polyamic acid salt having a structural unit represented by the following general formula (1). The (A1) polyimide precursor is converted into polyimide by applying heat (e.g., above 200°C) for cyclization. The following general formula (1): [Chemical 32] {wherein, _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, _R1 and _R2 are independently a hydrogen atom, the following general formula (2): [Chemical 33] (wherein, R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, 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) a monovalent organic group represented by the following general formula (25): [Chemical 34] (wherein R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, 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 from 2 to 10) represented by a monovalent organic ammonium ion or a saturated aliphatic group having 1 to 4 carbon atoms; wherein R ₁ and R ₂ are not both hydrogen atoms}.

In the above general formula (1), the tetravalent organic group represented by _X1 is a tetravalent organic group having 6 to 40 carbon atoms, more preferably an aromatic group in which _-COOR1 and _-COOR2 are adjacent to -CONH-, or an alicyclic aliphatic group.

In the general formula (1), _X1 can be selected from the following general formulas (3) to (6): [Chemistry 36] [Chemistry 37] [Chemistry 38] (wherein, R ₆ , R ₇ and R ₈ are independently an oxygen atom, a sulfur atom or a divalent organic group; R ₉ and R ₁₀ are 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) at least one organic group.

In one embodiment, _X1 in the general formula (1) is preferably selected from the following formula (20): One or more species from the indicated group.

In another embodiment, _X1 in the general formula (1) is preferably selected from the following general formulas (11) to (14): [Chemistry 41] [Chemistry 42] [Chemistry 43] One or more or two or more organic groups.

In another embodiment, _X1 in the general formula (1) is preferably an organic group including the above-mentioned general formulae (12) and (3), an organic group including the above-mentioned general formulae (11) and (13), or an organic group including the general formula (14).

In the above general formula (1), the tetravalent organic group represented by _X1 is preferably at least one selected from 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride (BPADA).

The structure of _X1 may be one or a combination of two or more. From the viewpoint of improving the resolution, a combination of two or more is more preferred.

In the above general formula (1), in order to achieve both heat resistance and photosensitivity, the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms, for example, the following formula (15) can be cited: The structure represented by, and the following formula (16): [Chemical 45] The structure represented by {wherein, R ₂₃ and R ₂₄ each independently represent a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ) or a butyl group (-C ₄ H ₉ )} is not limited thereto.

In one embodiment, _Y1 in the general formula (1) is preferably selected from the following general formulas (7) to (10): (In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different) [Chemical 47] (In the formula, R ₁₅ to R ₂₂ are hydrogen atoms, halogen atoms, monovalent organic groups with 1 to 5 carbon atoms, or hydroxyl groups, and they may be different or the same) [Chemical 48] (In the formula, R ₂₃ is a divalent group, R ₂₄ to R ₃₁ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and they may be the same or different) [Chemistry 49] (wherein, R ₃₂ and R ₃₃ are divalent groups, R ₃₄ and R ₃₅ are hydrogen atoms, halogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different) at least one organic group.

In another embodiment, _Y1 in the general formula (1) is preferably one or more organic groups selected from the general formulae (7), (9) and (10).

In another embodiment, _Y1 in the general formula (1) is preferably selected from the following general formulas (21) to (23): [Chemistry 51] [Chemistry 52] One or more organic groups.

Furthermore, the structure of _Y1 may be one type or a combination of two or more types.

In the above general formula (1), the divalent organic group represented by _Y1 is preferably at least one selected from diaminodiphenyl ether (DADPE), p-phenylenediamine (pPD), and 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) in terms of achieving both heat resistance and photosensitivity.

Furthermore, the (A1) polyimide precursor preferably comprises a precursor represented by the general formula (1), wherein at least one of _R1 and _R2 comprises a group represented by the general formula (2) or (25), and a double bond is present at the end of _R1 and _R2 comprising the group represented by the general formula (2) or (25).

[(A1) Preparation method of polyimide precursor] The polyimide precursor represented by the general formula (1) in the present embodiment can be obtained, for example, by reacting a tetracarboxylic dianhydride comprising the above-mentioned quadrivalent organic group _X1 having 6 to 40 carbon atoms and (a) an alcohol formed by bonding a monovalent organic group represented by the general formula (2) and a hydroxyl group to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as acid/ester), and then condensing the tetracarboxylic acid with a diamine comprising the above-mentioned divalent organic group _Y1 having 6 to 40 carbon atoms.

(Preparation of Acid/Ester) In the present embodiment, the tetracarboxylic dianhydride containing a tetravalent organic group _X1 having 6 to 40 carbon atoms may be exemplified by: pyromellitic dianhydride, diphenyl ether-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'-isopropyldiphenoxy)diphthalic anhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and the like. These may be used alone or in combination of two or more.

(a) Examples of aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms formed by bonding a monovalent organic group represented by the general formula (2) 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.

The content of the above-mentioned component (a) in the negative photosensitive resin composition is preferably more than 80 mol% relative to the total content of _R1 and _R2 . If the content of the component (a) exceeds 80 mol%, the desired photosensitivity can be obtained, which is preferred. The content of the above-mentioned component (a) in the negative photosensitive resin composition is preferably more than 85 mol%, more preferably more than 90 mol%, and more preferably more than 95 mol% relative to the total content of _R1 and _R2 .

By stirring, dissolving and mixing the tetracarboxylic dianhydride and the alcohol in a reaction solvent at a reaction temperature of 20 to 50° C. for 4 to 10 hours in the presence of an alkaline catalyst such as pyridine, a half-esterification reaction of the dianhydride can be carried out to obtain the desired acid/ester.

The reaction solvent is preferably one that dissolves the acid/ester and the polycondensation product of the acid/ester and diamines, i.e., the polyimide precursor, and examples thereof include: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-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, xylene, and the like. They may be used alone or in combination of two or more, as needed.

(Preparation of polyimide precursor) The polyimide precursor that can be used in the embodiment can be obtained by the following method: a known dehydration condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. is added to the above-mentioned acid/ester body (typically, the solution in the above-mentioned reaction solvent) under ice cooling to convert the acid/ester body into a polyanhydride, and then a diamine having a carbon number of 6 to 40 in the general formula (1) is added _dropwise thereto, which is separately dissolved or dispersed in the solvent, and condensation is carried out.

Diamines containing a divalent organic group _Y1 suitable for use in the present invention include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diamino Benzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone 1,4-Bis(4-aminophenyl)benzene, 1,3-Bis(4-aminophenyl)benzene, 9,10-Bis(4-aminophenyl)anthracene, 2,2-Bis(4-aminophenyl)propane, 2,2-Bis(4-aminophenyl)hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)phenyl)propane, 2,2-Bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-Bis(3-aminopropyldimethylsilyl)benzene, di-ortho-toluidine, 9,9-Bis(4-aminophenyl)fluorene; compounds in which a portion of the hydrogen atoms on the benzene rings are substituted by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, 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.

Among them, 4,4'-diaminodiphenyl ether, p-phenylenediamine, 4,4-dimethyl-2,2'-diaminobiphenyl, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane are preferably used, and 4,4'-diaminodiphenyl ether, p-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane are more preferably used.

In order to improve the adhesion with various substrates, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane may be copolymerized.

After the reaction is completed, the water-absorbing byproduct of the dehydration condensation agent coexisting in the reaction solution is filtered and separated as needed, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component, and then the polymer is repeatedly dissolved and reprecipitated to purify the polymer, and then vacuum dried to isolate the target polyimide precursor. In order to improve the degree of purification, the polymer solution can also be filled with a cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

The molecular weight of the polyimide precursor (A1) is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 20,000 to 40,000 when measured by gel permeation chromatography as a weight average molecular weight in terms of polystyrene. 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 of relief patterns. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

(A2) Polyimide The (A2) polyimide used in this embodiment is described. The resin component in the photosensitive resin composition is a polyimide resin having a structural unit represented by the following general formula (24). [Chemical 53] {wherein, X ₂ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₂ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50} The resin represented by general formula (24) is particularly preferred in that it can exhibit sufficient membrane properties without undergoing chemical changes during the heat treatment step, and is therefore suitable for treatment at a lower temperature.

In the general formula (24), the divalent organic group represented by X ₂ and/or the tetravalent organic group represented by Y ₂ preferably contains an aromatic ring structure, and more preferably contains a benzene ring structure, from the viewpoint of heat resistance.

From the viewpoint of solubility in an organic solvent, it is preferred that at least one of X ₂ and Y ₂ is a group containing a fluorine atom, and it is preferred that both X ₂ and Y ₂ are groups containing a fluorine atom.

In the general formula (24), the tetravalent organic group represented by _X2 and/or the divalent organic group represented by _Y2 preferably has a structure in which 2 to 6 benzene rings are linked via a single bond or a divalent linking group. 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 straight chain or branched chain.

(A2) Polyimide can be obtained by reacting tetracarboxylic acid, its corresponding tetracarboxylic dianhydride, dichlorotetracarboxylic acid diester, etc. with diamine, its corresponding diisocyanate compound, trimethylsilylated diamine, etc. Polyimide can be generally obtained by dehydrating and ring-closing polyamide by heating or chemical treatment based on acid or alkali, and the polyamide is one kind of polyimide precursor obtained by reacting tetracarboxylic dianhydride with diamine.

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 1,1-bis(3,4-dihydroxyphenyl)ethane dianhydride, 1,1-bis(2,3-dihydroxyphenyl)ethane dianhydride, bis(3,4-dihydroxyphenyl)methane dianhydride, bis(2,3-dihydroxyphenyl)methane dianhydride, bis(3,4-dihydroxyphenyl)methane dianhydride, bis(2,3-dihydroxyphenyl)methane dianhydride, bis(3,4-dihydroxyphenyl)sulfone Dianhydride, bis(3,4-dihydroxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dihydroxyphenyl)fluoric acid dianhydride, 9,9-bis{4-(3,4-dihydroxyphenoxy)phenyl}fluoric acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10 Aromatic tetracarboxylic dianhydrides such as perylene tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, and 2,2-bis(3,4-dihydroxyphenyl)hexafluoropropane dianhydride, aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride and 1,2,3,4-cyclopentane tetracarboxylic dianhydride, and compounds represented by 3,3',4,4'-diphenylsulfonate tetracarboxylic dianhydride.

Among them, it is preferred to use pyromellitic dianhydride (PMDA), diphenyl ether-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'-diphenylsulfonate tetracarboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA), and these can be used alone or in combination of two or more.

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'-diaminodiphenylsulfone, 3,3'-dimethylbenzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-Bis(p-aminophenyl)hexafluoropropane, bis(trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydiphenylamine (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2, 2'-Bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DFPOB), 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-diaminotoluene trifluoride (3,5-DABTF), 3,5-diamino-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)benzidine (6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenylphosphine (3FCDAM), 3,6-diamino-9,9-diphenylphosphine The compounds represented, etc.

The ratio of diamine to dianhydride used is basically 1:1 in terms of molar ratio. However, in order to obtain the desired terminal structure, one of them may be used in excess. Specifically, by using diamine in excess, the end (both ends) of the polyimide (A2) easily becomes an amine group. On the other hand, by using dianhydride in excess, the end (both ends) of the polyimide (A2) easily becomes an anhydride group. As described above, in this embodiment, polyimide (A2) preferably has an anhydride group at its end. Therefore, in this embodiment, it is preferred to use dianhydride in excess when synthesizing polyimide (A2).

Certain reagents may also react with the amine group and/or anhydride group at the end of the polyimide obtained by condensation to impart desired functional groups to the end of the polyimide.

Regarding the molecular weight of (A2) polyimide, when measured by a weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography, it is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, and particularly preferably 10,000 to 50,000. When the weight average molecular weight is 5,000 or more, the mechanical properties are good, so it is preferred. On the other hand, when the weight average molecular weight is 150,000 or less, the dispersibility in the developer and the resolution performance of the relief pattern are good, so it is preferred. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight is obtained based on a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

(B) Photopolymerization initiator The (B) photopolymerization initiator in this embodiment is described. As the (B) photopolymerization initiator, a compound previously used as a photopolymerization initiator for UV curing can be arbitrarily selected.

(B) Photopolymerization initiators that can be used include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, benzophenone derivatives such as dibenzyl ketone and fluorenone, acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 9-thiothiophenone, , 2-methyl 9-oxosulfuron , 2-isopropyl 9-oxysulfide and diethyl 9-oxysulfide 9-Oxysulfuron derivatives, benzoyl derivatives such as benzoyl dimethyl ketone and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-bis(4'-diazolidine benzylmethylene)-4-methylcyclohexanone and 2,6'-bis(4'-diazolidine benzylmethylene)cyclohexanone, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, Oxime, such as 1-phenylpropanedione-2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, N-arylglycine such as N-phenylglycine, peroxides such as benzoyl peroxide, aromatic biimidazoles, and titanocenes. Among them, the above oximes are preferred from the viewpoint of photosensitivity.

The amount of (B) photopolymerization initiator is 0.1 to 20 parts by weight relative to 100 parts by weight of (A) resin, preferably 2 to 15 parts by weight from the viewpoint of photosensitivity. By adding 0.1 parts by weight or more of (B) photopolymerization initiator relative to 100 parts by weight of (A) resin, the photosensitivity of the photosensitive resin composition is excellent, while by adding 20 parts by weight or less, the thick film curing property of the photosensitive resin composition is excellent.

(C) Nitrogen-containing heterocyclic compound The (C) nitrogen-containing heterocyclic compound of this embodiment is described. The (C) nitrogen-containing heterocyclic compound is not particularly limited as long as it is a π-conjugated molecule containing a nitrogen atom, and azole derivatives, trioxane derivatives, purine derivatives, etc. can be used.

Since nitrogen atoms form strong coordination with the d orbital of copper atoms through electron donation and counter-donation, the more nitrogen atoms contained in one molecule of the nitrogen-containing heterocyclic compound (C), the better. Specifically, tetrazoles, i.e., tetrazole compounds having a tetrazole skeleton, are preferred.

Furthermore, from the viewpoint of enhancing the interaction with the resin, the (C) nitrogen-containing heterocyclic compound preferably has an amino group.

Examples of oxazole derivatives include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-bis(α,α-dimethylbenzyl)phenyl)-benzotriazole, and 2-(3,5-bis(α,α-dimethylbenzyl)phenyl)-benzotriazole. The present invention also includes benzotriazole, ...

Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-aminoadenine, The invention also includes 1-methyl-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine and the like and derivatives thereof, preferably 8-azaadenine.

Specific examples of triazine derivatives include 1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 1,3,5-triazine-2,4,6-triol, 1,3,5-triazolidine-2,4,6-trione, 2,4,6-triphenyl-1,3,5-triazine, 2,4,6-trimethoxy-1,3,5-triazine, 2,4-dimethoxy-1,3,5-triazine, methyl isocyanurate, 1,3,5-triazine-2,4,6-trithiol, 1,3,5-triazine-2,4,6-triamine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-1,3 ,5-triazolidine-2-one, 6-amino-1,3,5-tri𠯤-2,4-diol, 6-amino-1,3,5-tri𠯤-2,4-dione, 2,4-diamino-6-butylamino-1,3,5-tri𠯤, 2,4-diamino-6-diethylamino-1,3,5-tri𠯤, benzoguanamine, 2,4,6-tri(4-pyridyl)-1,3,5-tri𠯤, 2,4-diamino-6-methyl-1,3,5-tri𠯤, 2,4-diamino-6-methoxy-1,3,5-tri𠯤, 2,4-diamino-6-hydroxy-1,3,5-tri𠯤, triallyl cyanurate, etc.

The amount of the nitrogen-containing heterocyclic compound (C) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the resin (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the nitrogen-containing heterocyclic compound (C) such as the azole compound is 0.1 parts by mass or more relative to 100 parts by mass of the resin (A), the photosensitive resin composition of the present invention has excellent adhesion to copper or copper alloy even when formed on copper or copper alloy and exposed to a high temperature environment. On the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent.

(D) Solvent The (D) solvent in this embodiment is described. As the (D) solvent, from the viewpoint of solubility in the (A1) polyimide precursor, it is preferred to use a polar organic solvent. Specifically, examples thereof include: N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, etc., which can be used alone or in combination of two or more. The Hansen solubility parameter of the solvent (D) in this embodiment may not meet the following range: △D: 15.2-21.2 △P: 8.9-14.9 △H: 9.0-14.3.

Depending on the coating film thickness and viscosity required for the negative photosensitive resin composition, the above solvent can be used in an amount of, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, relative to 100 parts by mass of the resin (A).

Furthermore, from the viewpoint of improving the storage stability of the negative photosensitive resin composition, a solvent containing an alcohol is preferred. The alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and having no olefinic double bond, and specific examples include: alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol; 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-hydroxy isobutyric acid esters; and diols such as ethylene glycol and propylene glycol. Among them, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters and ethanol 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.

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 mass % to 50 mass %, more preferably 10 mass % to 30 mass %, based on the mass of the total solvent. When the content of the alcohol having no olefinic double bond is 5 mass % or more, the storage stability of the negative photosensitive resin composition is good. On the other hand, when the content is 50 mass % or less, the solubility of the polyimide precursor (A1) is good, which is preferred.

(E) Precipitation inhibitor for preventing precipitation of the nitrogen-containing heterocyclic compound (C) The precipitation inhibitor for the nitrogen-containing heterocyclic compound (C) as the (E) component of the present embodiment is described. The (E) precipitation inhibitor in the present invention is defined based on the Hansen Solubility Parameters (HSP). The Hansen Solubility Parameters are different from the usual solubility parameters and include three items: the energy △D generated by the intermolecular dispersion force, the energy △P generated by the intermolecular dipole interaction, and the energy △H generated by the intermolecular hydrogen bond. The characteristic of the (E) anti-precipitation agent in the present invention is that HSP has the following range: △D: 15.2～21.2 △P: 8.9～14.9 △H: 9.0～14.3 values. (E) The HSP of the anti-precipitation agent is preferably within the following range: △D: 16.2-20.2 △P: 9.9-13.9 △H: 9.3-13.3, more preferably within the following range: △D: 16.7-19.7 △P: 10.4-13.4 △H: 9.8-12.8, further preferably within the following range: △D: 17.2-19.2 △P: 10.9-12.9 △H: 10.3-12.3.

According to the present invention, it is found that by adding a compound having a precipitation prevention function and specified by the above HSP to a photosensitive resin composition, precipitation can be suppressed during low temperature storage or frozen storage, thereby providing a cured film having excellent adhesion and suppressed migration even on copper or copper alloy. The detailed mechanism of exerting the above effect is not clear, but it is presumed to be as follows.

Regarding the Hansen Solubility Parameter (HSP), it is believed that if two substances with similar intermolecular interactions are easily dissolved in each other, then the three items of energy △D generated by the intermolecular dispersion force, energy △P generated by the intermolecular dipole interaction, and energy △H generated by the intermolecular hydrogen bond, which have close values, can be used as indicators of solubility difficulty. According to the present invention, this idea is applied to the anti-precipitation function. According to the analysis of the inventors and others, the precipitate generated in the photosensitive resin composition containing the (C) nitrogen-containing heterocyclic compound such as tetrazole compound is an aggregate formed by the (C) nitrogen-containing heterocyclic compound itself. The reason for the formation of aggregates is that the affinity between the compounds and the surrounding polymers, compounds or solvents is relatively low, and the interaction between the compounds is more Gibbs-stable than when dispersed in the system. That is, by mixing compounds with similar HSP values as (E) precipitation inhibitors, the dispersion of (C) nitrogen-containing heterocyclic compounds can be promoted and the formation of aggregates can be inhibited.

According to the present invention, based on the technical ideas described above, it is found that compounds with specific △D, △P, and △H have the function of preventing precipitation. In addition, the adhesion or migration inhibition effect on copper wiring is manifested by the coordination determined by the electron supply and reverse supply of nitrogen atoms and copper atoms d orbits, so it is more ideal that the nitrogen-containing heterocyclic compound exists efficiently on the copper surface. The inventors of the present invention and others speculate that by inhibiting the precipitation of (C) nitrogen-containing heterocyclic compounds or their aggregates and forming a dispersed state of (C) nitrogen-containing heterocyclic compounds, the adhesion to copper wiring and the inhibition of migration can be improved.

The HSP value is derived from the solubility parameter calculation software HSPiP (Hansen Solubility Parameters in Practice).

The precipitation in the present invention refers to the precipitation generated when the photosensitive resin composition is stored at a low temperature below 0°C. The (E) precipitation inhibitor has the function of preventing the precipitation.

From the viewpoint of the anti-precipitation function and the action mechanism of the present invention, the anti-precipitation agent (E) preferably contains a urea skeleton such as N,N-bismethoxymethylurea and/or contains a sulfur atom such as tetramethylene sulfone, 2-acetylthiophene, etc., and from the same viewpoint, preferably has an amide skeleton.

(E) The precipitation inhibitor is not particularly limited as long as it is a compound having a Hansen solubility parameter within a specific range, and examples thereof include the compounds shown in the following table.

[Table 1-1] Compound Name △D △P △H Acetaniline 20.6 14.4 13.5 Acetic anhydride 16.0 11.7 10.2 Acrylamide 15.8 12.1 12.8 Ethylene Nitrate 15.9 8.9 12.9 Chloroacetaldehyde 16.2 14.0 9.0 Chloroacetic acid 17.7 10.4 12.3 2-Chloroacrylic acid 19.1 9.4 12.4 N,N-Diethylformamide 16.4 11.4 9.2 Diethylene glycol monoethyl ether 16.1 9.2 12.2 N,N-Dimethylacetamide 16.8 11.5 9.4 Dimethylethanolamine 16.1 9.2 14.0 Dimethylformamide (DMF) 17.4 13.7 11.3 Ethyl carbamate 16.8 10.1 13.0 Ethyl cyanoacrylate 15.2 10.3 9.0 Ethyl isothiocyanate 17.2 14.7 9.0 Ethyl methanesulfonate 16.9 9.3 9.6 Ethylenediamine 17.7 11.0 9.8 Hydroxyethyl acrylate 16.0 13.2 13.4 Isocyanic acid 15.8 10.5 13.6 Isopropylamine 18.8 13.4 11.2 Methacrylamide 15.8 11.0 11.6 3-Methylisothiazol 19.4 14.8 11.8 2,3-Epoxy-l-propionaldehyde 17.5 13.4 9.8 Propionamide 16.7 14.6 11.5 2-Pyrrolidone 18.2 12.0 9.0 Pyrrole 19.2 11.0 10.0 Succinaldehyde 16.8 9.8 10.5 Tetramethylenesulfone 18.2 11.0 9.1 Thiocyanate 16.8 8.9 10.9

[Table 1-2] Compound Name △D △P △H Triethyl phosphate 16.7 11.4 9.2 Trifluoroacetic acid 15.6 9.7 11.4 Trimethyl phosphate 15.7 10.5 10.2 Salicylic acid 19.0 10.5 12.0 1,3-Bis(4-methoxyphenyl)urea 17.8 14.9 11.9 2-Acetylthiophene 19.1 12.2 9.3 Benzoin 19.9 9.7 10.7 Benzimidazole 20.6 14.9 11.0 2-Methylpyridine 18.3 12.3 10.5 4-Nitrophenol 20.0 14.5 14.2 3,4-Dinitrophenol 19.5 12.8 14.3 N-Ethylformamide 16.2 10.0 14.0 Maleic anhydride 19.5 13.3 11.9 Pyrazole 20.2 10.4 12.4 Methyl cyanoacetate 16.9 14.9 9.9 Benzamide 21.2 14.7 11.2 2-Chloroacetamide 17.6 12.4 12.8 n-Butylamide 16.9 13.7 12.3 Nitroglycerin (glyceryl trinitrate) 16.9 13.0 10.9 2,4,6-Tribromophenol 20.6 10.2 14.1 Tetrabromobisphenol A 20.2 9.1 13.8 Vanillin (4-hydroxy-3-methoxybenzaldehyde) 19.4 9.8 11.2 saccharin 21.1 12.5 9.8 Cycloheximide 18.3 11.0 13.8 caffeine 19.5 10.1 13.0 Salicylic acid 19.0 9.0 13.7 Spermidine 16.7 11.2 12.0 Acetaminophen 17.8 10.5 13.9 Glyceryl diacetate 16.4 8.9 14.2

[Table 1-3] Compound Name △D △P △H 2,6-Dichloro-7-methylpurine 20.5 11.7 14.2 Purine 20.5 11.7 14.2 Pyrimidine 20.5 9.4 11.3 Glyceryl Carbonate Acetate 17.1 14.7 9.2

Among the compounds in the above table, from the viewpoint of precipitation inhibition performance, the above (E) precipitation inhibitor is preferably selected from acetaniline, acetic anhydride, acrylamide, ethylene dichloride, N,N-diethylformamide, diethylene glycol monoethyl ether, N,N-dimethylacetamide, dimethylethanolamine, ethyl carbamate, ethyl cyanoacrylate, ethyl isothiocyanate, ethyl methanesulfonate, ethyleneimide, 2-hydroxyethyl acrylate, isocyanic acid, isothiocyanate, methacrylamide, 3-methylisothiocyanate, propionamide, 2-pyrrolidone, pyrrole, succinaldehyde, tetramethylene sulfone. At least one of the group consisting of thiocyanate, triethyl phosphate, trifluoroacetic acid, trimethyl phosphate, salicylic aldehyde, 1,3-bismethoxymethylurea, 2-acetylthiophene, benzoin, 2-methylpyrrolidone, 4-nitrophenol, 3,4-dinitrophenol, N-ethylformamide, maleic anhydride, pyrazole, ethyl cyanoacetate, benzamide, n-butylamide, vanillin, 1,2-benzoisothiazol-3(2H)-one, 1,1-dioxide (also known as saccharin), cycloheximide, caffeine, salicylic acid, spermidine, acetaminophen, diacetin and pyrimidine.

The amount of the anti-precipitation agent (E) is preferably in the range of 0.01 to 50 parts by weight, more preferably in the range of 1 to 20 parts by weight, relative to 100 parts by weight of the resin (A).

Other components In this embodiment, the negative photosensitive resin composition may further contain components other than the above-mentioned components (A) to (E). Examples of other components include: resin components other than the above-mentioned resin (A), sensitizers, monomers having photopolymerizable unsaturated bonds, bonding aids, thermal polymerization inhibitors, hindered phenol compounds, organic titanium compounds, etc.

In the embodiment, the negative photosensitive resin composition may further contain resin components other than the above-mentioned (A) resin. Examples of the resin components that the negative photosensitive resin composition may contain include: polyazole, polyazole precursor, phenolic resin, polyamide, epoxy resin, silicone resin, acrylic resin, etc. The amount of the resin components is preferably in the range of 0.01 to 20 parts by weight relative to 100 parts by weight of the (A) resin.

In this embodiment, a sensitizer may be added to the negative photosensitive resin composition to improve the photosensitivity. Examples of the sensitizer include: michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethyl Aminocinnamyl indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenyl)-benzothiazole, 2-(p-dimethylaminophenyl vinyl)benzothiazole, 2-(p-dimethylaminophenyl vinyl)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminobenzylidene)acetone Coumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4- isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-benzimidazole, 1-phenyl-5-benzyltetrazol, 2-benzylthiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, etc. These can be used alone or in combination of plural types (e.g., 2 to 5 types).

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

In the present embodiment, in order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily formulated into the negative photosensitive resin composition. Such a monomer is preferably a (meth) acrylic compound that undergoes a free radical polymerization reaction by a photopolymerization initiator, and examples thereof include: mono- or di-acrylates and methacrylates of ethylene glycol or polyethylene glycol represented by diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or tri-acrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, diacrylate of 1,6-hexanediol, and dimethacrylate of 1,6-hexanediol. and dimethacrylate, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, phenyl trimethacrylate, isobutyl acrylate and isobutyl methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trihydroxymethylpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri- or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds, but are not particularly limited thereto.

The amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass based on 100 parts by mass of the resin (A).

In this embodiment, in order to improve the adhesion between the film formed using the negative photosensitive resin composition and the substrate, an adhesion aid can be optionally formulated into the negative photosensitive resin composition. Examples of the auxiliary agent include γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidyloxypropyl methyl dimethoxysilane, γ-butyl propyl methyl dimethoxysilane, 3-methacryloxypropyl dimethoxymethyl silane, 3-methacryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidylpropyl silane, diethoxy-3-glycidyloxypropyl methyl silane, N-(3-diethoxymethylsilylpropyl) dimethoxyimide, Silane coupling agents such as N-[3-(triethoxysilyl)propyl]phthalamide, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, and aluminum-based bonding agents such as tri(ethyl acetylacetate), aluminum tri(acetylacetonate), and diisopropyl aluminum acetylacetate.

Among the bonding agents, silane coupling agents are more preferably used from the viewpoint of bonding strength. The amount of the bonding agent is preferably in the range of 0.5 to 25 parts by weight relative to 100 parts by weight of the resin (A).

In this embodiment, a thermal polymerization inhibitor may be optionally formulated in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition when it is stored in a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, 4-tert-butyl o-catechol, phenanthridine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol diethyl 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.

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

In this embodiment, in order to suppress discoloration on copper, a hindered phenol compound can be optionally formulated into the negative photosensitive resin composition.

Examples of the hindered phenol compound include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl- 6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-phenylpropionamide), 2,2'-methylene-bis(4-methyl-6 -tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1 ,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri[4-(1-ethylpropyl)-3 -hydroxy-2,6-dimethylbenzyl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 5-Tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4 ,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-3-hydroxy- The present invention also includes, but is not limited to, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-2,5-dimethylbenzyl)-2,4,6-(1H,3H,5H)-trione.

Among them, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-trioxathia-2,4,6-(1H,3H,5H)-trione is particularly preferred.

The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the resin (A), and more preferably 0.5 to 10 parts by weight from the viewpoint of photosensitivity characteristics. When the blending amount of the hindered phenol compound is 0.1 parts by weight or more relative to 100 parts by weight of the resin (A), for example, when a negative photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or a copper alloy can be prevented. On the other hand, when the blending amount is 20 parts by weight or less, the photosensitivity is excellent, so it is preferred.

In the photosensitive resin composition of the present embodiment, an organic titanium compound may be used to increase the elongation after the wet heat durability test. The organic titanium compound that can be used is not particularly limited as long as it is an organic chemical substance bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of organic titanium compounds are shown in the following I) to VII): I) Titanium chelate compounds: Among them, in terms of obtaining storage stability and good patterns of negative photosensitive resin compositions, titanium chelates having two or more alkoxy groups are more preferred, and specific examples are titanium bis(triethanolamine)diisopropoxide, titanium bis(2,4-pentanedioate)di-n-butanol, titanium bis(2,4-pentanedioate)diisopropoxide, titanium bis(tetramethylpimelic acid)diisopropoxide, titanium diisopropoxidebis(ethyl acetylacetate), etc.

II) Tetraalkoxy titanium compounds: for example, titanium tetra-n-butoxide, titanium tetraethanol, titanium tetra(2-ethylhexyl)ol, titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethylol, titanium tetramethoxypropoxide, titanium tetramethylphenol, titanium tetra-n-nonoxide, titanium tetra-n-propoxide, titanium tetrastearylol, titanium tetra[bis{2,2-(allyloxymethyl)butanol}], and the like.

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

IV) Monoalkoxy titanium compounds: for example, titanium tri(dioctyl phosphate) isopropylate, titanium tri(dodecylbenzene sulfonate) isopropylate, etc.

V) Titanium oxide compounds: for example, bis(glutaric acid)titanium oxide, bis(tetramethylpimelic acid)titanium oxide, phthalocyanine titanium oxide, etc.

VI) Titanium tetraacetylpyruvate compound: for example, titanium tetraacetylpyruvate.

VII) Titanium ester coupling agent: for example, isopropyl tri(dodecylbenzenesulfonyl)titanium ester, etc.

In the above I) to VII), from the viewpoint of exhibiting better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound. Titanium diisopropylate bis(ethyl acetylacetate), titanium tetra-n-butoxide and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

The amount of the organic titanium compound added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of the polyamide used as component (A). If the amount added is less than 0.01 parts by weight, the desired adhesion may not be exhibited, and if it exceeds 10 parts by weight, the storage stability may be poor.

Method for producing a hardened relief pattern In the present embodiment, a method for producing a hardened relief pattern can be provided, which comprises the following steps (1) to (4): (1) coating the negative photosensitive resin composition of the present embodiment on a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heating the relief pattern to form a hardened relief pattern.

Each step is described below.

(1) Step of coating the negative photosensitive resin composition of the embodiment on a substrate to form a photosensitive resin layer on the substrate In this step, the negative photosensitive resin composition of the embodiment is coated on a substrate and then dried as needed to form a photosensitive resin layer. The coating method can use a method previously used for coating photosensitive resin compositions, such as a method of coating using a rotary coater, a rod coater, a doctor blade coater, a curtain coater, a screen printer, etc., a method of spray coating using a spray coater, etc.

The coating film containing the negative photosensitive resin composition can be dried as needed, and the drying method can be, for example, air drying, heat drying using an oven or a heating plate, vacuum drying, etc. In addition, the coating film is preferably dried under conditions that do not cause imidization of the (A1) polyimide precursor in the negative photosensitive resin composition. Specifically, when air drying or heat drying is performed, the drying can be performed at 20°C to 140°C and for 1 minute to 1 hour. In the above manner, a photosensitive resin layer can be formed on the substrate.

(2) Exposure of the photosensitive resin layer In this step, an exposure device such as a contact aligner, a mirror projection exposure machine, a stepper, etc. is used to expose the photosensitive resin layer formed in the above step (1) through a patterned mask or grating or directly through an ultraviolet light source.

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

(3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. The developing method for developing the exposed (irradiated) photosensitive resin layer can be selected from any of the previously known photoresist developing methods, such as the rotary spray method, the liquid coating method, and the immersion method accompanied by ultrasonic treatment. In addition, after development, for the purpose of adjusting the shape of the relief pattern, post-development baking with any combination of temperature and time can be performed as needed. The developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent. Good solvents are preferably N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. Poor solvents are preferably toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water, etc. When a good solvent and a poor solvent are mixed for use, it is preferred to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more solvents, for example, several solvents, may be used in combination.

(4) Step of heating the embossed pattern to form a hardened embossed pattern In this step, the embossed pattern obtained by the above-mentioned development is heated to disperse the photosensitive component, and the (A1) polyimide precursor is imidized to convert it into a hardened embossed pattern containing polyimide. The heat curing method can be selected from various methods such as a method using a heating plate, a method using an oven, and a method using a temperature-raising oven with a settable temperature program. Heating can be performed at 200°C to 400°C for 30 minutes to 5 hours. The ambient gas during heat curing can be air, or an inert gas such as nitrogen or argon.

Semiconductor device In this embodiment, a semiconductor device having a hardened relief pattern obtained by the above-mentioned method for manufacturing a hardened relief pattern is also provided. Therefore, a semiconductor device can be provided, which has a substrate as a semiconductor element and a hardened relief pattern of polyimide formed on the substrate by the above-mentioned method for manufacturing a hardened relief pattern. In addition, the present invention can also be applied to a method for manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-mentioned method for manufacturing a hardened relief pattern as a part of the steps. The semiconductor device of the present invention can be manufactured in the following manner, that is, the hardened relief pattern formed by the above-mentioned hardened relief pattern manufacturing method is formed into a surface protection film, an interlayer insulation film, an insulation film for redistribution, a protective film for a flip chip device, or a protective film for a semiconductor device with a bump structure, etc., and combined with a known semiconductor device manufacturing method.

Display device In this embodiment, a display device is provided, which has a display element and a hardened film disposed on the upper part of the display element, and the hardened film is the above-mentioned hardened relief pattern. Here, the hardened relief pattern can be laminated directly in contact with the display element, or can be laminated with other layers sandwiched therebetween. For example, the hardened film can be exemplified as: surface protection film of TFT liquid crystal display element and color filter element, insulating film and flattening film, protrusion for MVA (Multi-Domain Vertical Alignment) type liquid crystal display device, and partition wall for cathode of organic EL (Electroluminescence) element.

The negative photosensitive resin composition of the present invention can be used not only for the semiconductor devices mentioned above, but also for interlayer insulation of multilayer circuits, covering coatings of flexible copper-clad boards, solder resists, and liquid crystal alignment films. [Example]

The present invention is specifically described below by way of examples, but the present invention is not limited thereto. In the examples, comparative examples and preparation examples, the physical properties of the polymer or negative photosensitive resin composition were measured and evaluated according to the following methods.

(1) Copper Migration Evaluation A 6-inch silicon wafer (manufactured by Fujimi Corporation, thickness 625±25 μm) was sputter-coated with Ti to a thickness of 200 nm and copper to a thickness of 400 nm in sequence using a sputtering device (model L-440S-FHL, manufactured by CANON ANELVA). Subsequently, a photosensitive polyamide composition prepared by the method described below was spin-coated on the wafer using a coating developer (model D-Spin60A, manufactured by SOKUDO) and dried to form a coating film with a thickness of 10 μm. Using a mask with a test pattern, the coating film was irradiated with an energy of 300 mJ/ ^cm2 using a parallel light mask aligner (model PLA-501FA, manufactured by CANON). Next, the coating film was spray-developed using cyclopentanone as a developer using a coating developer (model D-Spin60A, manufactured by SOKUDO Co., Ltd.) and then rinsed using propylene glycol methyl ether acetate to obtain a relief pattern on the copper.

The wafer with the relief pattern formed on the copper was subjected to a heat treatment at 200°C for 2 hours in a nitrogen environment using a temperature-programmed curing furnace (model VF-2000, manufactured by Koyo Lindberg). In this way, a hardened relief pattern containing polyimide resin with a thickness of about 6 to 7 μm was obtained on the copper.

The occurrence of copper migration was confirmed by the following high-temperature storage test for the hardened relief pattern obtained. First, the wafer with the hardened relief pattern formed on the copper was heated at 150°C for 168 hours in an air with a humidity of 5% using a temperature-programmed curing furnace (model VF-2000, manufactured by Koyo Lindberg). Then, the polyimide resin layer on the copper was cut using a focused ion beam processing observation device JIB4000 (manufactured by JEOL Ltd.) to obtain a cross-section of the interface between the polyimide resin and the copper.

The cross section of the polyimide resin layer and the copper interface was observed by FE-SEM (model S-4800, manufactured by Hitachi High-Technologies Corporation). The thickness of the migration layer generated at the interface was measured using the length measurement program on the FE-SEM. The measured thickness was evaluated based on the following criteria. "S": The thickness of the copper migration is 0 nm or more and less than 25 nm "A": The thickness of the copper migration is 25 nm or more and less than 50 nm "B": The thickness of the copper migration is 50 nm or more and less than 75 nm "C": The thickness of the copper migration is 75 nm or more

(2) Evaluation of copper adhesion The photosensitive resin composition prepared by the method described below was coated on a 6-inch silicon wafer pre-sputter-coated with Ti and Cu in the same manner as the above-mentioned hardened relief pattern and pre-baked, and then heat-treated at 230°C for 2 hours in a nitrogen environment using a temperature-programmed curing furnace (model VF-2000, manufactured by Koyo Lindberg), thereby obtaining a hardened relief pattern containing resin with a thickness of about 10 μm on Cu. For the film after heat treatment, the adhesion characteristics between the copper substrate and the hardened resin coating were evaluated based on the following criteria according to the cross-cut method of the JIS K 5600-5-6 standard. "S": The number of grids of the hardened resin coating on the substrate is 100 "A": The number of grids of the hardened resin coating on the substrate is 70 to 99 "B": The number of grids of the hardened resin coating on the substrate is 40 to 69 "C": The number of grids of the hardened resin coating on the substrate is less than 40

(3) Evaluation of precipitation The photosensitive resin composition prepared by the method described below was stored at -20°C for 1 month, coated on a 6-inch silicon wafer and pre-baked, and then the number of foreign matter contained in the polyimide resin film on the wafer was measured using a wafer surface inspection device WM-75 (manufactured by TOPCON Co., Ltd.). The evaluation criteria are as follows. "S": less than 1,000 precipitates with a diameter of 1 μm or less "A": more than 1,000 and less than 5,000 precipitates with a diameter of 1 μm or less "B": more than 5,000 and less than 10,000 precipitates with a diameter of 1 μm or less "C": more than 10,000 precipitates with a diameter of 1 μm or less

(Experimental evaluation method)

<Production Example 1> (Synthesis of polymer A-1 as (A) resin) 155 g (0.5 mol) of 4,4'-oxydiphthalic anhydride (ODPA) was added to a 2-liter separable flask, 135 g (1.04 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 79.1 g of pyridine was added while stirring and stirred for 16 hours.

Next, under ice cooling, a solution prepared by dissolving 203 g of dicyclohexylcarbodiimide (DCC) in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, and then 89 g (0.44 mol) of diaminodiphenyl ether (DADPE) suspended in 280 ml of γ-butyrolactone was added over 60 minutes while stirring. The reaction mixture was further stirred at room temperature for 4 hours, 40 ml of ethanol was added and stirred for 1 hour, and then 1 liter of γ-butyrolactone was added. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 4 liters of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was separated by filtration and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 30 liters of water to precipitate the polymer, and the obtained precipitate was separated by filtration, and then vacuum dried to obtain a powdered polymer (polymer A-1). The molecular weight of polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 24,000.

<Production Example 2> (Synthesis of polymer A-2 as (A) resin) Except for using 147 g (0.5 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155 g of ODPA in Production Example 1, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A-2. The molecular weight of polymer A-2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.

<Production Example 3> (Synthesis of polymer A-3 as (A) resin) Except for using 94 g (0.44 mol) of 2,2'-dimethyl-4,4-diaminobiphenyl (m-TB) instead of 89 g of DADPE in Production Example 1, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A-3. The molecular weight of polymer A-3 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 26,000.

<Production Example 4> (Synthesis of polymer A-4 as (A) resin) Except for using 46 g (0.44 mol) of p-phenylenediamine (pPD) instead of 89 g of DADPE in Production Example 1, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A-4. The molecular weight of polymer A-4 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 19,000.

<Production Example 5> (Synthesis of polymer A-5 as (A) resin) Except for using 94 g (0.44 mol) of 2,2'-dimethyl-4,4-diaminobiphenyl (m-TB) instead of 89 g of DADPE in Production Example 2, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A-5. The molecular weight of polymer A-5 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 25,000.

<Production Example 6> (Synthesis of polymer A-6 as (A) resin) Except for using 176 g (0.44 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) instead of 89 g of DADPE in Production Example 1, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A-6. The molecular weight of polymer A-6 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 25,000.

<Production Example 7> (Synthesis of polymer A-7 as (A) resin) Except for using 223 g (0.44 mol) of 4,4'-(4,4'-isopropyldiphenyloxy)diphthalic anhydride (BPADA) instead of 155 g of ODPA in Production Example 3, the reaction was carried out in the same manner as described in the above Production Example 3 to obtain polymer A-7. The molecular weight of polymer A-7 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 25,000.

<Production Example 8> (Synthesis of polymer A-8 as (A) resin) Except that 124 g (0.4 mol) of ODPA and 29 g (0.1 mol) of BPDA were used instead of 155 g of ODPA in Production Example 1, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A-8. The molecular weight of polymer A-8 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.

<Production Example 9> (Synthesis of polymer A-9 as (A) resin) Other than using ODPA 62g (0.2 mol) and pyromellitic dianhydride (PMDA) 65g (0.3 mol) instead of ODPA 155g in Production Example 1, and using m-TB 94g (0.44 mol) instead of DADPE 89g, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A-9. The molecular weight of polymer A-9 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.

<Production Example 10> (Synthesis of polymer A-10 as (A) resin) Except for using 94 g (0.44 mol) of m-TB instead of 89 g of DADPE in Production Example 8, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A-10. The molecular weight of polymer A-10 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.

<Production Example 11> (Synthesis of polymer A-11 as (A) resin) Into a 3 L separable glass flask equipped with a stirring device and a stirring blade, 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 DMAc were added and stirred to dissolve TFMB and 6FDA in DMAc. Further, the mixture was stirred continuously at room temperature for 12 hours under a nitrogen flow to carry out a polymerization reaction, thereby obtaining a polyamide solution.

After adding 16 g of pyridine to the obtained polyamide solution, 82 g of acetic anhydride was added dropwise at room temperature. Thereafter, the liquid temperature was maintained at 20 to 100° C. and stirred for 24 hours to carry out an imidization reaction, thereby obtaining a polyimide solution.

In a 5 L container, the obtained polyimide solution was added to 1,000 g of methanol while stirring to precipitate the polyimide resin. Thereafter, the solid polyimide resin was filtered and separated using a vacuum filter, and then washed with 1,000 g of methanol. Subsequently, it was dried at 100°C for 24 hours using a vacuum dryer, and then dried at 200°C for 3 hours. Through the above steps, a polyimide powder having an anhydride group at the end, namely polymer (A-11), was obtained. The molecular weight of polymer A-11 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 25,000.

<Example 1> A negative photosensitive resin composition was prepared using polymer A according to the following method, and the prepared composition was evaluated. 100 g of polymer A ((A1) polyimide precursor), 2.0 g of TR-PBG-3057 ((B) photopolymerization initiator), 3 g of 5-amino-1H-tetrazole ((C) nitrogen-containing heterocyclic compound), 4 g of N,N-bismethoxymethylurea ((E) precipitation inhibitor), 10 g of tetraethylene glycol dimethacrylate (NK ESTER 4G, Shin-Nakamura Chemical Co., Ltd.), and 2.0 g of KBE-585A (Shin-Etsu Chemical Co., Ltd.) were dissolved in 160 g of γ-butyrolactone (hereinafter referred to as solvent D-1, referred to as GBL) and 40 g of dimethyl sulfoxide (hereinafter referred to as solvent D-2, referred to as DMSO). By further adding a small amount of the solvent, the viscosity of the obtained solution was adjusted to about 40 poise to prepare a negative photosensitive resin composition. The composition was evaluated according to the above method.

<Examples 2 to 30 and Comparative Examples 1 to 5> Except for preparing the mixture in the mixing ratio (mass ratio) shown in Table 3, the same negative photosensitive resin composition as in Example 1 was prepared and the same evaluation as in Example 1 was performed. The description of the abbreviations in Table 3 is shown in Table 2. The evaluation results are shown in Table 4.

[Table 2-1] Polymer A Anhydride 1 Anhydride 2 Diamine A-1 ODPA DADPE A-2 BPDA DADPE A-3 ODPA m-TB A-4 ODPA p-phenylenediamine A-5 BPDA m-TB A-6 ODPA BAPP A-7 BPADA mxD A-8 ODPA BPDA DADPE A-9 ODPA PMDA mxD A-10 ODPA BPDA mxD A-11 6FDA TFMB

[Table 2-2] Compound B Photoinitiator B-1 TR-PBG-3057 Compound C Nitrogen-containing heterocyclic compounds C-1 5-Amino-1H-tetrazolyl C-2 1H-Tetrazole C-3 3,5-Diamino-1,2,4-triazole Compound D Solvent △D △P △H D-1 γ-Butyrolactone 18.0 16.6 7.4 D-2 Dimethyl sulfoxide 18.4 16.4 10.2 Compound E Anti-leaching agent △D △P △H E-1 N,N'-Bismethoxymethylurea 17.8 14.9 11.9 E-2 Tetramethylenesulfone 18.2 11.0 9.1 E-3 2-Acetylthiophene 19.1 12.2 9.3 E-4 Maleic anhydride 19.5 13.3 11.9 E-5 Isopropylamine 18.8 13.4 11.2 E-6 2-Methylpyridine 18.3 12.3 10.5 E-7 Ethyl carbamate 16.8 10.1 13.0 E-8 caffeine 19.5 10.1 13.0 E-9 Ethylenediamine 17.7 11.0 9.8 E-10 Pyrrole 19.2 11.0 10.0 E-11 Methacrylamide 15.8 11.0 11.6 E-12 Vanillin 19.4 9.8 11.2 E-13 Dinitrophenol 19.5 12.8 14.3 E-14 Acetaminophen 17.8 10.5 13.9 E-15 Salicylic acid 19.0 10.5 12.0 E-16 Isocyanic acid 15.8 10.5 13.6 E-17 Ethyl methacrylate cyanate 15.2 10.3 9.0 E-18 Trifluoroacetic acid 15.6 9.7 11.4 E-19 Glyceryl diacetate 16.4 8.9 14.2 E-20 acetone 15.5 10.4 7.0 E-21 3-Methoxy-N,N-dimethylpropionamide 17.1 10.5 8.9 Compound F Crosslinking agent F-1 NK ESTER 4G

[Table 3] Polymer 1 Photopolymerization initiator Tetrazolyl compounds Solvent 1 Solvent 2 Anti-leaching agent Crosslinking agent Type quantity Type quantity Type quantity Type quantity Type quantity Type quantity Type quantity Embodiment 1 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 2 A-2 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 3 A-3 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 4 A-4 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 5 A-5 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 6 A-6 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 7 A-7 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 8 A-8 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 9 A-9 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 10 A-10 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 11 A-11 100 B-1 2 C-1 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 12 A-1 100 B-1 2 C-2 3 D-1 160 D-2 40 E-1 4 F-1 10 Embodiment 13 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-2 4 F-1 10 Embodiment 14 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-3 4 F-1 10 Embodiment 15 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-4 4 F-1 10 Embodiment 16 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-5 4 F-1 10 Embodiment 17 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-6 4 F-1 10 Embodiment 18 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-7 4 F-1 10 Embodiment 19 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-8 4 F-1 10 Embodiment 20 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-9 4 F-1 10 Embodiment 21 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-10 4 F-1 10 Embodiment 22 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-11 4 F-1 10 Embodiment 23 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-12 4 F-1 10 Embodiment 24 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-13 4 F-1 10 Embodiment 25 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-14 4 F-1 10 Embodiment 26 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-15 4 F-1 10 Embodiment 27 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-16 4 F-1 10 Embodiment 28 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-17 4 F-1 10 Embodiment 29 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-18 4 F-1 10 Embodiment 30 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-19 4 F-1 10 Comparison Example 1 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-20 4 F-1 10 Comparison Example 2 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 E-21 4 F-1 10 Comparison Example 3 A-1 100 B-1 2 C-3 3 D-1 160 D-2 40 E-1 4 F-1 10 Comparison Example 4 A-1 100 B-1 2 - - D-1 160 D-2 40 E-1 4 F-1 10 Comparison Example 5 A-1 100 B-1 2 C-1 3 D-1 160 D-2 40 - - F-1 10

[Table 4] Copper adhesion Copper migration Separation Embodiment 1 A A A Embodiment 2 A A A Embodiment 3 A A B Embodiment 4 A A A Embodiment 5 A A A Embodiment 6 A S S Embodiment 7 A S S Embodiment 8 A S S Embodiment 9 A S S Embodiment 10 A A A Embodiment 11 A A A Embodiment 12 A A A Embodiment 13 A A S Embodiment 14 A A S Embodiment 15 A S S Embodiment 16 A S S Embodiment 17 S S S Embodiment 18 A A S Embodiment 19 A A S Embodiment 20 A S S Embodiment 21 A S S Embodiment 22 A A A Embodiment 23 A A A Embodiment 24 A A A Embodiment 25 A A A Embodiment 26 A A A Embodiment 27 A A A Embodiment 28 A A A Embodiment 29 A A A Embodiment 30 A A A Comparison Example 1 B B C Comparison Example 2 B B C Comparison Example 3 A B C Comparison Example 4 C C A Comparison Example 5 C C C

Claims (20)

A negative photosensitive resin composition is characterized by comprising: (A) at least one resin selected from (A1) a polyimide precursor and (A2) a polyimide; (B) a photopolymerization initiator; (C) a nitrogen-containing heterocyclic compound; and (D) a solvent, wherein the polyimide precursor (A1) is of the following general formula (1):

{wherein, _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 independently a hydrogen atom, the following general formula (2):

(wherein, R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, 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) a monovalent organic group represented by the following general formula (25):

(wherein R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, 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) represented by a monovalent organic ammonium ion or a saturated aliphatic group having 1 to 4 carbon atoms; wherein R ₁ and R ₂ are not both hydrogen atoms}, the polyamic acid ester or polyamic acid salt represented by (A2) is the following general formula (24):

(wherein X ₂ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₂ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50), the photosensitive resin composition further contains the (E) precipitation inhibitor of the (C) nitrogen-containing heterocyclic compound, the (C) nitrogen-containing heterocyclic compound is a tetrazole compound, and the Hansen Solbility parameter (HSP) of the (E) precipitation inhibitor is in the following range: ΔD: 15.2 to 21.2 ΔP: 8.9 to 14.9 ΔH: 9.0 to 14.3. The negative photosensitive resin composition of claim 1, wherein the Hansen solubility parameter of the above-mentioned (E) anti-precipitation agent is in the following range: △D: 16.2~20.2 △P: 9.9~13.9△H: 9.3~13.3. The negative photosensitive resin composition of claim 1 or 2, wherein the Hansen solubility parameter of the above-mentioned (E) anti-precipitation agent is in the following range: △D: 16.7~19.7△P: 10.4~13.4△H: 9.8~12.8. The negative photosensitive resin composition of claim 1 or 2, wherein the Hansen solubility parameter of the above-mentioned (E) anti-precipitation agent is in the following range: △D: 17.2~19.2△P: 10.9~12.9△H: 10.3~12.3. A negative photosensitive resin composition as claimed in claim 1 or 2, wherein the tetrazole compound is 5-amino-1H-tetrazole. The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (1), _X1 is one or more organic groups selected from the following general formulas (3) to (6):

(wherein, R ₆ , R ₇ and R ₈ are independently an oxygen atom, a sulfur atom, or a divalent organic group; R ₉ and R ₁₀ are 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 negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (1), _Y1 is one or more organic groups selected from the following general formulas (7) to (10):

(In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are hydrogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different) [Chemical 10]

(In the formula, R ₁₅ to R ₂₂ are hydrogen atoms, halogen atoms, monovalent organic groups with 1 to 5 carbon atoms, or hydroxyl groups, and they may be different or the same.)

(In the formula, R ₂₃ is a divalent group, R ₂₄ to R ₃₁ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and they may be the same or different)

(In the formula, R ₃₂ and R ₃₃ are divalent groups, R ₃₄ and R ₃₅ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different). The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (1), _Y1 is one or more organic groups selected from the following general formulas (7), (9) and (10):

(In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are hydrogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different)

(In the formula, R ₂₃ is a divalent group, R ₂₄ to R ₃₁ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, and they may be the same or different)

The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (1), _X1 is one or more organic groups selected from the following general formulas (11) to (14):

[Chemistry 18]

The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (1), _X1 is an organic group selected from two or more of the following general formulas (11) to (14):

The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (1), _X1 is an organic group comprising the following general formulas (12) and (13):

The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (1), _X1 is an organic group comprising the following general formulas (11) and (13):

The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (1), _X1 is an organic group comprising the following general formula (14):

The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (1), _Y1 is one or more organic groups selected from the following general formulas (21) to (23):

The negative photosensitive resin composition of claim 1 or 2, wherein the anti-precipitation agent (E) is selected from acetaniline, acetic anhydride, acrylamide, ethylene dinitrile, N,N-diethylformamide, diethylene glycol monoethyl ether, N,N-dimethylacetamide, dimethylethanolamine, ethyl carbamate, ethyl cyanoacrylate, ethyl isothiocyanate, ethyl methanesulfonate, ethyleneimide, 2-hydroxyethyl acrylate, isocyanic acid, isocyanic acid

Azoles, methacrylamide, 3-methylisothiazolyl

Azoles, propionamide, 2-pyrrolidone, pyrrole, succinaldehyde, tetramethylene sulfone, thiocyanate, triethyl phosphate, trifluoroacetic acid, trimethyl phosphate, salicylic acid, 1,3-bismethoxymethylurea, 2-acetylthiophene, benzoin, 2-methylpyridine

, 4-nitrophenol, 3,4-dinitrophenol, N-ethylformamide, maleic anhydride, pyrazole, ethyl cyanoacetate, benzamide, n-butylamide, vanillin, saccharin, cycloheximide, caffeine, salicylic acid, spermidine, acetaminophen, diacetin and pyrimidine. The negative photosensitive resin composition of claim 1 or 2, wherein the anti-precipitation agent (E) comprises a urea skeleton or an amide skeleton. A negative photosensitive resin composition as claimed in claim 1 or 2, wherein the anti-precipitation agent (E) contains a sulfur atom. A method for producing a hardened relief pattern, comprising the following steps: (1) applying a negative photosensitive resin composition as described in any one of claims 1 to 17 on a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heating the relief pattern to form a hardened relief pattern. As in the method of claim 18, wherein the substrate is formed of copper or a copper alloy. A semiconductor device comprising a hardened relief pattern obtained by the manufacturing method of claim 18 or 19.