TW202342592A - Polyimide precursor, negative photosensitive resin composition, and method for producing cured relief pattern using same - Google Patents

Abstract

Provided are a polyimide precursor, a negative photosensitive resin composition, and a method for producing a cured relief pattern using the same. A negative photosensitive resin composition containing (A) a polyimide precursor containing a structural unit represented by general formula (1) and (B) a solvent. In formula (1), X1 represents a tetravalent organic group having 4-40 carbon atoms and optionally containing a heteroatom; y1 represents a divalent organic group having 6-40 carbon atoms and optionally containing a heteroatom; r1 and R2 are each independently one selected from the group consisting of a hydrogen atom, a monovalent organic group having 1-40 carbon atoms and optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure. At least one of R1 and R2 is a monovalent organic group having a heterocyclic structure, or at least one of OR1 and OR2 is a monovalent organic group in which the proportion of the number of heteroatoms among constituent atoms other than hydrogen atoms is 42% or more.

Description

Polyimide precursor, negative photosensitive resin composition, and method for manufacturing hardened relief pattern using same

The present invention relates to a polyimide precursor, a negative photosensitive resin composition, and a method for manufacturing a hardened relief pattern using the same.

Previously, polyimide resin, which has excellent heat resistance, electrical properties, and mechanical properties, has been used in insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, etc. of semiconductor devices. Among the polyimide resins, those provided in the form of a photosensitive polyimide precursor composition can be easily transformed by coating, exposure, development, and thermal imidization treatment utilizing curing of the composition. Forms a heat-resistant embossed pattern film. This photosensitive polyimide precursor composition has the characteristic of significantly shortening the steps compared with previous non-photosensitive polyimide materials.

In addition, semiconductor devices (hereinafter also referred to as "devices") are mounted on printed circuit boards in various ways depending on the purpose. Previous components were usually manufactured by wire bonding using thin wires from the component's external terminals (soldering pads) to the lead frame. However, as the speed of components progresses and the operating frequency reaches gigahertz (GHz), the difference in wiring length of each terminal in the installation will affect the operation of the component. Therefore, in the installation of high-end components, the length of the installation wiring must be accurately controlled, and it is difficult to meet this requirement in wire bonding.

Therefore, flip-chip mounting has been proposed, which involves forming a rewiring layer on the surface of a semiconductor wafer, forming bumps (electrodes) thereon, and then flipping the wafer (flip-chip) to directly mount it on a printed circuit board. In this flip-chip mounting, the wiring distance can be accurately controlled, so it is used in high-end components that process high-speed signals, or in mobile phones due to its small mounting size, and the demand is rapidly expanding. Furthermore, a semiconductor wafer mounting technology called fan-out wafer-level packaging (FOWLP) has recently been proposed. This technology dices the wafers that have been completed in the pre-process to produce single wafers, and rearranges the single wafers on the support. The wafer is sealed with molding resin, and the support is peeled off to form a rewiring layer. Fan-out wafer-level packaging has the following advantages: it can not only make the package highly thin, but also achieve high-speed transmission or low cost. [Prior technical literature] [Patent Document]

[Patent Document 1] International Publication No. 2021/215374 [Patent Document 2] International Publication No. 2020/189358 [Patent Document 3] International Publication No. 2017/038598 [Patent Document 4] International Publication No. 2020/026840

[Problem to be solved by the invention]

When using negative photosensitive polyimide, the following problems can be cited: the photosensitive side chains separated from the polyimide precursor during the curing process remain in the polyimide film, thereby preventing the copper substrate from being bonded to the polyimide film. The interaction of polyimide resin reduces the adhesion. On the other hand, if the separated photosensitive side chains volatilize from the film, it will significantly promote the hardening shrinkage during the curing process. Therefore, there is a need for a technology that does not reduce the adhesion when the photosensitive side chains remain in the polyimide film. .

It is known that a rust inhibitor having a heterocyclic structure is effective in bonding a polyimide film and a copper substrate. For example, in Patent Document 1, an additive having a heterocyclic structure is used to improve the adhesiveness with the substrate. However, the technology of Patent Document 1 is not intended to achieve both adhesion to the substrate and suppression of hardening shrinkage during the curing process.

In Patent Document 2, an attempt is made to improve the adhesion to the substrate by introducing a heterocyclic structure into the terminal structure or side chain structure of the polymer. However, the introduction of the heterocyclic structure of the terminal structure is not intended to take into account the adhesion to the substrate and the suppression of hardening shrinkage during the curing process. Furthermore, the introduction of the heterocyclic structure of the side chain structure is through the introduction of amide bonds. Hinder the imidization reaction in the curing process.

Therefore, the object of the present invention is to provide a negative photosensitive resin composition that fully promotes imidization during the curing process, has good adhesion to copper wiring, and can suppress hardening shrinkage during the curing process; and uses the negative photosensitive resin composition. A method for producing a hardened relief pattern using a photosensitive resin composition. [Technical means to solve problems]

Examples of embodiments of the present invention are described below. [1] A negative photosensitive resin composition containing: (A) a polyimide precursor containing a structural unit represented by the following general formula (1), and (B) a solvent. [Chemical 1] _{ In _formula ( ₁ ) _, They are each independently selected from the group consisting of hydrogen atoms, monovalent organic groups with 1 to 40 carbon atoms that may contain heteroatoms, and monovalent organic groups with heterocyclic structures, wherein R ₁ and R ₂ At least one of them is a monovalent organic group having a heterocyclic structure} [2] A negative photosensitive resin composition containing: (A) Polymer containing a structural unit represented by the following general formula (1) Amine precursor, and (B) solvent. [Chemicalization 2] _{ In _formula ( ₁ ) _, Each is independently one of the group consisting of a hydrogen atom, a monovalent organic group with a carbon number of 1 to 40 that may contain heteroatoms, and a monovalent organic group with a heterocyclic structure, wherein, in OR ₁ and OR ₂ At least one of them is a monovalent organic group in which the ratio of the number of heteroatoms among the constituent atoms other than hydrogen atoms is 42% or more} [3] For example, the negative photosensitive resin composition of item 1 or 2, which further contains ( C) Photopolymerization initiator. [4] The negative photosensitive resin composition according to any one of items 1 to 3, wherein at least one of R ₁ and R ₂ is a monovalent organic group containing a heterocyclic structure containing a nitrogen atom. [5] The negative photosensitive resin composition according to any one of items 1 to 4, wherein at least one of R ₁ and R ₂ is a monovalent organic group containing a 5-membered ring heterocyclic structure containing a nitrogen atom. [6] The negative photosensitive resin composition according to any one of items 1 to 5, wherein among all the structural units of the above-mentioned (A) polyimide precursor, at least one of R ₁ and R ₂ has ( Meth)acrylate group. [7] The negative photosensitive resin composition according to any one of items 1 to 6, wherein among all the structural units of the above-mentioned (A) polyimide precursor, R ₁ and R ₂ have a total of 2 or more ( Meth)acrylate group. [8] The negative photosensitive resin composition according to any one of items 1 to 7, wherein at least one of R ₁ and R ₂ is a group represented by the following general formula (3). [Chemical 3] {In formula (3), Ar is the above-mentioned heterocyclic structure, the dotted line is a single bond bonded to the oxygen atom of formula (1), R ₃ , R ₄ and R ₅ are independently hydrogen atoms or carbon atoms with 1 to 3 carbon atoms. Monovalent organic group, R ₆ and R ₇ are each independently a divalent organic group with a carbon number of 1 to 10 that may contain heteroatoms} [9] The negative photosensitive resin composition of any one of items 1 to 8, At least one of R ₁ and R ₂ is a monovalent organic group having a heterocyclic structure, and the heterocyclic structure is triazole or tetrazole. [10] The negative photosensitive resin composition according to any one of items 1 to 9, wherein more than 10 mol% of the total R ₁ and R ₂ of the polyimide precursor (A) have the above heterocyclic structure and/or a structure with a higher ratio of the number of heteroatoms mentioned above. [11] The negative photosensitive resin composition according to any one of items 1 to 10, which further contains (D) a monomer having a polymerizable functional group. [12] The negative photosensitive resin composition according to any one of items 1 to 11, wherein the monomer (D) having a polymerizable functional group has two or more polymerizable functional groups. [13] The negative photosensitive resin composition according to any one of items 1 to 12, wherein the monomer (D) having a polymerizable functional group has three or more polymerizable functional groups. [14] The negative photosensitive resin composition according to any one of items 1 to 13, wherein X ₁ contains at least one selected from the group consisting of the following general formulas (8) to (11). [Chemical 4] [Chemistry 5] [Chemical 6] [Chemical 7] [15] The negative photosensitive resin composition according to any one of items 1 to 14, wherein the above Y ₁ contains at least one selected from the group consisting of the following general formulas (12) to (15). [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 11] {In the formula, R ₁₁ is each independently a monovalent organic group with a carbon number of 1 to 10 that may contain a halogen atom, and a is an integer from 0 to 4 respectively} [16] Such as the negative form of any one of items 1 to 15 A photosensitive resin composition further containing 0.1 to 40 parts by mass of the thermal base generating agent (E) based on 100 parts by mass of the polyimide precursor (A). [17] A method for manufacturing a hardened relief pattern, which includes the following steps: (1) Coating the negative photosensitive resin composition according to any one of items 1 to 16 on the substrate to form a The steps of forming a photosensitive resin layer; (2) The step of exposing the above-mentioned photosensitive resin layer; (3) The step of developing the above-mentioned exposed photosensitive resin layer to form a relief pattern; and (4) The step of forming the above-mentioned relief The pattern is heated to form a hardened relief pattern. [18] A polyimide precursor containing a structural unit represented by the following general formula (1). [Chemical 12] _{ In _formula ( ₁ ) _, They are each independently selected from the group consisting of hydrogen atoms, monovalent organic groups with 1 to 40 carbon atoms that may contain heteroatoms, and monovalent organic groups with heterocyclic structures, wherein R ₁ and R ₂ At least one of them is a monovalent organic group having a heterocyclic structure} [19] A polyimide precursor containing a structural unit represented by the following general formula (1). [Chemical 13] _{ In _formula ( ₁ ) _, Each is independently one of the group consisting of a hydrogen atom, a monovalent organic group with a carbon number of 1 to 40 that may contain heteroatoms, and a monovalent organic group with a heterocyclic structure, wherein, in OR ₁ and OR ₂ At least one of them is an organic radical in which the ratio of the number of heteroatoms among the constituent atoms other than hydrogen atoms is 42% or more} [Effects of the Invention]

According to the present invention, a negative photosensitive resin composition is provided that fully promotes imidization during the curing process, has good adhesion to copper wiring, and can suppress hardening shrinkage during the curing process; and uses the negative photosensitive resin composition Method for producing hardened relief patterns from resin compositions.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the spirit. Throughout this specification, structures represented by the same symbol in the general formula may be the same or different from each other when there are plural structures in the molecule.

<Negative photosensitive resin composition> The negative photosensitive resin composition of the present invention contains (A) a polyimide precursor containing a structural unit represented by the following general formula (1), and (B) a solvent . [Chemical 14]

In formula (1), X ₁ is a 4-valent organic group with 4 to 40 carbon atoms that may contain heteroatoms, Y ₁ is a 2-valent organic group with 6 to 40 carbon atoms that may contain heteroatoms, and R ₁ and R ₂ are respectively It is independently selected from the group consisting of hydrogen atoms, monovalent organic groups with 1 to 40 carbon atoms that may contain heteroatoms, and monovalent organic groups with heterocyclic structures. Among them, at least one of R ₁ and R ₂ is a monovalent organic group having a heterocyclic structure, or at least one of OR ₁ and OR ₂ is the ratio of the number of heteroatoms among the constituent atoms other than hydrogen atoms ( Hereinafter, also referred to as "heteroatom ratio") is 42% or more of monovalent organic groups. At least one of R ₁ and R ₂ may have a heterocyclic structure and the atomic ratio is 42% or more. Furthermore, the calculation of the heteroatom ratio includes the oxygen atom in the ester bond where R ₁ and R ₂ are directly bonded (oxygen atoms derived from the side chain compound). Therefore, when referring to heteroatom ratios, they are expressed as "OR ₁ " and "OR ₂ ".

The negative photosensitive resin composition of the present invention uses an organic group having a heterocyclic structure and/or a structure with a high heteroatom ratio (hereinafter, also referred to as a "high heteroatom structure") in the side chain structure of the polymer. , the side chains separated from the polyimide precursor during the curing process remain in the polyimide film to inhibit the hardening shrinkage during the curing process, and can inhibit the decrease in copper adhesion caused by the remaining side chains, but it does not Not limited to theory. In addition, the organic groups with heterocyclic structures and/or high heteroatom structures in the side chains are bonded not through amide bonds but through ester bonds, thereby suppressing the hindrance of the amide imidization reaction during the curing process. As a result, it is considered that the imidization is sufficiently promoted during the curing process, the adhesion to copper wiring is good, and the hardening shrinkage during the curing process can be suppressed.

(A) Polyimide precursor (A) Polyimide precursor system The resin component contained in the negative photosensitive resin composition is converted into polyimide by performing heat cyclization treatment. The polyimide precursor system has a polyimide precursor having a structure represented by the above general formula (1).

_In the general formula ( ₁ ), the tetravalent organic group represented by An aromatic group or an alicyclic aliphatic group in which _{the 2-} group and -CONH- group are ortho-positioned to each other. Examples of the _tetravalent organic group _represented by and the base of the structure represented by each formula of (X ₁ -2), but is not limited to these. [Chemical 15] [Chemical 16]

In the formulas (X ₁ -1) and (X ₁ -2), R6 is selected from the group consisting of a hydrogen atom, a fluorine atom, a C ₁ to C ₁₀ hydrocarbon group, and a C ₁ to C ₁₀ fluorine-containing hydrocarbon group. For a base of 1, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4. The structure of X ₁ can be one type or a combination of two or more types. The X 1 group having a structure represented by each of the above-mentioned formulas (X ₁ -1) and (X _{1 -2} ) is particularly preferred in terms of both heat resistance and photosensitive characteristics, and further preferably the above-mentioned formula (X ₁ -1) Structure represented by various formulas.

As the X ₁ group, among the structures represented by the above formula (X ₁ -1), particularly the structures represented by each of the following formulas, from the viewpoint of acyl imidization rate, degassing property, copper adhesion and chemical resistance Better. [Chemical 17] In the above formula, R6 and m have the same meanings respectively as R6 and m in the above formula (X ₁ -1).

X ₁ is more preferably selected from the group consisting of the following general formulas (8) to (11) from the viewpoint of imidization rate, degassing property, copper adhesion and chemical resistance. At least one. [Chemical 18] [Chemical 19] [Chemistry 20] [Chemistry 21]

In the above-mentioned general formula (1), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms in terms of both heat resistance and photosensitive properties. Examples thereof include: the following formula The structures represented by the formulas (Y ₁ -1) and (Y ₁ -2) are not limited to these. [Chemistry 22] [Chemistry 23]

In formulas (Y ₁ -1) and (Y ₁ -2), R6 is selected from the group consisting of a hydrogen atom, a fluorine atom, a C ₁ to C ₁₀ hydrocarbon group, and a C ₁ to C ₁₀ fluorine-containing hydrocarbon group. A base of 1 valence, and n is an integer selected from 0 to 4. In addition, the structure of Y ₁ may be one type or a combination of two or more types. The Y 1 group having a structure represented by each of the above-mentioned formulas (Y ₁ -1) and (Y _{1 -2} ) is particularly preferred in terms of both heat resistance and photosensitive characteristics, and more preferably the above-mentioned formula (Y ₁ -1) Structure represented by various formulas.

As the Y ₁ group, among the structures represented by the above-mentioned formula (Y ₁ -1), particularly the structures represented by the following formulas are related to the acyl imidization rate, degassing property, copper adhesion, and chemical resistance. Better from a perspective. [Chemistry 24] In the above formula, R6 and n have the same meanings respectively as R6 and n in the above formula (Y ₁ -1).

Y ₁ is more preferably selected from the group consisting of the following general formulas (12) to (15) from the viewpoint of imidization rate, degassing property, copper adhesion and chemical resistance. At least one. [Chemical 25] [Chemical 26] [Chemical 27] [Chemical 28]

In the formulas (12) to (15), R ₁₁ can each independently be a monovalent organic group having 1 to 10 carbon atoms that may contain a halogen atom, such as a monovalent organic group having 1 to 5 carbon atoms or 1 to 3 carbon atoms. Hydrocarbyl or alkyl. a is an integer from 0 to 4, preferably 0 to 2, more preferably 0 or 1, and may also be 0.

Preferably, at least one of R ₁ and R ₂ in the above general formula (1) contains a polymerizable group selected from the group consisting of an acid polymerizable group, an alkali polymerizable group, and a radical polymerizable group. base. Here, the acid polymerizable group, the alkali polymerizable group, and the radical polymerizable group refer to groups that can be polymerized by the action of an acid, a base, or a radical, respectively.

From the viewpoint of adhesiveness, (A) at least one of R ₁ and R ₂ in the polyimide precursor is a monovalent organic group having a heterocyclic structure and/or a high heteroatom structure. From the viewpoint of adhesiveness, the heteroatom ratio of at least one of R ₁ and R ₂ is preferably 42% or more, more preferably 43% or more, and still more preferably 44% or more. The upper limit of the heteroatom ratio that can be combined with these lower limits is not particularly limited as long as it does not reach 100%, and may be, for example, 60% or less, 55% or less, or 50% or less.

R ₁ and R ₂ are preferably monovalent organic groups having a heterocyclic structure and/or a high heteroatom structure and having a carbon number of 1 to 40. From the viewpoint of resolution, 1 to 40 carbon atoms are preferred. The valent organic group is preferably a group represented by the following general formula (2). [Chemical 29]

In formula (2), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer from 1 to 10, preferably an integer from 1 to 5 or An integer from 1 to 3. For example, the group represented by general formula (2) is preferably a group represented by the following formula. [Chemical 30] In the formula, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. More specific examples of the monovalent organic group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and the like. R ₃ is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably a hydrogen atom.

At least one of R ₁ and R ₂ is preferably a monovalent organic group having a heterocyclic structure and/or a high heteroatom structure. There is no particular limitation. From the perspective of suppressing hardening shrinkage during the curing process, it is preferred. In order to further have a (meth)acrylyl group. For example, it is further preferred that at least one of R ₁ and R ₂ be a group represented by the following general formula (3). [Chemical 31]

In formula (3), Ar is a heterocyclic structure, the dotted line is a single bond bonded to the oxygen atom of formula (1), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a valence of 1 to 3 carbon atoms. Organic group, R ₆ and R ₇ are each independently a divalent organic group having a carbon number of 0 to 10 that may contain a hetero atom, preferably a divalent organic group having a carbon number of 1 to 10, or a divalent organic group having a carbon number of 1 to 10 that may contain a hetero atom. A divalent organic group of 5, or a divalent organic group having 1 to 3 carbon atoms.

More specific examples of the monovalent organic group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and the like. R ₃ is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably a hydrogen atom. More specifically, examples of the divalent organic group having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptyl, and octylene. Base, nonyl, decyl, and its structural isomers, etc. R ₆ and R ₇ are each independent, preferably a group selected from the group consisting of a divalent organic group with 1 to 3 carbon atoms containing a thioether bond, a methylene group, an ethylene group and a propylene group, more preferably It is a divalent organic group with 1 to 3 carbon atoms containing a thioether bond, or a methylene group.

Preferably, in at least one structural unit of (A) polyimide precursor, at least one of R ₁ and R ₂ has a (meth)acrylate group, and more preferably, in (A) polyimide Among all the structural units of the precursor, at least one of R ₁ and R ₂ has a (meth)acrylate group. Preferably, in at least one structural unit of (A) polyimide precursor, both R ₁ and R ₂ have (meth)acrylate groups, and more preferably, in (A) polyimide precursor Among all the structural units, R ₁ and R ₂ have a total of 2 or more (meth)acrylate groups. That is, it means that R ₁ and R ₂ have a total of two or more (meth)acrylate groups in the following manner: R ₁ has two or more (meth)acrylate groups, and R ₂ does not have to have (meth)acrylate groups. group) acrylate group, or R ₁ does not have a (meth)acrylate group, R ₂ may have 2 or more (meth)acrylate groups, or R ₁ may have 1 or more (meth)acrylate groups , R ₂ also has one or more (meth)acrylate groups. The reason why hardening shrinkage during the curing process is suppressed by having at least one of R ₁ and R ₂ , preferably a side chain having a heterocyclic structure and/or a high heteroatom structure, a (meth)acrylyl group Without being limited to a theory, the inventors believe that the reason is as follows: (thermal polymerization of meth)acrylyl groups inhibits the volatilization of photosensitive side chains separated from the polyimide precursor during the curing process, thereby inhibiting curing shrinkage.

From the viewpoint of adhesiveness, at least one of R ₁ and R ₂ is preferably a monovalent organic group having a heterocyclic structure and/or a high heteroatom structure, preferably a heterocyclic structure containing a nitrogen atom. The monovalent organic group is more preferably a monovalent organic group containing a 5-membered ring heterocyclic structure containing a nitrogen atom. From the viewpoint of adhesion, the heterocyclic structure is preferably a triazole or tetrazole structure.

From the viewpoint of copper adhesion, based on the total molar number of _R1 and _R2 , the ratio of monovalent organic groups having a heterocyclic structure and/or a high heteroatom structure is preferably 10 mol% or more. By introducing more than 10 mol%, copper adhesion is further improved.

(A) Method for Preparing Polyimide Precursor As a method for preparing (A) Polyimide Precursor, for example, the following method can be cited: making the tetracarboxylic dianhydride containing the above-mentioned 4-valent organic group X ₁ and Partially esterified tetracarboxylic acid (hereinafter, also referred to as "partially esterified tetracarboxylic acid") is prepared by reacting an alcohol with a polymerizable group selected from the group consisting of an acid polymerizable group, an alkali polymerizable group, and a radical polymerizable group, and any other alcohol. called acid/ester body). Then, (A) polyimide precursor is obtained by performing amide polycondensation on the partially esterified tetracarboxylic acid (acid/ester body) and the diamine containing the above-mentioned divalent organic group _Y1 . As a method of introducing a heterocyclic structure and/or a high heteroatom structure into at least one of R ₁ and R ₂ , for example, by reacting the tetracarboxylic dianhydride containing the above 4-valent organic group X ₁ with the above alcohol , also reacts with an alcohol having a heterocyclic structure and/or a high heteroatom structure to prepare a tetracarboxylic acid (acid/ester body) having a heterocyclic structure and/or a high heteroatom structure. Then, the obtained tetracarboxylic acid (acid/ester body) and the diamine containing the above-mentioned divalent organic group Y ₁ are subjected to amide polycondensation to obtain the (A) polyimide precursor of the present invention.

(Preparation of Acid/Ester Body) The tetracarboxylic dianhydride containing a tetravalent organic group X ₁ that is preferably used to prepare the polyimide precursor (A) is preferably a compound represented by the following formula. [Chemical 32] In the above formula, X ₁ is defined in the above general formula (1). This X ₁ is more preferably a structure represented by the above-mentioned general formula (X ₁ -1) and (X ₁ -2), and further preferably is a structure represented by the above-mentioned general formula (X ₁ -1).

Particularly preferred examples of tetracarboxylic dianhydride include: pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (alias: oxydiphthalic dianhydride) , referred to as "ODPA"), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (referred to as "BPDA" 》), diphenylcarboxylic acid-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. Particularly preferred examples include: pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited to these. Of course, these can be used alone, or two or more of them can be mixed and used.

As an alcohol having a polymerizable group selected from the group consisting of an acid polymerizable group, an alkali polymerizable group, and a radical polymerizable group, which is preferably used for preparing the polyimide precursor (A), for example, Examples: 2-hydroxyethyl methacrylate, 2-propenyloxyethanol, 1-acryloxy-3-propanol, 2-acrylamideethanol, hydroxymethylvinylketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3 acrylate -Butoxypropyl ester, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethanol, 1-methyl Acryloxy-3-propanol, 2-methacrylamide ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxymethacrylate Hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, glyceryl diacrylate, 1-(acryloxy)-3-(methacryloxy) base)-2-propanol, glyceryl dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, etc.

Examples of alcohols having a heterocyclic structure that are preferably used to prepare (A) the polyimide precursor include: alcohols having a hydroxyl group and a heterocyclic ring. The alcohol having a hydroxyl group and a heterocyclic ring is not limited, and examples thereof include N-(2-hydroxyethyl)phthalimide, 3-furanmethanol, and 2,4-dimethyl-6- Hydroxypyrimidine, 2-Hydroxymethyl-1-methylimidazole, 7-ethyl-3-indoleethanol, mesozolin, (5-phenylisothazol-3-yl)methanol, 3-hydroxyisobutanol Azole-5-carboxylic acid methyl ester, Carazolol, etc. Among these, the alcohol having a heterocyclic structure is preferably an alcohol having a heterocyclic ring and a (meth)acrylyl group. The compound having a heterocyclic ring and a (meth)acrylyl group can be synthesized from, for example, an epoxy compound and a heterocyclic compound having a nucleophilic functional group represented by a thioether group, a carboxyl group, a hydroxyl group, and the like. The epoxy compound is not limited, and examples thereof include glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether (available from Mitsubishi Chemical Co., Ltd., for example), and the like. The heterocyclic compound having a nucleophilic functional group is not limited, and examples thereof include 3-mercaptotriazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, and 5-mercaptotriazole. 1-methyltetrazole, 5-mercapto-1-phenyltetrazole, 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole, 1-(4-carboxyphenyl)-5-mercapto -1H-tetrazole, 1H-tetrazole-5-acetic acid, 5-mercapto-1-methyltetrazole, 1-(4-ethoxyphenyl)-5-mercapto-1H-tetrazole, 4-( 1H-tetrazol-5-yl)benzoic acid, 5-mercapto-1-(4-methoxyphenyl)-1H-tetrazole, 1-(3-acetamidephenyl)-5-mercaptotetrazole , 5-benzotriazolecarboxylic acid, N-phthalylglycine, 1H-benzotriazole-1-methanol, 3-mercapto-1,2,4-triazole, 1-methyl Pyrazole-5-carboxylic acid, 1-methylpyrazole-3-carboxylic acid, 1,3-dimethyl-1H-pyrazole-5-carboxylic acid, 1-methylpyrazole-4-carboxylic acid, 1-methyl-3-(trifluoromethyl)pyrazole-4-carboxylic acid, pyrazole-3-carboxylic acid, pyrazole-4-carboxylic acid, 3-carboxyindazole, etc.

The above-mentioned tetracarboxylic dianhydride and alcohol are stirred in a solvent, dissolved and mixed, whereby the acid anhydride group of the tetracarboxylic dianhydride undergoes an esterification reaction, thereby obtaining the desired acid/ester body. The reaction is preferably carried out in the presence of an appropriate alkaline catalyst such as pyridine. The reaction conditions are not limited, but for example, it is preferable to react at a temperature of 20°C to 50°C for 4 hours to 10 hours.

(Preparation of polyimide precursor) In the above acid/ester body (typically, a solution dissolved in the following solvent), under cooling in an ice bath, add and mix an appropriate dehydration condensation agent, such as bicyclic Hexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole , N,N'-dibutylene imide carbonate, etc., can make the acid/ester body into a polyanhydride. In a solution containing the polyanhydride, the diamine containing the divalent organic group Y 1 is added dropwise so that the diamine containing the divalent organic group Y ₁ is additionally dissolved or dispersed in the solvent, and amide condensation polymerization is performed, whereby the target polyimide precursor can be obtained. In addition, depending on the reactivity of the raw material, 1-hydroxybenzotriazole, etc. can be used. As an alternative, the acid part of the above acid/ester body is chlorinated using thionite chloride, etc., and then reacted with a diamine in the presence of a base such as pyridine, thereby obtaining the target polyimide precursor. .

As the diamine containing the divalent organic group Y ₁ , a compound represented by the formula: H ₂ NY ₁ -NH ₂ {wherein, Y ₁ is defined in the above general formula (1)} is preferred. This Y ₁ is more preferably a structure represented by each of the above general formulas (Y ₁ -1) and (Y ₁ -2).

More preferred examples of the diamine include: p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (alias: 4,4'-oxydiphenylamine, abbreviated as "ODA"), 3,4'-Diaminodiphenyl ether, 3,3'-Diaminodiphenyl ether, 4,4'-Diaminodiphenyl sulfide, 3,4'-Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide Diphenyl, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3, 4'-Diaminobenzophenone, 3,3'-Diaminobenzophenone, 4,4'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis (3-Aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]terine, bis[4-(3-aminophenoxy)phenyl]terine, 4,4 -Bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis [4-(3-Aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10 -Bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[ 4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-amino) Propyldimethylsilyl)benzene, o-dimethylsilyl)benzene, 9,9-bis(4-aminophenyl)benzene, etc., and those in which part of the hydrogen atoms on the benzene ring is substituted with a methyl group, 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, etc., but are not limited thereto. These may be used alone, or two or more of them may be mixed and used.

After the amide polycondensation reaction is completed, the water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are filtered and separated if necessary, and then poor solvents such as water, aliphatic lower alcohols, or their mixtures are added to the obtained polymer components. The polymer components are precipitated, and then the re-dissolution and reprecipitation operations are repeated to refine the polymer and then vacuum-dried to isolate the target polyimide precursor. In order to improve the degree of purification, the polymer solution can be passed through a column in which an anion exchange resin or a cation exchange resin or both are swollen and filled with an appropriate organic solvent, thereby removing ionic impurities.

The molecular weight of the polyimide precursor (A) is preferably 8,000 to 150,000, more preferably 9,000 to 50,000 when measured as a polystyrene-reduced weight average molecular weight by gel permeation chromatography. . When the weight average molecular weight is above 8,000, the mechanical properties are good. When the weight average molecular weight is below 150,000, the dispersibility to the developer is good and the resolution of the relief pattern is good. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight average molecular weight was obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select the organic solvent-based standard sample "STANDARD SM-105" manufactured by Showa Denko Co., Ltd.

As (A) the polyimide precursor, a non-photosensitive polyimide precursor prepared using only an alcohol having no polymerizable group can be mixed with a photosensitive polyimide precursor. In this case, from the viewpoint of resolution, the compounding amount of the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

(B)Solvent Examples of the solvent include amide, terine, urea and its derivatives, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. Specifically, for example, N-methyl-2 can be used -Pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyltrisoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofuranmethanol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, hydroxyline, dichloromethane, 1,2-dichloro Ethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, 1,3,5-trimethylbenzene, etc. Among them, from the viewpoint of the solubility of the resin and the stability of the resin composition, it is preferably selected from the group consisting of N-methyl-2-pyrrolidone, dimethylsyanoxide, tetramethylurea, butyl acetate, One or more of the group consisting of ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofuran methanol .

Among such solvents, those that completely dissolve (A) the polyimide precursor are particularly preferred, and suitable examples include N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, γ-butyrolactone, etc. The solvent is further preferably a solvent other than an amide solvent. Due to its strong interaction, amide solvents will hinder the interaction between the substrate and the polymer, thereby reducing the adhesion to the substrate. Therefore, among the above-mentioned solvents, at least one solvent selected from the group consisting of dimethylstyrene, tetramethylurea, and γ-butyrolactone is particularly preferred.

The content of the solvent in the negative photosensitive resin composition is preferably 100 parts by mass or more and 1,000 parts by mass or less, 120 parts by mass or more and 700 parts by mass or less, based on 100 parts by mass of the polyimide precursor (A). Or more than 125 parts by mass and less than 500 parts by mass.

(C) Photopolymerization initiator The negative photosensitive resin composition of the present invention may further contain (C) a photopolymerization initiator. As the photopolymerization initiator, a photoradical polymerization initiator or a photoacid generator is preferred.

Examples of the photoradical polymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, and dibenzylketone. , benzophenone compounds such as fentanone, acetophenone compounds such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone; 9- oxygen sulfur𠮿 , 2-Methyl-9-oxosulfide𠮿 , 2-isopropyl-9-oxosulfide𠮿 , diethyl-9-oxosulfide𠮿 Etc. 9-oxysulfur𠮿 Compounds; benzil compounds such as benzil, benzil dimethyl ketal, benzo-β-methoxyethyl acetal; benzoin compounds such as benzoin and benzoin methyl ether; 1-phenyl-1, 2-Butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1, 2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenyl Glycerin-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxyglycerin-2-(O-benzoyl)oxime and other oxime compounds; N-phenylglycan N-arylglycine compounds such as amines; peroxides such as benzyl perchloride, aromatic biimidazole compounds, titanocene compounds, etc.

(C) The photopolymerization initiator is not limited to the above examples. Among the above-mentioned photopolymerization initiators, a photoradical polymerization initiator is more preferred, and particularly in terms of sensitivity, an oxime compound is more preferred.

When the negative photosensitive resin composition contains (C) photopolymerization initiator, the compounding amount is preferably 0.1 or more parts by mass, 20 parts by mass or more relative to 100 parts by mass of (A) polyimide precursor. 1 part by mass or more and 8 parts by mass or less. If the amount of (C) photopolymerization initiator is 0.1 parts by mass or more, the sensitivity or pattern formability will be good, and if it is 20 parts by mass or less, a cured photosensitive resin layer of the negative photosensitive resin composition will be present. The tendency of things to become good.

(D) Photopolymerizable monomer In order to improve the resolution of the relief pattern, the negative photosensitive resin composition may optionally contain a monomer (also referred to as "photopolymerizable") with a photopolymerizable unsaturated bond (also referred to as "polymerizable functional group"). "Single"). As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferred, and is not particularly limited to the following. Examples thereof include: monoacrylate of ethylene glycol. , diacrylate, monomethacrylate, and dimethacrylate; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of polyethylene glycol; monoacrylate of propylene glycol, Diacrylate, monomethacrylate, and dimethacrylate; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of polypropylene glycol; monoacrylate, diacrylate of glycerin , triacrylate, monomethacrylate, dimethacrylate, and trimethacrylate; cyclohexane diacrylate and dimethacrylate; 1,4-butanediol diacrylate and Dimethacrylate; diacrylate and dimethacrylate of 1,6-hexanediol; diacrylate and dimethacrylate of neopentyl glycol; monoacrylate and diacrylate of bisphenol A , monomethacrylate, and dimethacrylate; benzene trimethacrylate; isopropyl acrylate and isopropyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives ; Trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; Diacrylate, triacrylate, tetraacrylate, dimethacrylate, trimethacrylate, and tetramethylacrylate of pentaerythritol acrylates; and compounds such as ethylene oxide adducts or propylene oxide adducts of these compounds.

In terms of small curing shrinkage during curing, the (D) photopolymerizable monomer preferably has two or more polymerizable functional groups, and more preferably has three or more polymerizable functional groups.

When the negative photosensitive resin composition contains the above-mentioned photopolymerizable unsaturated monomer for improving the resolution of the relief pattern, the compounding amount of the photopolymerizable unsaturated monomer is relative to (A) the polyester. 100 parts by mass of the imine precursor, preferably not less than 1 part by mass and not more than 50 parts by mass.

(E) Thermal base generator The negative photosensitive resin composition may contain (E) a thermal base generator. The so-called base generator refers to a compound that generates a base by heating. By containing a thermal base generator, the imidization of the negative photosensitive resin composition can be further accelerated. This can improve the adhesion during low-temperature curing.

The type of the thermal base generator is not particularly limited, but examples thereof include an amine compound protected by a tertiary butoxycarbonyl group and the thermal base generator shown in Patent Documents 3 and 4. However, it is not limited to these, and other well-known thermal base generating agents can also be used.

Examples of the amine compound protected by the third butoxycarbonyl group include: ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4- Amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2- Amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol Hexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamine ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperdine 4-(3-Hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinemethanol Aldyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxy Bis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3- Aminopropyl) ether, 1,11-diamino-3,6,9-triox undecane, diethylene glycol bis(3-aminopropyl) ether, etc., as well as amino acids and their Compounds in which the amine group of the derivative is protected by a tert-butoxycarbonyl group are not limited thereto.

Examples of the thermal base generator compound having a urea structure include [Chemical 33] described in Patent Document 4. etc., but are not limited to these.

When the negative photosensitive resin composition contains (E) a thermal base generator, the compounding amount is preferably from 0.1 to 40 parts by mass relative to 100 parts by mass of the (A) polyimide precursor. More preferably, it is not less than 0.5 parts by mass and not more than 30 parts by mass, and still more preferably not less than 1 part by mass and not more than 25 parts by mass, for example, it is not less than 0.5 parts by mass and not more than 20 parts by mass. The above-mentioned compounding amount is preferably 0.1 parts by mass or more from the viewpoint of the imidization acceleration effect, and is preferably 30 parts from the viewpoint of the physical properties of the cured photosensitive resin layer of the negative photosensitive resin composition. parts by mass or less.

The negative photosensitive resin composition may further contain components other than the above-mentioned (A) to (E) components. The components other than components (A) to (E) are not limited, and examples thereof include rust inhibitors, hindered phenol compounds, organic titanium compounds, adhesion assistants, sensitizers, thermal polymerization inhibitors, and the like.

Rust inhibitor When a negative photosensitive resin composition is used to form a cured film on a substrate containing copper or a copper alloy, the negative photosensitive resin composition may optionally contain a rust inhibitor in order to suppress discoloration of the copper. Examples of rust inhibitors include azole compounds, purine compounds, and the like.

Examples of the azole compound include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, and 5-benzene Base-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-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl) methyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'- Hydroxy-5'-tertiary octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole Triazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole , 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

Particularly preferred ones include 5-amino-1H-tetrazole, tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. One type of these azole compounds may be used, or a mixture of two or more types may be used.

Specific examples of the purine compound include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9- Methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyl Adenine, 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-nitrogen Heteroxanthine, 8-azahypoxanthine, etc. and their derivatives.

When the negative photosensitive resin composition contains a rust inhibitor, the compounding amount is preferably from 0.01 to 20 parts by mass, more preferably 0.03 parts by mass relative to 100 parts by mass of the polyimide precursor (A) It is more than 10 parts by mass and not more than 10 parts by mass, and more preferably not less than 0.05 parts by mass and not more than 5 parts by mass, for example, it can be not less than 0.01 parts by mass and not more than 5 parts by mass. When the compounding amount of the rust inhibitor is 0.01 parts by mass or more relative to 100 parts by mass of (A) the polyimide precursor, and when the negative photosensitive resin composition is formed on copper or a copper alloy, Discoloration of the copper or copper alloy surface is suppressed, and on the other hand, when the amount is 20 parts by mass or less, the sensitivity is excellent.

Hindered phenol compounds In order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of hindered phenol compounds include: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 3-(3,5- Di-tert-butyl-4-hydroxyphenyl)octadecylpropionate, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)isooctylpropionate, 4,4 '-Methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-ydenine 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- Phenylpropylamine), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol) Tributylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-isocyanurate) Tributyl-4-hydroxybenzyl) ester, 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-tris-2,4,6-(1H,3H,5H) -Triketone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-( 1H,3H,5H)-trione, 1,3,5-tris(4-dibutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2 ,4,6-(1H,3H,5H)-trione, 1,3,5-tris[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-di Methyl-4-phenylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl) -3-Hydroxy-2,5,6-trimethylbenzyl)-1,3,5-trimethylbenzyl-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-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1 ,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3- Hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl -3-Hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-th Tributyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5 -Tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)- Triketone, etc., but are not limited thereto. Among these, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4 is particularly preferred ,6-(1H,3H,5H)-triketone, etc.

When the negative photosensitive resin composition contains a hindered phenol compound, the compounding amount is preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 100 parts by mass of the polyimide precursor (A). More than 10 parts by mass and less than 10 parts by mass. When the compounding amount of the hindered phenol compound is 0.1 parts by mass or more relative to 100 parts by mass of the polyimide precursor (A), for example, when a negative photosensitive resin composition is formed on copper or a copper alloy, It prevents discoloration and corrosion of copper or copper alloy. On the other hand, when it is 20 parts by mass or less, the sensitivity is excellent.

Organotitanium compounds The negative photosensitive resin composition may contain an organic titanium compound. By containing an organic titanium compound in a negative photosensitive resin composition, a photosensitive resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

Examples of organic titanium compounds that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. The following I) to VII) show specific examples of organic titanium compounds: I) Titanium chelate compounds: Among them, in terms of the storage stability of the negative photosensitive resin composition being better and obtaining a good hardened pattern, More preferred is a titanium chelate compound having two or more alkoxy groups. Specific examples are titanium bis(triethanolamine)diisopropoxide, titanium bis(2,4-glutarate)di(n-butoxide), titanium bis(2,4-glutarate)diisopropoxide, titanium bis(2,4-glutarate)diisopropoxide, Tetramethyl pimelic acid) titanium diisopropoxide, bis(acetyl ethyl acetate) titanium diisopropoxide, etc. II) Titanium tetraalkoxide compounds: for example, titanium tetrakis (n-butoxide), titanium tetraethoxide, titanium tetrakis (2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxide Titanium methoxypropoxide, titanium tetramethylphenolate, titanium tetrakis (n-nonyl alcohol), titanium tetrakis (n-propyl alcohol), titanium tetrastearylate, tetrakis[bis{2,2-(allyloxymethyl) )butanol}] titanium, etc. III) Titanium compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(eta ⁵ -2,4-dicyclopentadien-1-yl)bis(2,6-difluorophenyl) Titanium, bis(eta ⁵ -2,4-dicyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, etc. V) Oxytitanium compounds: for example, bis(glutaric acid)oxytitanium, bis(tetramethylpymelyl)oxytitanium, phthalocyanine titanyloxy, etc. VI) Titanium tetraacetylpyruvate compound: for example, titanium tetraacetylpyruvate, etc. VII) Titanate coupling agent: for example, tris(dodecylbenzenesulfonyl)isopropyl titanate, etc.

Among them, the organic titanium compound is preferably selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) titanium compound from the viewpoint of exhibiting better chemical resistance. At least one compound in the group. Particularly preferred are bis(ethyl acetyl acetate) titanium diisopropoxide, tetrakis(n-butoxide)titanium, and bis(eta ⁵ -2,4-dicyclopentadien-1-yl)bis(2,6 -Difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

When the negative photosensitive resin composition contains an organic titanium compound, the compounding amount is preferably from 0.05 to 10 parts by mass, more preferably from 0.1 to 100 parts by mass of the polyimide precursor (A). More than 2 parts by mass and less than 2 parts by mass. When the blending amount is 0.05 parts by mass or more, the obtained hardened pattern exhibits good heat resistance and chemical resistance. On the other hand, when the blending amount is 10 parts by mass or less, the negative photosensitive resin composition is preserved Excellent stability.

Then auxiliary In order to improve the adhesion between the film formed using the negative photosensitive resin composition and the base material, the negative photosensitive resin composition may optionally contain an adhesive auxiliary agent. As the adhesive agent, aluminum-based adhesive agent, silane coupling agent, etc. can be used.

Examples of aluminum-based adhesive additives include tris(acetyl ethyl acetate)aluminum, tris(acetyl pyruvate) aluminum, ethylaluminum acetyl acetate diisopropyl, and the like.

Examples of the silane coupling agent include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-silane. Glyceroxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacrylyl Oxypropyltrimethoxysilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-hydride Glyceroxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalide Methylamide, 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-phenylamino Propyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, 3-mercaptopropyl Trimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name KBM803, Chisso Co., Ltd.: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: product Name SIM6475.0), 3-Mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: brand name LS1375, manufactured by Azmax Co., Ltd.: brand name SIM6474.0), mercaptomethyltrimethoxysilane Silane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxy silane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxysilane Dipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldipropoxysilane Ethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethylethoxysilane Oxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutan Triethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: Trade name LS3610, Azmax Co., Ltd. Manufacture: Trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (Manufactured by Azmax Co., Ltd.: Trade name SIU9058.0), N-(3-diethoxymethoxysilane) propyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxy Propoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N- (3-Methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea , N-(3-Tripropoxysilylethyl)urea, N-(3-Tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl) Urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilyl) Butyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethyl Oxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0) Manufactured by Azmax Co., Ltd.: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd. Co., Ltd.: Trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylethyl) Methylethyl)pyridine, (3-triethoxysilylpropyl)-tert-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, Tetraethoxysilane, tetra-n-propoxysilane, tetrakis-isopropoxysilane, tetrakis-n-butoxysilane, tetrakis-butoxysilane, tetrakis-butoxysilane oxyethoxysilane), tetrakis(methoxy n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilane) Silyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene , bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-( Triethoxysilyl)propyl]tetrasulfide, di-tert-butoxydiethyloxysilane, di-isobutoxyaluminumoxytriethoxysilane, phenylsilanetriol, methyl phenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol , tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethane phenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol Alcohol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenyl Silanol, tert-butyldiphenylsilanol, triphenylsilanol, etc. Furthermore, examples of the silane coupling agent include, but are not limited to, silane coupling agents having structures represented by the following formulas (S-1). [Chemical 34]

Among these adhesive agents, in terms of adhesive strength, a silane coupling agent is more preferably used. As the silane coupling agent, among the above-mentioned silane coupling agents, from the viewpoint of storage stability, it is preferable to use one selected from the group consisting of phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, and dimethoxysilane. Phenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and those having the above formula (S-1) One or more of the group of silane coupling agents with structures represented by the formulas.

When the negative photosensitive resin composition contains an adhesive agent, the compounding amount of the adhesive agent is preferably from 0.01 to 25 parts by mass relative to 100 parts by mass of the polyimide precursor (A), or More preferably, it is 0.5 parts by mass or more and 20 parts by mass or less. When using a silane coupling agent, the compounding amount is preferably from 0.01 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A).

Sensitizer In order to improve the sensitivity, the negative photosensitive resin composition may optionally contain a sensitizer. Examples of the sensitizer include Michelone, 4,4'-bis(diethylamino)benzophenone, and 2,5-bis(4'-diethylaminobenzophenone). Methyl)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-dimethylaminocinnamonide Indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminobenzene 1,3-bis(4'-dimethylaminophenylidene)benzothiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-ethyl-7-dimethyl Aminocoumarin, 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-𠰌linylbenzophenone, isoamyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole , 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoethyl, 2-(p-dimethylaminostyryl) Benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These can be used individually or in combination of 2 to 5 types, for example.

When the negative photosensitive resin composition contains a sensitizer for increasing sensitivity, the compounding amount is preferably 0.1 part by mass or more and 25 parts by mass relative to 100 parts by mass of the polyimide precursor (A) the following.

thermal polymerization inhibitor In order to improve the stability of the viscosity and sensitivity especially when stored in a solution containing a solvent, the negative photosensitive resin composition may optionally contain a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors that can be used include: hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenylnaphthalene, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-Cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1- Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso- N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc.

＜Manufacturing method of hardened relief pattern＞ The manufacturing method of the hardened relief pattern of the present invention includes: (1) The step of coating the negative photosensitive resin composition of the present invention on a substrate to form a photosensitive resin layer on the substrate (resin layer forming step); (2) The step of exposing the above-mentioned photosensitive resin layer (exposure step); (3) The step of developing the exposed photosensitive resin layer to form a relief pattern (relief pattern forming step); and (4) A step of heat-treating the above-mentioned relief pattern to form a hardened relief pattern (hardened relief pattern forming step).

(1) Resin layer formation step In this step, the negative photosensitive resin composition is coated on the substrate, and then dried if necessary to form a photosensitive resin layer. As a coating method, a method previously used for coating a negative photosensitive resin composition can be used, such as by a spin coater, a rod coater, a blade coater, a curtain coater, a mesh A method of coating with a plate printing machine, etc., a method of spray coating with a spray coater, etc.

If necessary, the coating film containing the negative photosensitive resin composition can be dried. As drying methods, air drying; heating drying using an oven or heating plate; vacuum drying and other methods can be used. Specifically, in the case of air drying or heat drying, drying can be performed at 20°C to 150°C for 1 minute to 1 hour. In the above manner, a photosensitive resin layer can be formed on the substrate.

(2)Exposure step In this step, exposure devices such as contact exposure machines, mirror projection exposure machines, stepper machines, etc. are used to perform the above-mentioned processing through a photomask or reticle with a pattern or directly through an ultraviolet light source. The formed photosensitive resin layer is exposed. By this exposure, the polymerizable group of the (A) polyimide precursor contained in the negative photosensitive resin composition is cross-linked by the action of the (C) photopolymerization initiator. Due to this cross-linking, the exposed portion becomes insoluble in the developer described below, so a relief pattern can be formed.

Thereafter, for the purpose of improving the sensitivity, etc., post-exposure baking (PEB) or pre-development baking or both of them can be implemented with any combination of temperature and time as necessary. The baking conditions are preferably a temperature of 40°C to 120°C and a time of 10 seconds to 240 seconds, but the baking conditions are not limited to this range as long as the characteristics of the negative photosensitive resin composition of the present invention are not hindered.

(3) Embossed pattern formation step In this step, the unexposed portion of the exposed photosensitive resin layer is removed by development. As a development method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from previously known photoresist development methods, such as spin spray method, liquid coating method, immersion method accompanied by ultrasonic treatment, etc. And use. After development, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking using any combination of temperature and time can be performed if necessary.

As a developer used for development, for example, a good solvent for a negative photosensitive resin composition, or a combination of this good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ -Butyrolactone, α-acetyl-γ-butyrolactone, etc. As the lean solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferred. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent based on the solubility of the polymer in the negative photosensitive resin composition. Two or more solvents may be used, for example, several types may be used in combination.

(4) Hardened relief pattern formation step In this step, the relief pattern obtained by the above-mentioned development is subjected to heat treatment to disperse the photosensitive components, and the polyimide precursor (A) is imidized, thereby converting it into a polyimide-containing polyimide precursor. Hardened embossed pattern. As a heat treatment method, various methods can be selected, 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 control program. The heat treatment can be performed at 160°C to 350°C for 30 minutes to 5 hours, for example. The temperature of the heat treatment is preferably 200°C or lower, more preferably 180°C or lower. As the ambient gas during heating and hardening, air can be used, or inert gases such as nitrogen and argon can be used.

Furthermore, the exposed photosensitive resin layer has a crosslinked structure formed by crosslinking the polymerizable groups of the polyimide precursor (A). However, it is believed that the cross-linked structure is detached from the polymer during the heating step of forming the hardened relief pattern, and the amide acid structure generated by the detachment closes the ring to form a amide imine ring structure, thereby obtaining a hardened polyamide containing polyimide. Embossed pattern.

<Polyimide cured film> The present invention also provides a cured film formed from the negative photosensitive resin composition of the present invention. The cured film formed from the above-mentioned negative photosensitive resin composition is considered to contain a polyimide having a structure represented by the following general formula (4). [Chemical 35]

In the general formula (4), X ₁ and Y ₁ are respectively the same as X ₁ and Y ₁ in the general formula (1). The preferred X ₁ and Y ₁ in the general formula (1) are also preferred in the polyimide of the general formula (4) for the same reason.

＜Semiconductor Device＞ The present invention also provides a semiconductor device having a hardened relief pattern obtained from the above-mentioned negative photosensitive resin composition. Specifically, a semiconductor device having a base material as a semiconductor element and a hardened relief pattern is provided. The hardened relief pattern can be produced by the above-mentioned method for producing a hardened relief pattern using the above-mentioned negative photosensitive resin composition. In the present invention, there is also provided a method of manufacturing a semiconductor device using a semiconductor element as a base material and including the above-mentioned method of manufacturing a hardened relief pattern of this embodiment as a part of the steps. In this case, it can be produced by forming the hardened embossed pattern formed by the method of manufacturing the hardened embossed pattern of the present invention into a surface protective film, an interlayer insulating film, and an insulating film for rewiring of a semiconductor device. , protective films for flip-chip devices, or protective films for semiconductor devices with bump structures, etc., and combined with known manufacturing methods of semiconductor devices.

＜Display device＞ The present invention also provides a display device including a display element and a cured film provided on the upper part of the display element, and the cured film is the above-mentioned cured relief pattern. Here, the hardened relief pattern can be directly connected to the display element and laminated, or can be laminated with other layers in between. The cured film can be used, for example, in surface protective films, insulating films, planarizing films, etc. for TFT (thin-film transistor, thin film transistor) liquid crystal display elements and color filter elements; MVA (Multi-Domain Vertical Alignment, multi-domain Protrusions for vertical alignment) type liquid crystal display devices; partition walls for cathodes of organic EL (Electroluminescence, electroluminescence) elements; etc.

In addition to being used in semiconductor devices as mentioned above, the negative photosensitive resin composition of the present invention can also be used for interlayer insulation of multilayer circuits, cover coatings of flexible copper foil boards, solder resist films, liquid crystal alignment films, etc. [Example 1]

Hereinafter, embodiments of the present invention will be described in detail through examples, but the present invention is not limited thereto. In the Examples, Comparative Examples, and Production Examples, the physical properties of the polyimide precursor or the negative photosensitive resin composition were measured and evaluated according to the following methods.

＜Measurement conditions＞ (1) Weight average molecular weight Using gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) of each resin was measured according to the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Pipe string: Shodex KD-805/KD-804/KD-803 series manufactured by Showa Denko Co., Ltd. Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd. Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL/min.

(2) Preparation of cured film on Cu On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm), a sputtering device (type L-440S-FHL, manufactured by CANON ANELVA Co., Ltd.) was used to sequentially sputter 200 nm thick Ti, 400 nm thick Cu. Then, the negative photosensitive resin composition prepared by the following method was spin-coated on the wafer using a coating developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and the wafer was heated at 110° C. using a heating plate. Pre-bake for 180 seconds to form a coating film. Using a temperature-increasing programmable curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.), the obtained coating film was heated for 2 hours under a nitrogen atmosphere at the temperatures listed in Tables 2 and 3, thereby curing the coating on Cu. An approximately 10 μm thick cured film containing resin was obtained.

(3) Evaluation of copper adhesion The cured film obtained by processing the negative photosensitive resin composition prepared by the following method by the above method was evaluated based on the following criteria based on the cross cutting method of JIS K 5600-5-6 standard. Adhesion properties between coating films. A: The number of grids of the cured resin coating adhered to the substrate is 80 or more and 100 or less. B: The number of grids of the hardened resin coating adhered to the substrate is 60 or more and less than 80 C: The number of grids of the hardened resin coating adhered to the substrate is from 40 to less than 60 D: The number of grids of the hardened resin coating adhered to the substrate does not reach 40

(4) Evaluation of residual film rate after hardening The remaining film rate of the cured film obtained in (2) was calculated as follows. Residual film rate after hardening [%] = (Film thickness after hardening [μm]) ÷ (Film thickness before hardening [μm]) × 100 The remaining film rate obtained by the above formula was evaluated based on the following criteria. AA: The residual film rate after hardening is more than 93% A: The residual film rate after hardening is more than 90% and less than 93% B: The residual film rate after hardening is more than 85% and less than 90% C: The residual film rate after hardening is more than 80% and less than 85%

The film thickness after curing and the film thickness before curing were measured using a stylus profile analyzer (trade name "P-17" from Tencor Corporation).

(5) Measurement of the acyl imidization rate The above-mentioned cured embossed pattern resin portion was measured using an ATR-FTIR measurement device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) using a Si incane, and the peak intensity of 1380 cm ^-1 was divided. Using the peak intensity of 1500 cm ^-1 and using the value obtained as the imidization index, calculate the imidization index of the films of each Example and Comparative Example divided by the film obtained by curing the resin composition at 350°C. The value obtained from the imidization index was used as the imidization rate. The imidization rate was evaluated based on the following criteria. A: The imidization rate is 95% or more. B: The imidization rate is 90% or more and less than 95%. C: The imidization rate is 80% or more and less than 90%. D: The imidization rate is 90% or more and less than 90%. Less than 80%

<Synthesis Example 1> (Synthesis of Heterocyclic Compound 1) 8.81 g (0.062 mol) of glycidyl methacrylate (GMA), 30.0 g of γ-butyrolactone, and 0.63 g (0.006 mol) into a 100 mL three-necked flask, add dropwise 6.27 g (0.062 mol) of 3-mercaptotriazole, and stir overnight to obtain a γ-butyrolactone solution of heterocyclic compound 1. Heterocyclic compound 1 is a compound shown below. The heteroatom ratio of heterocyclic compound 1 is calculated as {( 3＋1＋3)/(3＋1＋3+9)}×100=44%. It is shown in Table 1 as "heteroatom ratio of side chain compound". The same applies to other side chain compounds below. [Chemical 36]

(Synthesis of polymer A-1 as precursor of (A) polyimide) Put 31.0 g (0.1 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) into a 1 L separable flask, and add 40.0 g of γ-butyrolactone. Next, 50.9 g of a γ-butyrolactone solution of heterocyclic compound 1 (heterocyclic compound 1: 0.062 mol) and 19.0 g of 2-hydroxyethyl methacrylate (HEMA, 0.15 mol) were added, and 15.8 g of pyridine was added while stirring. Then, stir at room temperature overnight.

Next, while stirring the obtained reaction mixture, 30.0 g (0.20 mol) of 1-hydroxybenzoethazole (HOBt) was added, and then dicyclohexylcarbodiimide (DCC) was added over 20 minutes while cooling in an ice bath. ) 40.4 g (0.20 mol) was dissolved in 40.0 g of γ-butyrolactone, and then 2,2-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter BAPP )35.2 g (0.09 mol) was suspended in 35.0 g of γ-butyrolactone. After stirring at room temperature for 4 hours, 18 g of ethanol was added, and the mixture was further stirred for 1 hour. Next, 140 g of γ-butyrolactone was added. The reaction mixture is filtered, and the precipitate generated in the reaction system is removed to obtain a reaction liquid.

The obtained reaction liquid was added to 1.2 kg of ethanol to precipitate the crude polymer. The precipitated crude polymer was obtained by filtration, and dissolved in 300 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 2.0 kg of water to reprecipitate the polymer. The obtained reprecipitate was collected by filtration and then dried in vacuum to obtain a powdery polymer (polymer A-1). The molecular weight of polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 15,000.

＜Synthesis example 2＞ (Synthesis of polymer A-2 as precursor of (A) polyimide) The same procedure as in Synthesis Example 1 was used except that the γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1 was changed from 50.9 g to 17.0 g (heterocyclic compound 1: 0.021 mol) and the HEMA 19.0 g was changed to 24.4 g. The reaction was carried out in the same manner as described to obtain polymer A-2. The molecular weight of polymer A-2 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 23,000.

＜Synthesis Example 3＞ (Synthesis of polymer A-3 as precursor of (A) polyimide) The same procedure as described in Synthesis Example 1 except that 21.8 g (0.1 mol) of pyromellitic anhydride (PMDA) was used instead of 31.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Synthesis Example 1. The reaction was carried out in the same manner to obtain polymer A-3. The molecular weight of polymer A-3 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 16,000.

＜Synthesis Example 4＞ (Synthesis of polymer A-4 as precursor of (A) polyimide) In addition to using 29.4 g (0.1 mol) of 4,4'-biphenyltetracarboxylic dianhydride (hereinafter BPDA) instead of 31.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Synthesis Example 1, the same The reaction was carried out in the same manner as described in Synthesis 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 result was that the weight average molecular weight (Mw) was 15,000.

＜Synthesis Example 5＞ (Synthesis of polymer A-5 as precursor of (A) polyimide) Except that 52.0 g (0.1 mol) of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride (hereinafter BisDA) was used instead of 4,4'-oxydibenzoyl in Synthesis Example 1. Except for 31.0 g of phthalic dianhydride (ODPA), the reaction was carried out in the same manner as described in Synthesis Example 1 above to obtain polymer A-5. The molecular weight of polymer A-5 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 18,000.

＜Synthesis example 6＞ (Synthesis of polymer A-6 as precursor of (A) polyimide) Except using 17.2 g (0.083 mol) of 4,4-diaminodiphenyl ether instead of 35.2 g of BAPP in Synthesis Example 1, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer A-6. . The molecular weight of polymer A-6 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 17,000.

＜Synthesis Example 7＞ (Synthesis of polymer A-7 as precursor of (A) polyimide) Except that 17.7 g (0.083 mol) of m-toluidine was used instead of 35.2 g of BAPP in Synthesis Example 1, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer A-7. The molecular weight of polymer A-7 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 17,000.

＜Synthesis example 8＞ (Synthesis of polymer A-8 as precursor of (A) polyimide) Except that 9.0 g (0.083 mol) of p-phenylenediamine was used instead of 35.2 g of BAPP in Synthesis Example 1, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer A-8. The molecular weight of polymer A-8 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 18,000.

<Synthesis Example 9> (Synthesis of Heterocyclic Compound 2) Put 8.81 g of GMA, 30.0 g of γ-butyrolactone and 0.63 g of triethylamine (TEA) into a 100 mL three-necked flask, and add 5-mercapto-1- 7.20 g of methyltetrazole and stirred overnight to obtain a γ-butyrolactone solution of heterocyclic compound 2. Heterocyclic compound 2 is a compound shown below. [Chemical 37]

(Synthesis of polymer A-9 as precursor of (A) polyimide) It was synthesized as above except that 51.8 g of γ-butyrolactone solution of heterocyclic compound 2 was used instead of 50.9 g of γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1, and HOBt was changed to 0 g (not used). The reaction was carried out in the same manner as described in 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 result was that the weight average molecular weight (Mw) was 20,000.

＜Synthesis Example 10＞ (Synthesis of polymer A-10 as precursor of (A) polyimide) In Synthesis Example 9, except that 50.9 g of the γ-butyrolactone solution of heterocyclic compound 2 was changed to 17.3 g (heterocyclic compound 2: 0.021 mol), and 19.0 g of HEMA was changed to 24.4 g, the same results were obtained as in Synthesis Example 9. The reaction was carried out in the same manner as described to obtain polymer A-10. The molecular weight of polymer A-10 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 22,000.

＜Synthesis Example 11＞ (Synthesis of polymer A-11 as precursor of (A) polyimide) In addition to changing 50.9 g of the γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) into N-(2-hydroxyethyl)phthalimide (NHPA, table "Heterocyclic Compound 3") 11.9 g (0.062 mol), except that HOBt 30.0 g was changed to 0 g (not used), and the reaction was carried out in the same manner as described in the above Synthesis Example 1 to obtain polymer A- 11. The molecular weight of polymer A-11 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 18,000.

＜Synthesis Example 12＞ (Synthesis of polymer A-12 as precursor of (A) polyimide) In addition to changing 50.9 g of the γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) into N-(2-hydroxyethyl)phthalimide (NHPA) 4.00 g (0.021 mol), except that HEMA 19.0 g was changed to 24.4 g, and HOBt 30.0 g was changed to 0 g (not used), the reaction was carried out in the same manner as described in the above Synthesis Example 1 to obtain polymer A- 12. The molecular weight of polymer A-12 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 20,000.

＜Synthesis Example 13＞ (Synthesis of polymer A-13 as precursor of (A) polyimide) In addition to changing 50.9 g of the γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) into 6.08 g (0.062 mol) of 3-furanmethanol ("heterocyclic compound 4" in the table) , except that HOBt 30.0 g was changed to 0 g (not used), the reaction was carried out in the same manner as described in the above Synthesis Example 1, and polymer A-13 was obtained. The molecular weight of polymer A-13 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 23,000.

＜Synthesis Example 14＞ (Synthesis of polymer A-14 as precursor of (A) polyimide) In addition to changing 50.9 g of the γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) into 2,4-dimethyl-6-hydroxypyrimidine (heterocyclic compound 5 in the table 》) 7.70 g (0.062 mol), except that HOBt 30.0 g was changed to 0 g (not used), the reaction was carried out in the same manner as described in the above Synthesis Example 1, and polymer A-14 was obtained. The molecular weight of polymer A-14 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 15,000.

＜Synthesis Example 15＞ (Synthesis of polymer A-15 as precursor of (A) polyimide) In addition to changing 50.9 g of the γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) into 2-hydroxymethyl-1-methylimidazole ("heterocyclic compound 6" in the table ) 6.95 g (0.062 mol), except that 30.0 g of HOBt was changed to 0 g (not used), and the reaction was carried out in the same manner as described in Synthesis Example 1 above, to obtain polymer A-15. The molecular weight of polymer A-15 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 24,000.

<Synthesis Example 16> (Synthesis of polymer A-16 as precursor of (A) polyimide) In addition to changing 50.9 g of the γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) into 7-ethyl-3-indoleethanol ("heterocyclic compound 7" in the table) 11.7 g (0.062 mol), except that 30.0 g of HOBt was changed to 0 g (not used), and the reaction was carried out in the same manner as described in the above Synthesis Example 1 to obtain polymer A-16. The molecular weight of polymer A-16 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 22,000.

＜Synthesis Example 17＞ (Synthesis of polymer A-17 as precursor of (A) polyimide) Put 31.0 g (0.1 mol) of ODPA into a 1 L separable flask, and add 40.0 g of γ-butyrolactone. Next, 26.5 g of HEMA was added, and 15.8 g of pyridine was added while stirring. Then, the mixture was stirred at 40° C. for 4 hours using an oil bath to obtain a reaction mixture. After the reaction is completed, cool to room temperature and leave for 16 hours.

Next, while stirring the obtained reaction mixture, a solution of 40.4 g of DCC dissolved in 40 g of γ-butyrolactone was added over 40 minutes while cooling in an ice bath, and then 35.2 g (0.086 mol) of BAPP was added over 20 minutes. ) was suspended in 35.0 g of γ-butyrolactone. After stirring at room temperature for 4 hours, 9.0 g of ethanol was added, and the mixture was further stirred for 1 hour. Next, 140 g of γ-butyrolactone was added. The reaction mixture is filtered, and the precipitate generated in the reaction system is removed to obtain a reaction liquid.

The obtained reaction liquid was added to 600 g of ethanol to precipitate the crude polymer. The precipitated crude polymer was obtained by filtration, and dissolved in 300 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 1 kg of water to reprecipitate the polymer. The obtained reprecipitate was collected by filtration and then dried in vacuum to obtain a powdery polymer (polymer A-17). The molecular weight of polymer A-17 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 25,000.

＜Synthesis Example 18＞ (Synthesis of polymer A-18 as precursor of (A) polyimide) Except that 35.2 g (0.09 mol) of BAPP in Synthesis Example 1 was changed into 22.3 g (0.09 mol) of bis(3-aminophenyl)trine, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain Polymer A-18. The molecular weight of polymer A-18 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 19,000.

<Synthesis Example 19> (Synthesis of Urea Compound 1) 10.5 g of 1-aminoethoxyethanol (AEE) and 26.0 g of γ-butyrolactone were put into a 100 mL three-necked flask and cooled to 0 degrees. 15.5 g of Karenz MOI (trade name; Showa Denko Co., Ltd.) was added dropwise to obtain a γ-butyrolactone solution of urea compound 1. Urea compound 1 is a compound shown below. [Chemical 38]

(Synthesis of polymer A-19 as precursor of (A) polyimide) Put 31.0 g (0.1 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) into a 1 L separable flask, and add 37.5 g of γ-butyrolactone. Next, 32.2 g of a γ-butyrolactone solution of urea compound 1 (urea compound 1: 0.062 mol) and 18.2 g of 2-hydroxyethyl methacrylate (hereinafter: HEMA, 0.14 mol) were added, and 15.8 g of pyridine was added while stirring. , stirred at 40°C for 5 hours using an oil bath to obtain a reaction mixture. After the reaction is completed, cool to room temperature and leave for 16 hours.

Next, while stirring the obtained reaction mixture, a solution of 40.7 g of dicyclohexylcarbodiamide (DCC) dissolved in 50 g of γ-butyrolactone was added over 40 minutes while cooling in an ice bath, and then After 60 minutes, add a suspension obtained by suspending 35.2 g (0.086 mol) of BAPP in 150 g of γ-butyrolactone. After stirring at room temperature for 2 hours, 9.0 g of ethanol was added, and the mixture was further stirred for 1 hour. Next, 70 g of γ-butyrolactone was added. The reaction mixture is filtered, and the precipitate generated in the reaction system is removed to obtain a reaction liquid.

The obtained reaction liquid was added to 1.2 kg of ethanol to precipitate the crude polymer. The precipitated crude polymer was obtained by filtration, and dissolved in 300 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 3.5 kg of water to reprecipitate the polymer. The obtained reprecipitate was collected by filtration and then dried in vacuum to obtain a powdery polymer (polymer A-19). The molecular weight of polymer A-19 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 29,000.

＜Synthesis Example 20＞ (Synthesis of polymer A-20 as precursor of (A) polyimide) In addition to changing 50.9 g of the γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1 into 10.80 g of 1-(4-aminobenzyl)-1,2,4-triazole (heterocyclic compound 1: 0.062 mol ), the reaction was carried out in the same manner as described in Synthesis Example 1 above to obtain polymer A-20. The molecular weight of polymer A-20 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 14,000.

<Example 1> A negative photosensitive resin composition was prepared by the following method using polyimide precursor A-1, and the prepared composition was evaluated. (A) Polyimide precursor A-1: 100 g was dissolved in γ-butyrolactone (hereinafter, referred to as GBL): 100 g. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 40 poise, and it was used as a negative photosensitive resin composition. The composition was evaluated according to the method described above.

<Example 2> A negative photosensitive resin composition was prepared by the following method using polyimide precursor A-1, and the prepared composition was evaluated. A-1 as (A) polyimide precursor: 100 g, 1-phenyl-1,2-propanedione-2-(O-ethoxy) as (C) photopolymerization initiator Carbonyl)-oxime (hereinafter referred to as PDO, C-1): 3 g dissolved in γ-butyrolactone (hereinafter referred to as GBL): 100 g. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 40 poise, and it was used as a negative photosensitive resin composition. The composition was evaluated according to the method described above.

<Example 3> A negative photosensitive resin composition was prepared by the following method using polyimide precursor A-1, and the prepared composition was evaluated. A-1 as (A) polyimide precursor: 100 g, 1-phenyl-1,2-propanedione-2-(O-ethoxy) as (C) photopolymerization initiator Carbonyl)-oxime (hereinafter referred to as PDO, C-1): 3 g, pentaerythritol tetraacrylate (Shin Nakamura Chemical A-TMMT) as (D) polymerizable monomer: 20 g (D-1) dissolved in γ -Butyrolactone (hereinafter referred to as GBL): 100 g. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 40 poise, and it was used as a negative photosensitive resin composition. The composition was evaluated according to the method described above.

<Examples 4 to 23, Comparative Examples 1 to 5> Except using the polymer, photoinitiator, polymerizable monomer, and solvent shown in Tables 2 and 3, the same negative photosensitive resin composition as in Examples 1 to 3 was prepared, and evaluated according to the above method.

<Example 24> A negative photosensitive resin composition was prepared by the following method using polyimide precursor A-1, and the prepared composition was evaluated. A-1 as (A) polyimide precursor: 100 g, 1-phenyl-1,2-propanedione-2-(O-ethoxy) as (C) photopolymerization initiator Carbonyl)-oxime (hereinafter referred to as PDO, C-1): 3 g, as (D) polymerizable monomer pentaerythritol tetraacrylate: 20 g (D-1), as (E) thermal base generating agent ( E-1): 20 g was dissolved in γ-butyrolactone (hereinafter referred to as GBL): 100 g. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 40 poise, and a negative photosensitive resin composition was prepared. The composition was evaluated according to the method described above.

[Table 1] Table 1. Types of polyimide precursors Polyimide precursor skeleton Anhydride Diamine side chain compounds Heteroatom ratio of side chain compounds Import volume Synthesis example 1 A-1 ODPA BAPP Heterocyclic compounds 1 44% 30% Synthesis example 2 A-2 ODPA BAPP Heterocyclic compounds 1 44% 10% Synthesis example 3 A-3 PMDA BAPP Heterocyclic compounds 1 44% 30% Synthesis example 4 A-4 BPDA BAPP Heterocyclic compounds 1 44% 30% Synthesis example 5 A-5 sDA BAPP Heterocyclic compounds 1 44% 30% Synthesis example 6 A-6 ODPA DADPE Heterocyclic compounds 1 44% 30% Synthesis Example 7 A-7 ODPA mTB Heterocyclic compounds 1 44% 30% Synthesis example 8 A-8 ODPA p-PhD Heterocyclic compounds 1 44% 30% Synthesis example 9 A-9 ODPA BAPP Heterocyclic compounds 2 47% 30% Synthesis example 10 A-10 ODPA BAPP Heterocyclic compounds 2 47% 10% Synthesis Example 11 A-11 ODPA BAPP Heterocyclic compounds 3 29% 30% Synthesis example 12 A-12 ODPA BAPP Heterocyclic compounds 3 29% 10% Synthesis example 13 A-13 ODPA BAPP Heterocyclic compounds 4 29% 30% Synthesis Example 14 A-14 ODPA BAPP Heterocyclic compounds 5 33% 30% Synthesis Example 15 A-15 ODPA BAPP Heterocyclic compound 6 40% 30% Synthesis Example 16 A-16 ODPA BAPP Heterocyclic compounds 7 14% 30% Synthesis Example 17 A-17 ODPA BAPP without - 0% Synthesis example 18 A-18 ODPA 3,3'-DAS Heterocyclic compounds 1 44% 30% Synthesis example 19 A-19 ODPA BAPP Urea compound 1 39% 30%

[Table 2] Table 2. Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 (A) Polyimide precursor A-1 100 100 100 100 100 100 100 A-2 100 A-3 A-4 A-5 A-6 A-7 A-8 A-9 100 A-10 100 A-11 100 A-12 100 A-13 100 A-14 100 A-15 100 A-16 100 A-17 A-1S A-19 A-20 (B)Solvent GBL 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 NMP 100 (C) Photopolymerization initiator C-1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 (D)Polymerizable monomer D-1 20 20 20 20 20 20 20 20 20 20 20 D-2 20 D-3 20 D-4 20 (E) Thermal base generator E-1 process Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 performance Copper tight connection A A A C A C B C C C B B B A A A hardened film residue C B A A A A C C C C C B A B B AA acyl imidization rate B B B B B B B B B B B B B B B B

[table 3] table 3. Example Comparative example 17 18 19 20 twenty one twenty two twenty three twenty four 1 2 3 4 5 (A) Polyimide precursor A-1 100 100 A-2 A-3 100 A-4 100 A-5 100 A-6 100 A-7 100 A-8 100 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 100 100 A-18 100 A-19 100 A-20 100 (B)Solvent GBL 100 100 100 100 100 100 100 100 100 100 100 100 100 NMP (C) Photopolymerization initiator C-1 3 3 3 3 3 3 3 3 3 3 3 3 3 (D)Polymerizable monomer D-1 20 20 20 20 20 20 20 20 20 20 20 20 20 D-2 D-3 D-4 (E) Thermal base generator E-1 20 process Hardening temperature (℃) 230 230 230 230 230 230 170 170 230 230 170 230 230 performance Copper tight connection A A A A A A C A D C D D A hardened film residue A A A A A A A A A A A C A acyl imidization rate B B B B B B C B B B D A D

C-1: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (PDO) D-1: Pentaerythritol tetraacrylate D-2: 2-hydroxy methacrylate Ethyl ester D-3: Tricyclodecane dimethanol diacrylate (Shin Nakamura Chemical Industry A-DCP) D-4: Dipentaerythritol polyacrylate (Shin Nakamura Chemical Industry A-DPH) E-1: Represented by the following formula of compounds. [Chemical 39] [Industrial availability]

By using the negative photosensitive resin composition of the present invention, it is possible to obtain a cured relief pattern with high copper adhesion and less shrinkage of the film during the heating step after thermal curing. The negative photosensitive resin composition of the present invention can be preferably used in the field of photosensitive materials useful in the production of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (19)

A negative photosensitive resin composition containing: (A) a polyimide precursor containing a structural unit represented by the following general formula (1), and (B) a solvent; [Chemical 1] _{ In _formula ( ₁ ) _, They are each independently selected from the group consisting of hydrogen atoms, monovalent organic groups with 1 to 40 carbon atoms that may contain heteroatoms, and monovalent organic groups with heterocyclic structures, wherein R ₁ and R ₂ At least one of them is a monovalent organic group having a heterocyclic structure}. A negative photosensitive resin composition containing: (A) a polyimide precursor containing a structural unit represented by the following general formula (1), and (B) a solvent; [Chemical 2] _{ In _formula ( ₁ ) _, Each is independently one of the group consisting of a hydrogen atom, a monovalent organic group with a carbon number of 1 to 40 that may contain heteroatoms, and a monovalent organic group with a heterocyclic structure, wherein, in OR ₁ and OR ₂ At least one of them is a monovalent organic group in which the ratio of the number of heteroatoms among the constituent atoms other than hydrogen atoms is 42% or more}. The negative photosensitive resin composition of Claim 1 or 2, which further contains (C) a photopolymerization initiator. The negative photosensitive resin composition of claim 1 or 2, wherein at least one of R ₁ and R ₂ is a monovalent organic group containing a heterocyclic structure containing a nitrogen atom. The negative photosensitive resin composition of claim 1 or 2, wherein at least one of R ₁ and R ₂ is a monovalent organic group containing a 5-membered ring heterocyclic structure containing a nitrogen atom. The negative photosensitive resin composition of claim 1 or 2, wherein among all the structural units of the above-mentioned (A) polyimide precursor, at least one of R ₁ and R ₂ has a (meth)acrylate group. . The negative photosensitive resin composition of claim 1 or 2, wherein among all the structural units of the above-mentioned (A) polyimide precursor, R ₁ and R ₂ have a total of more than 2 (meth)acrylate groups. . The negative photosensitive resin composition of claim 1 or 2, wherein at least one of R ₁ and R ₂ is a group represented by the following general formula (3); [Chemical 2] {In formula (3), Ar is the above-mentioned heterocyclic structure, the dotted line is a single bond bonded to the oxygen atom of formula (1), R ₃ , R ₄ and R ₅ are independently hydrogen atoms or carbon atoms with 1 to 3 carbon atoms. Monovalent organic group, R ₆ and R ₇ are each independently a divalent organic group having 1 to 10 carbon atoms which may contain heteroatoms}. The negative photosensitive resin composition of claim 1 or 2, wherein at least one of R ₁ and R ₂ is a monovalent organic group having a heterocyclic structure, and the heterocyclic structure is triazole or tetrazole. The negative photosensitive resin composition of claim 1 or 2, wherein more than 10 mol% of the total _R1 and _R2 of the polyimide precursor (A) have the above heterocyclic structure and/or the above heteroatom A structure with a high ratio of numbers. The negative photosensitive resin composition of Claim 1 or 2, which further contains (D) a monomer having a polymerizable functional group. The negative photosensitive resin composition of claim 1 or 2, wherein the monomer (D) having a polymerizable functional group has two or more polymerizable functional groups. The negative photosensitive resin composition of claim 1 or 2, wherein the monomer (D) having a polymerizable functional group has three or more polymerizable functional groups. The negative photosensitive resin composition of claim 1 or 2, wherein X ₁ contains at least one selected from the group consisting of the following general formulas (8) to (11); [Chemical 3] [Chemical 4] [Chemistry 5] [Chemical 6] . The negative photosensitive resin composition of claim 1 or 2, wherein the above Y ₁ contains at least one selected from the group consisting of the following general formulas (12) to (15); [Chemical 7] [Chemical 8] [Chemical 9] [Chemical 10] {In the formula, R ₁₁ is each independently a monovalent organic group having 1 to 10 carbon atoms that may contain a halogen atom, and a is each independently an integer from 0 to 4}. The negative photosensitive resin composition of claim 1 or 2 further contains 0.1 to 40 parts by mass of (E) thermal base generating agent based on 100 parts by mass of the above-mentioned (A) polyimide precursor. . A method of manufacturing a hardened relief pattern, which includes the following steps: (1) The step of coating the negative photosensitive resin composition of claim 1 or 2 on a substrate to form a photosensitive resin layer on the substrate; (2) The step of exposing the above-mentioned photosensitive resin layer; (3) The step of developing the above-mentioned exposed photosensitive resin layer to form a relief pattern; and (4) The step of heat-treating the above-mentioned embossed pattern to form a hardened embossed pattern. A polyimide precursor containing a structural unit represented by the following general formula (1); [Chemical 11] _{ In _formula ( ₁ ) _, They are each independently selected from the group consisting of hydrogen atoms, monovalent organic groups with 1 to 40 carbon atoms that may contain heteroatoms, and monovalent organic groups with heterocyclic structures, wherein R ₁ and R ₂ At least one of them is a monovalent organic group having a heterocyclic structure}. A polyimide precursor containing a structural unit represented by the following general formula (1); [Chemical 11] _{ In _formula ( ₁ ) _, Each is independently one of the group consisting of a hydrogen atom, a monovalent organic group with a carbon number of 1 to 40 that may contain heteroatoms, and a monovalent organic group with a heterocyclic structure, wherein, in OR ₁ and OR ₂ At least one of them is a monovalent organic group in which the ratio of the number of heteroatoms among the constituent atoms other than hydrogen atoms is 42% or more}.