JP2023120162A - Polyimide precursor, negative photosensitive resin composition, and method for producing cured relief pattern using the same - Google Patents

Abstract

To provide a negative photosensitive resin composition which has good adhesion to copper wiring and can suppress curing shrinkage.SOLUTION: The negative photosensitive resin composition contains (A) a polyimide precursor containing a structural unit represented by general formula (1) and (B) a solvent. In the formula (1), X1 represents a C4-40 tetravalent organic group which may contain a heteroatom; Y1 represents a C6-40 divalent organic group which may contain a heteroatom; and R1 and R2 each independently represent one selected from the group consisting of a hydrogen atom, a C1-40 monovalent organic group which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present disclosure relates to a polyimide precursor, a negative photosensitive resin composition, a method for producing a cured relief pattern using the same, and the like.

BACKGROUND ART Conventionally, polyimide resins, which have excellent heat resistance, electrical properties and mechanical properties, have been used as insulating materials for electronic parts, passivation films, surface protective films, interlayer insulating films, etc. for semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor composition can easily form a heat-resistant relief pattern film by thermal imidization treatment by applying, exposing, developing, and curing the composition. can be formed. Such a photosensitive polyimide precursor composition has the feature of enabling a significant reduction in the process compared to conventional non-photosensitive polyimide materials.

By the way, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards by various methods according to their purposes. A conventional element is generally manufactured by a wire bonding method in which a thin wire is used to connect an external terminal (pad) of the element to a lead frame. However, today, when the speed of devices has increased and the operating frequency has reached GHz, the difference in the wiring length of each terminal in mounting affects the operation of the device. Therefore, in mounting elements for high-end applications, it is necessary to accurately control the length of the mounting wiring, and it has become difficult to satisfy this requirement with wire bonding.

Therefore, flip-chip mounting has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, the chip is flipped over, and the chip is directly mounted on a printed circuit board. . Since this flip-chip mounting can accurately control the wiring distance, it has been adopted for high-end devices that handle high-speed signals, and for mobile phones due to its small mounting size, and demand is growing rapidly. . More recently, a pre-processed wafer is diced to produce individual chips, the individual chips are reconstructed on a support, sealed with mold resin, and a rewiring layer is formed after removing the support. A semiconductor chip mounting technique called fan-out wafer level package (FOWLP) has been proposed. The fan-out wafer level package has the advantage of being able to reduce the height of the package, as well as high-speed transmission and cost reduction.

WO2021/215374 WO2020/189358 WO2017/038598 WO2020/026840

When using a negative photosensitive polyimide, the photosensitive side chains dissociated from the polyimide precursor during the curing process remain in the polyimide film, inhibiting the interaction between the copper substrate and the polyimide resin, resulting in a decrease in adhesion. is a problem. On the other hand, if the separated photosensitive side chains volatilize from the film, it will significantly accelerate curing shrinkage during the curing process, so the photosensitive side chains should remain in the polyimide film and adhesion should not be reduced. I needed technology.

It is known that a rust inhibitor having a heterocyclic structure is effective for adhesion between a polyimide film and a copper substrate. For example, in Patent Document 1, an additive having a heterocyclic structure is used to improve adhesion to a substrate. However, the technique of Patent Document 1 does not aim at achieving both adhesion to a substrate and suppression of curing shrinkage during a curing process.

In Patent Document 2, an attempt is made to improve adhesion to a substrate by introducing a heterocyclic structure into the terminal structure or side chain structure of a polymer. However, the introduction of a heterocyclic structure into the terminal structure does not aim at achieving both adhesion to the substrate and suppression of curing shrinkage during the curing process. was introduced via the , and inhibited the imidization reaction during the curing process.

Therefore, the present disclosure provides a negative photosensitive resin composition that sufficiently promotes imidization during the curing process, has good adhesion to copper wiring, and can suppress curing shrinkage during the curing process, and An object of the present invention is to provide a method for producing a cured relief pattern using the negative photosensitive resin composition.

Examples of embodiments of the present disclosure are listed below.
[1]
(A) a polyimide precursor containing a structural unit represented by the following general formula (1); and (B) a negative photosensitive resin composition containing a solvent.
{In formula (1), X ₁ is a tetravalent organic group having 4 to 40 carbon atoms which may contain a heteroatom, and Y ₁ is a divalent organic group having 6 to 40 carbon atoms which may contain a heteroatom. and R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure One selected, provided that at least one of R ₁ and R ₂ is a monovalent organic group having a heterocyclic structure. }
[2]
(A) a polyimide precursor containing a structural unit represented by the following general formula (1); and (B) a negative photosensitive resin composition containing a solvent.
{In formula (1), X ₁ is a tetravalent organic group having 4 to 40 carbon atoms which may contain a heteroatom, and Y ₁ is a divalent organic group having 6 to 40 carbon atoms which may contain a heteroatom. and R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure It is one selected type, provided that at least one of OR ₁ and OR ₂ is a monovalent organic group in which the number of heteroatoms accounts for 42% or more of the constituent atoms excluding hydrogen atoms. }
[3]
(C) The negative photosensitive resin composition according to item 1 or 2, further comprising a photopolymerization initiator.
[4]
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 having a heterocyclic structure containing a nitrogen atom.
[5]
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 consisting of a 5-membered heterocyclic ring structure containing a nitrogen atom. .
[6]
The negative photosensitive resin according to any one of items 1 to 5, wherein at least one of R ₁ and R ₂ in all structural units of the (A) polyimide precursor has a (meth)acrylate group. Composition.
[7]
7. The negative photosensitive material according to any one of items 1 to 6, wherein R ₁ and R ₂ in all structural units of the (A) polyimide precursor have a total of two or more (meth)acrylate groups. elastic resin composition.
[8]
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).
{In formula (3), Ar is the heterocyclic structure, the dashed line is a single bond bonding to the oxygen atom in formula (1), and 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 R ₆ and R ₇ are each independently a divalent organic group having 1 to 10 carbon atoms which may contain a heteroatom. }
[9]
9. The negative photosensitive material according to any one of items 1 to 8, 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. elastic resin composition.
[10]
Any one of items 1 to 9, wherein 10 mol% or more of all R ₁ and R ₂ in the polyimide precursor (A) has the heterocyclic structure and/or a structure with a high proportion of heteroatoms. The negative photosensitive resin composition according to .
[11]
(D) The negative photosensitive resin composition according to any one of Items 1 to 10, further comprising a monomer having a polymerizable functional group.
[12]
12. The negative photosensitive resin composition according to any one of items 1 to 11, wherein the (D) monomer having a polymerizable functional group has two or more polymerizable functional groups.
[13]
13. The negative photosensitive resin composition according to any one of items 1 to 12, wherein the (D) monomer having a polymerizable functional group has 3 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).
[15]
The negative photosensitive resin composition according to any one of items 1 to 14, wherein Y ₁ contains at least one selected from the group consisting of the following general formulas (12) to (15).
{In the formula, each R ₁₁ is independently a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, and each a is independently an integer of 0 to 4. }
[16]
The negative photosensitive material according to any one of items 1 to 15, further comprising (E) a thermal base generator of 0.1 parts by mass or more and 40 parts by mass or less relative to 100 parts by mass of the (A) polyimide precursor. elastic resin composition.
[17]
The following steps:
(1) applying the negative photosensitive resin composition according to any one of items 1 to 16 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a hardened relief pattern, comprising the step of heat-treating the relief pattern to form a hardened relief pattern.
[18]
A polyimide precursor comprising a structural unit represented by the following general formula (1).
{In formula (1), X ₁ is a tetravalent organic group having 4 to 40 carbon atoms which may contain a heteroatom, and Y ₁ is a divalent organic group having 6 to 40 carbon atoms which may contain a heteroatom. and R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure One selected, provided that at least one of R ₁ and R ₂ is a monovalent organic group having a heterocyclic structure. }
[19]
A polyimide precursor comprising a structural unit represented by the following general formula (1).
{In formula (1), X ₁ is a tetravalent organic group having 4 to 40 carbon atoms which may contain a heteroatom, and Y ₁ is a divalent organic group having 6 to 40 carbon atoms which may contain a heteroatom. and R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure It is one selected type, provided that at least one of OR ₁ and OR ₂ is an organic group in which the number of heteroatoms accounts for 42% or more of the constituent atoms excluding hydrogen atoms. }

According to the present disclosure, a negative photosensitive resin composition that sufficiently promotes imidization during the curing process, has good adhesion to copper wiring, and can suppress curing shrinkage during the curing process, and A method for producing a cured relief pattern using the negative photosensitive resin composition is provided.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present disclosure. Throughout this specification, structures represented by the same reference numerals in general formulas may be the same or different from each other when multiple structures exist in a molecule.

<Negative photosensitive resin composition>
The negative photosensitive resin composition of the present disclosure is
(A) a polyimide precursor containing a structural unit represented by the following general formula (1); and (B) a negative photosensitive resin composition containing a solvent.

In formula (1), X ₁ is a tetravalent organic group having 4 to 40 carbon atoms which may contain a heteroatom, and Y ₁ is a divalent organic group having 6 to 40 carbon atoms which may contain a heteroatom. and R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure It is one of the provided that 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 hetero It is a monovalent organic group having an atom number ratio (hereinafter also simply referred to as “hetero atom ratio”) of 42% or more. At least one of R ₁ and R ₂ may have a heterocyclic structure and a heteroatom ratio of 42% or more. The calculation of the heteroatom ratio includes oxygen atoms (oxygen atoms derived from side chain compounds) in the ester bonds directly bonded to R ₁ and R ₂ . Therefore, when referring to the heteroatom ratio, they are expressed as “OR ₁ ” and “OR ₂ ”.

Although not limited to theory, the negative photosensitive resin composition of the present disclosure has 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. By having an organic group having, the side chain dissociated from the polyimide precursor during the curing process remains in the polyimide film and suppresses curing shrinkage during the curing process, while suppressing the decrease in copper adhesion due to the remaining side chain. be able to. In addition, since the side chain heterocyclic ring structure and/or the organic group having a high heteroatom structure is bonded via an ester bond instead of an amide bond, inhibition of the imidization reaction during the curing process is suppressed. As a result, it is believed that the imidization is sufficiently promoted during the curing process, the adhesion to the copper wiring is good, and curing shrinkage during the curing process can be suppressed.

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

In general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties, and more preferably, -COOR ₁ group and -COOR ₂ group and -CONH- group are aromatic groups or alicyclic aliphatic groups in ortho position to each other. Examples of the tetravalent organic group represented by X ₁ include an aromatic ring-containing organic group having 6 to 40 carbon atoms, and specific examples include the following general formula (X ₁ -1) and Groups having structures represented by (X ₁ -2) may be mentioned, but not limited thereto.

In 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. A selected monovalent group, 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 may be one type or a combination of two or more types. The X ₁ group having a structure represented by each of the above formulas (X ₁ -1) and (X ₁ -2) is particularly preferable in terms of achieving both heat resistance and photosensitive properties, and more preferably the above formula ( It is a structure represented by each of X ₁ -1).

As the X ₁ group, among the structures represented by the above formula (X ₁ -1), in particular, the structures represented by the following formulas have imidization rate, degassing property, copper adhesion and chemical resistance is preferable from the viewpoint of
In the formula above, R6 and m have the same meanings as R6 and m in formula (X ₁ -1) above.

X ₁ is more preferably at least one 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.

In general formula (1) above, the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties. Structures represented by the following formulas (Y ₁ -1) and (Y ₁ -2) may be mentioned, but not limited thereto.

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. is a selected monovalent group and n is an integer selected from 0-4. Moreover, the structure of _Y1 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 formulas (Y ₁ -1) and (Y ₁ -2) is particularly preferable in terms of achieving both heat resistance and photosensitive properties, and more preferably the above formula (Y _1-1 ), respectively.

As the Y ₁ group, among the structures represented by the above formula (Y ₁ -1), in particular, the structures represented by the following formulas have imidization rate, degassing property, copper adhesion, and chemical resistance It is preferable from the viewpoint of sex.
In the above formula, R6 and n have the same meanings as R6 and n in the above formula (Y ₁ -1), respectively.

Y ₁ is more preferably at least one selected from the group consisting of the following general formulas (12) to (15) from the viewpoints of imidization rate, degassing property, copper adhesion and chemical resistance.

In formulas (12) to (15), each R ₁₁ is independently a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, such as 1 to 5 carbon atoms or 1 carbon atom. to 3 monovalent organic groups, hydrocarbon groups, or alkyl groups. a is an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, and may be 0;

At least one of R ₁ and R ₂ in the general formula (1) is a group containing a polymerizable group selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group. preferable. Here, the acid-polymerizable group, base-polymerizable group, and radical-polymerizable group refer to groups capable of being polymerized by the action of an acid, a base, or a radical, respectively.

From the viewpoint of adhesion, at least one of R ₁ and R ₂ in the polyimide precursor (A) is a monovalent organic group having a heterocyclic structure and/or a high heteroatom structure. From the viewpoint of adhesion, at least one of R ₁ and R ₂ may preferably have a heteroatom ratio of 42% or more, more preferably 43% or more, and even 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 is less than 100%, and may be, for example, 60% or less, 55% or less, or 50% or less.

R ₁ and R ₂ preferably have a heterocyclic structure and/or a high heteroatom structure, and may also have a monovalent organic group having 1 to 40 carbon atoms, from the viewpoint of resolution, The monovalent organic group having 1 to 40 carbon atoms is preferably a group represented by general formula (2) below.

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 of 1 to 10, preferably It is 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.
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 monovalent organic groups having 1 to 3 carbon atoms include methyl group, ethyl group, n-propyl group and isopropyl group. R ₃ is preferably a hydrogen atom or a methyl group, R ₄ and R ₅ are preferably hydrogen atoms.

At least one of R ₁ and R ₂ , preferably a monovalent organic group having a heterocyclic structure and/or a high heteroatom structure, is not particularly limited, but from the viewpoint of suppressing cure shrinkage during the curing process, ) It is preferable to further have an acrylic group. For example, at least one of R ₁ and R ₂ is more preferably a group represented by the following general formula (3).

In formula (3), Ar is a heterocyclic structure, the dashed line is a single bond bonding to the oxygen atom in formula (1), and R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a carbon a monovalent organic group having 1 to 3 numbers, and R ₆ and R ₇ are each independently a divalent organic group having 0 to 10 carbon atoms which may contain a heteroatom, preferably containing a heteroatom may be a divalent organic group having 1 to 10 carbon atoms, a divalent organic group having 1 to 5 carbon atoms, or a divalent organic group having 1 to 3 carbon atoms.

More specific examples of monovalent organic groups having 1 to 3 carbon atoms include methyl group, ethyl group, n-propyl group and isopropyl group. R ₃ is preferably a hydrogen atom or a methyl group, R ₄ and R ₅ are preferably hydrogen atoms. More specifically, the divalent organic group having 1 to 10 carbon atoms includes methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, and structural isomers thereof. R ₆ and R ₇ are each independently preferably a group selected from the group consisting of a divalent organic group having 1 to 3 carbon atoms containing a thioether bond, a methylene group, an ethylene group and a propylene group, more preferably is a divalent organic group having 1 to 3 carbon atoms containing a thioether bond, or a methylene group.

(A) In at least one structural unit of the polyimide precursor, at least one of R ₁ and R ₂ preferably has a (meth)acrylate group, and (A) In all structural units of the polyimide precursor, R ₁ and at least one of R ₂ more preferably has a (meth)acrylate group. (A) In at least one structural unit of the polyimide precursor, both R ₁ and R ₂ preferably have (meth)acrylate groups, and (A) In all structural units of the polyimide precursor, R ₁ and R More preferably, ₂ has a total of two or more (meth)acrylate groups. That is, R ₁ may have two or more (meth)acrylate groups and R ₂ may have no (meth)acrylate groups, or R ₁ may have no (meth)acrylate groups and R ₂ may have two or more (meth)acrylate groups, or R ₁ has one or more (meth)acrylate groups and R ₂ also has one or more (meth)acrylate groups By that is meant that R ₁ and R ₂ have in total two or more (meth)acrylate groups. The reason why at least one of R ₁ and R ₂ , preferably a side chain having a heterocyclic structure and/or a high heteroatom structure, has a (meth)acrylic group suppresses cure shrinkage during the curing process. Although not limited to theory, the inventors believe that thermal polymerization of the (meth)acrylic group suppresses volatilization of the photosensitive side chains separated from the polyimide precursor during the curing process, thereby suppressing curing shrinkage. I think that it is because it is done.

From the viewpoint of adhesion, at least one of R ₁ and R ₂ , preferably a monovalent organic group having a heterocyclic structure and/or a high heteroatom structure, is a monovalent organic group having a heterocyclic structure containing a nitrogen atom. is preferably a group, and more preferably a monovalent organic group having a 5-membered heterocyclic ring 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, the ratio of monovalent organic groups having a heterocyclic structure and/or a high heteroatom structure is preferably 10 mol % or more based on the total number of moles of R ₁ and R ₂ . By introducing 10 mol % or more, copper adhesion is further improved.

(A) Method for preparing a polyimide precursor (A) As a method for preparing a polyimide precursor, for example, a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group X ₁ , an acid polymerizable group, and a base polymerization A partially esterified tetracarboxylic acid (hereinafter referred to as an acid/ester form ) is prepared. Then, a partially esterified tetracarboxylic acid (acid/ester form) and a diamine containing the divalent organic group _Y1 described above are subjected to amide polycondensation to obtain (A) a polyimide precursor. mentioned. Methods for introducing a heterocyclic structure and/or a high heteroatom structure into at least one of R ₁ and R ₂ include, for example, a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group X ₁ and the above-mentioned A tetracarboxylic acid (acid/ester form) having a heterocyclic structure and/or a high heteroatom structure is prepared by reacting an alcohol having a heterocyclic structure and/or a high heteroatom structure in addition to the alcohol. Next, the polyimide precursor (A) of the present disclosure is obtained by subjecting the obtained tetracarboxylic acid (acid/ester form) and the diamine containing the divalent organic group _Y1 to amide polycondensation.

(Preparation of acid/ester form)
(A) As a tetracarboxylic dianhydride containing a tetravalent organic group _X1 , which is preferably used for preparing a polyimide precursor, a compound represented by the following formula is preferable.
In the above formula, X ₁ is as defined in general formula (1) above. This X ₁ is more preferably selected from the structures represented by the general formulas (X ₁ -1) and (X ₁ -2), and is represented by the general formula (X ₁ -1) Structures are more preferred.

As the tetracarboxylic dianhydride, particularly preferably, for example, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (also known as oxydiphthalic dianhydride, abbreviated as "ODPA") ), benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, biphenyl-3,3′,4,4′-tetracarboxylic dianhydride (abbreviated as “BPDA”), diphenylsulfone-3 ,3′,4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3′,4,4′-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane , 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane and the like. Pyromellitic anhydride, diphenyl ether-3,3′,4,4′-tetracarboxylic dianhydride, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, and biphenyl-3 are particularly preferred. ,3′,4,4′-tetracarboxylic dianhydrides, but are not limited to these. These may be used alone, or may be used in combination of two or more.

(A) Alcohol having a polymerizable group selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group, which is suitably used for preparing a polyimide precursor, includes, for example, 2 -hydroxyethyl methacrylate, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2 -hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl Acrylates, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy -3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, Glycerol diacrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate and the like can be mentioned.

(A) The alcohol having a heterocyclic structure, which is suitably used for preparing the polyimide precursor, includes an alcohol having a hydroxyl group and a heterocyclic ring. Examples of alcohols having a hydroxyl group and a heterocyclic ring include, but are not limited to, N-(2-hydroxyethyl)phthalimide, 3-furanmethanol, 2,4-dimethyl-6-hydroxypyrimidine, 2-hydroxymethyl-1-methyl imidazole, 7-ethyl-3-indoleethanol, hymexazole, (5-phenylisoxazol-3-yl)methanol, methyl 3-hydroxyisoxazole-5-carboxylate, carazolol and the like. Among these, the alcohol having a heterocyclic structure is preferably an alcohol having a heterocyclic ring and a (meth)acryl group. A compound having a heterocyclic ring and a (meth)acryl group can be synthesized, for example, from an epoxy compound and a heterocyclic compound having a nucleophilic functional group such as a sulfide group, a carboxyl group and a hydroxyl group. Epoxy compounds include, but are not limited to, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether (eg, available from Mitsubishi Chemical Corporation), and the like. Heterocyclic compounds having a nucleophilic functional group include, but are not limited to, 3-mercaptotriazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-mercapto-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-methoxy Phenyl)-1H-tetrazole, 1-(3-acetamidophenyl)-5-mercaptotetrazole, 5-benzotriazolecarboxylic acid, N-phthaloylglycine, 1H-benzotriazole-1-methanol, 3-mercapto-1,2 , 4-triazole, 1-methylpyrazole-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, and the like.

The above tetracarboxylic dianhydride and alcohol are stirred in a solvent to dissolve and mix, so that the esterification reaction of the acid anhydride group of the tetracarboxylic dianhydride proceeds to form the desired acid. / ester can be obtained. The reaction is preferably carried out in the presence of a suitable basic catalyst such as pyridine. Although the reaction conditions are not limited, for example, it is preferable to carry out the reaction at a temperature of 20° C. to 50° C. for 4 to 10 hours.

(Preparation of polyimide precursor)
To the above acid/ester form (typically in the form of a solution dissolved in a solvent described below), under ice cooling, a suitable dehydration condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2 -Dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. are added and mixed to convert the acid/ester into polyanhydride. can do. A diamine containing a divalent organic group Y ₁ is separately dissolved or dispersed in a solvent and added dropwise to the solution containing the polyanhydride, and amide polycondensation is performed to obtain the desired polyimide precursor. can be done. 1-Hydroxybenzotriazole or the like may also be used depending on the reactivity of the substrate. Alternatively, the acid moiety of the acid/ester compound is acid chlorided using thionyl chloride or the like, and then reacted with a diamine in the presence of a base such as pyridine to obtain the desired polyimide precursor. Obtainable.

Diamines containing a divalent organic group Y ₁ include those of the formula:
_{H2NY1 - NH2}
{In the formula, Y ₁ is defined in the above general formula (1). } is preferred. Y ₁ more preferably has a structure represented by each of the general formulas (Y ₁ -1) and (Y ₁ -2).

More preferred diamines include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (also known as 4,4'-oxydianiline, abbreviated as "ODA"), and 3,4'-diaminodiphenyl ether. , 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,4′- Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'- diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1, 3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl] Sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-amino phenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis (4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-( 4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolysine sulfone, 9,9-bis(4-aminophenyl)fluorene, etc., and their benzene rings Part of the above hydrogen atoms are substituted with a methyl group, ethyl group, hydroxymethyl group, hydroxyethyl group, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4 ,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl and the like, but are not limited thereto. These can be used alone, or two or more of them may be mixed and used.

After the completion of the amide polycondensation reaction, water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are filtered off if necessary, and a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is obtained. It is put into the obtained polymer component, the polymer component is precipitated, and the polymer is purified by repeating redissolution, reprecipitation, etc., and vacuum drying is performed to isolate the desired polyimide precursor. can do. In order to improve the degree of purification, the polymer solution is passed through a column filled with an anion exchange resin or a cation exchange resin or both of them swollen with a suitable organic solvent to remove ionic impurities. good too.

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

(A) As the polyimide precursor, a non-photosensitive polyimide precursor prepared using only the alcohol having no polymerizable group may be used by mixing with a photosensitive polyimide precursor. In this case, from the viewpoint of resolution, the 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 Solvents include amides, sulfoxides, urea and derivatives thereof, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. Specifically, for example, N-methyl-2 -pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate , ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene and the like can be used. Among them, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol, from the viewpoint of resin solubility and resin composition stability. One or more selected from the group consisting of monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

Among such solvents, those that completely dissolve (A) the polyimide precursor are particularly preferred, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl Sulfoxide, tetramethylurea, gamma-butyrolactone and the like are preferred. More preferably, the solvent is a solvent other than an amide solvent. Due to its strong interaction, amide-based solvents may inhibit the interaction between the substrate and the polymer, thereby reducing the adhesion to the substrate. Therefore, among the above solvents, at least one solvent selected from the group consisting of dimethylsulfoxide, tetramethylurea, and gamma-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, or 125 parts by mass or more and 500 parts by mass or less may be included.

(C) Photopolymerization Initiator The negative photosensitive resin composition of the present disclosure may further contain (C) a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator or a photoacid generator.

Examples of photoradical polymerization initiators include benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, and fluorenone, 2,2′-diethoxyacetophenone, 2 - acetophenone compounds such as hydroxy-2-methylpropiophenone and 1-hydroxycyclohexylphenyl ketone; thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; benzyl, benzyldimethylketal, benzyl-β- benzyl compounds such as 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, oxime compounds such as 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-aryls such as N-phenylglycine glycine compounds; peroxides such as benzoyl perchloride, aromatic biimidazole compounds, titanocene compounds, and the like.

(C) The photopolymerization initiator is not limited to those exemplified above. Among the above photopolymerization initiators, photoradical polymerization initiators are more preferred, and oxime compounds are even more preferred in terms of photosensitivity.

When the negative photosensitive resin composition contains (C) a photopolymerization initiator, the amount is preferably 0.1 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of (A) the polyimide precursor, or It is 1 part by mass or more and 8 parts by mass or less. (C) When the amount of the photopolymerization initiator is 0.1 parts by mass or more, the photosensitivity or patterning property is improved, and when it is 20 parts by mass or less, the photosensitivity after curing of the negative photosensitive resin composition The physical properties of the elastic resin layer tend to be improved.

(D) Photopolymerizable Monomer The negative photosensitive resin composition contains a monomer having a photopolymerizable unsaturated bond (also simply referred to as a “polymerizable functional group”) in order to improve the resolution of the relief pattern. (also simply referred to as "photopolymerizable monomer") may optionally be included. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following. Examples include ethylene glycol monoacrylate, diacrylate, monomethacrylate, and Dimethacrylates; Polyethylene glycol monoacrylates, diacrylates, monomethacrylates and dimethacrylates; Propylene glycol monoacrylates, diacrylates, monomethacrylates and dimethacrylates; Polypropylene glycol monoacrylates, diacrylates, monomethacrylates; and dimethacrylates; monoacrylates, diacrylates, triacrylates, monomethacrylates, dimethacrylates and trimethacrylates of glycerol; diacrylates and dimethacrylates of cyclohexane; diacrylates and dimethacrylates of 1,4-butanediol; diacrylates and dimethacrylates of neopentyl glycol; monoacrylates, diacrylates, monomethacrylates and dimethacrylates of bisphenol A; benzene trimethacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; diacrylates, triacrylates, tetraacrylates, dimethacrylates, trimethacrylates, and tetramethacrylates of pentaerythritol; and compounds such as ethylene oxide adducts or propylene oxide adducts of these compounds.

The (D) photopolymerizable monomer preferably has two or more polymerizable functional groups, and more preferably three or more polymerizable functional groups, because curing shrinkage during curing is small.

When the negative photosensitive resin composition contains the photopolymerizable unsaturated monomer for improving the resolution of the relief pattern, the amount of the photopolymerizable unsaturated monomer is (A) the polyimide precursor It is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the body.

(E) Thermal base generator The negative photosensitive resin composition may contain (E) a thermal base generator. A thermal base generator is 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 promoted. This can improve adhesion during low-temperature curing.

The type of thermal base generator is not particularly limited, but amine compounds protected by a tert-butoxycarbonyl group, and thermal base generators shown in Patent Documents 3 and 4 can be mentioned. However, it is not limited to these, and other known thermal base generators can be used.

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

As a thermal base generator compound having a urea structure, for example, as described in Patent Document 4,
etc., but not limited to these.

When the negative photosensitive resin composition contains (E) a thermal base generator, the amount thereof is preferably 0.1 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of (A) the polyimide precursor. more preferably 0.5 to 30 parts by mass, still more preferably 1 to 25 parts by mass, for example, 0.5 to 20 parts by mass. The above compounding amount is 0.1 parts by mass or more from the viewpoint of the imidization promoting effect, and preferably 30 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition. .

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

Corrosion preventive agent When a negative photosensitive resin composition is used to form a cured film on a substrate made of copper or a copper alloy, the negative photosensitive resin composition should be added to prevent discoloration of the copper. A rust agent may optionally be included. Examples of rust preventives include azole compounds and purine compounds.

Azole compounds include, for example, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl -2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, Hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like.

Particularly preferred are 5-amino-1H-tetrazole, tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. These azole compounds may be used singly or as a mixture of two or more.

Specific examples of purine compounds include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyl adenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-amino Adenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3- chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, etc., and derivatives thereof is mentioned.

When the negative photosensitive resin composition contains a rust preventive, the compounding amount is preferably 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, and 0.03 mass parts Part or more and 10 mass parts or less are more preferable, 0.05 mass parts or more and 5 mass parts or less are still more preferable, and for example, it may be 0.01 mass parts or more and 5 mass parts or less. When the amount of the antirust agent (A) per 100 parts by mass of the polyimide precursor is 0.01 parts by mass or more, when the negative photosensitive resin composition is formed on copper or a copper alloy, copper or copper Discoloration of the alloy surface is suppressed, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent.

Hindered Phenolic Compound The negative-acting photosensitive resin composition may optionally contain a hindered phenolic compound to inhibit discoloration on the copper surface. Hindered phenol compounds include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 -thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy- hydrocinnamamide), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl- tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3, 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2, 6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6 -dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6 -trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy -2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl -3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6 -ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t -butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4 -t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4 -t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like, which include It is not limited. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione and the like are particularly preferred.

When the negative photosensitive resin composition contains a hindered phenol compound, the amount is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, and 0.5 parts by mass Parts or more and 10 mass parts or less are more preferable. When the amount of the hindered phenol compound (A) per 100 parts by mass of the polyimide precursor is 0.1 parts by mass or more, for example, when a negative photosensitive resin composition is formed on copper or a copper alloy, copper Alternatively, discoloration and corrosion of the copper alloy are prevented, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent.

Organotitanium compound The negative photosensitive resin composition may contain an organotitanium compound. When the negative photosensitive resin composition contains an organic titanium compound, it is possible to form a photosensitive resin layer having excellent chemical resistance even when cured at a low temperature.

Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds. Specific examples of organotitanium compounds are shown below in I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the negative photosensitive resin composition is good and a good curing pattern can be obtained. Specific examples are titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate) , titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
II) Tetraalkoxytitanium compounds: for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide. , titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl) butoxide}] and the like.
III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η ⁵ - 2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium;
IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide and the like.
V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate.
VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

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

When the negative photosensitive resin composition contains an organic titanium compound, the amount thereof is preferably 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, and 0.1 part by mass. More than 2 mass parts or less is more preferable. When the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance, while when it is 10 parts by mass or less, the negative photosensitive resin composition is storage stable. Excellent in nature.

Adhesion Aid The negative photosensitive resin composition may optionally contain an adhesion aid in order to improve the adhesion between the film formed using the negative photosensitive resin composition and the substrate. As the adhesion aid, an aluminum-based adhesion aid, a silane coupling agent, or the like can be used.

Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

Silane coupling agents include, for example, γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane. , 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxy Propylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl] propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane ( Shin-Etsu Chemical Co., Ltd.: product name KBM803, Chisso Corporation: product name Sila Ace S810), 3-mercaptopropyltriethoxysilane (Azmax Co., Ltd.: product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane ( Shin-Etsu Chemical Co., Ltd.: product name LS1375, Azmax Co., Ltd.: product name SIM6474.0), Mercaptomethyltrimethoxysilane (Azmax Co., Ltd.: product name SIM6473.5C), Mercaptomethylmethyldimethoxysilane (Azmax Co., Ltd.) Manufacturer: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane Silane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane Silane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane Silane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, Azmax Co., Ltd.: trade name SIU9055.0), N-(3- trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tri Propoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxy Dipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxy silylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxy silylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (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 SLA0599.1), aminophenyltrimethoxysilane (Azmax Co., Ltd.: trade name SLA0599.1) Co., Ltd.: trade name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl) ) pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra- n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane), Tetrakis(ethoxyethoxysilane), Tetrakis(methoxyethoxyethoxysilane), Bis(trimethoxysilyl)ethane, Bis(trimethoxysilyl)hexane, Bis(triethoxysilyl)methane, Bis(triethoxysilyl)ethane, Bis(tri ethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di- t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylciphenylsilane diol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethyl isopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol and the like. In addition, silane coupling agents having structures represented by the following formula (S-1) are also included, but are not limited to these.

Among these adhesion aids, the silane coupling agent is more preferable from the point of adhesion. As the silane coupling agent, among the silane coupling agents described above, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxy It is preferable to use one or more selected from the group consisting of diphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and silane coupling agents having structures represented by the formula (S-1) above. .

When the negative photosensitive resin composition contains an adhesion aid, the amount of the adhesion aid is preferably 0.01 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of (A) the polyimide precursor, or 0.5 parts by mass or more and 20 parts by mass or less is more preferable. When the silane coupling agent is used, the blending amount is preferably 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyimide precursor (A).

Sensitizer The negative photosensitive resin composition may optionally contain a sensitizer in order to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal). ) cyclohexanone, 2,6-bis(4′-diethylaminobenzal)-4-methylcyclohexanone, 4,4′-bis(dimethylamino)chalcone, 4,4′-bis(diethylamino)chalcone, p-dimethylamino thinner mylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylamino) styryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene and the like. These can be used singly or in combination, for example of 2 to 5 types.

When the negative photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount is 0.1 parts by mass or more and 25 parts by mass with respect to 100 parts by mass of (A) the polyimide precursor The following are preferable.

Thermal polymerization inhibitor The negative photosensitive resin composition may optionally contain a thermal polymerization inhibitor in order to improve the stability of viscosity and photosensitivity, especially when stored in a solvent-containing solution. Thermal polymerization inhibitors include, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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 and the like can be used.

<Method for manufacturing cured relief pattern>
The method of manufacturing the cured relief pattern of the present disclosure comprises:
(1) a step of applying the above-described negative photosensitive resin composition of the present disclosure onto a substrate to form a photosensitive resin layer on the substrate (resin layer forming step);
(2) a step of exposing the photosensitive resin layer (exposure step);
(3) a step of developing the exposed photosensitive resin layer to form a relief pattern (step of forming a relief pattern);
(4) A step of heat-treating the relief pattern to form a cured relief pattern (a step of forming a cured relief pattern).

(1) Resin Layer Forming Step In this step, a negative photosensitive resin composition is applied onto a substrate and, if necessary, dried to form a photosensitive resin layer. Examples of the coating method include methods conventionally used for coating negative photosensitive resin compositions, such as spin coaters, bar coaters, blade coaters, curtain coaters, screen printers, and spraying with a spray coater. A coating method or the like can be used.

If necessary, the coating film containing the negative photosensitive resin composition can be dried. As a drying method, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are 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. As described above, a photosensitive resin layer can be formed on the substrate.

(2) Exposure step In this step, the photosensitive resin layer formed above is exposed to an ultraviolet light source directly or via a photomask or reticle having a pattern using an exposure device such as a contact aligner, mirror projection, or stepper. and so on. By this exposure, the polymerizable groups of (A) the polyimide precursor contained in the negative photosensitive resin composition are crosslinked by the action of (C) the photopolymerization initiator. This cross-linking renders the exposed portion insoluble in a developing solution, which will be described later, so that a relief pattern can be formed.

After that, for the purpose of improving photosensitivity, if necessary, post-exposure baking (PEB) or pre-development baking or both of these may be performed at any combination of temperature and time. The baking conditions are preferably a temperature of 40° C. to 120° C. and a time of 10 seconds to 240 seconds. The range is not limited.

(3) Relief Pattern Forming Step In this step, the unexposed portion of the exposed photosensitive resin layer is removed by development. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of conventionally known photoresist developing methods such as a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like can be used. method can be selected and used. After development, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking may be performed at any combination of temperature and time, if necessary.

A developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like. . Preferred examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Two or more kinds of solvents, for example, several kinds of solvents can be used in combination.

(4) Cured Relief Pattern Forming Step In this step, the relief pattern obtained by the above development is heat-treated to dilute the photosensitive component, and (A) the polyimide precursor is imidized to form a polyimide. Converts to a cured relief pattern. As the heat treatment method, various methods can be selected, such as a method using a hot plate, a method using an oven, and a method using a heating oven capable of setting a temperature program. The heat treatment can be performed, for example, at 160° C. to 350° C. for 30 minutes to 5 hours. The temperature of the heat treatment is preferably 200° C. or lower, more preferably 180° C. or lower. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

In addition, the photosensitive resin layer after exposure has a crosslinked structure formed by crosslinking the polymerizable groups of the (A) polyimide precursor. However, this crosslinked structure is eliminated from the polymer during heating in the step of forming the cured relief pattern, and the amic acid structure generated by the elimination closes the ring to form an imide ring structure, thereby forming a cured relief pattern made of polyimide. It is considered to be obtained.

<Polyimide cured film>
The present disclosure also provides a cured film formed from the negative photosensitive resin composition of the present disclosure. A cured film formed from the above negative photosensitive resin composition is considered to contain a polyimide having a structure represented by the following general formula (4).

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

<Semiconductor device>
The present disclosure also provides a semiconductor device having a cured relief pattern obtained from the negative-acting photosensitive resin composition described above. Specifically, a semiconductor device is provided having a substrate that is a semiconductor element and a cured relief pattern. The cured relief pattern may be produced by the method for producing a cured relief pattern described above using the negative photosensitive resin composition described above.
The present disclosure also provides a method of manufacturing a semiconductor device using a semiconductor element as a base material and including the above-described method of manufacturing a cured relief pattern of the present embodiment as part of the process. In this case, the cured relief pattern formed by the method for manufacturing a cured relief pattern of the present disclosure has a surface protective film of a semiconductor device, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure. It can be manufactured by forming it as a protective film or the like for a semiconductor device and combining it with a known method for manufacturing a semiconductor device.

<Display device>
The present disclosure also provides a display device comprising a display element and a cured film provided on top of the display element, wherein the cured film is the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. The cured film is applied to, for example, surface protective films, insulating films, flattening films, etc. of TFT liquid crystal display elements and color filter elements; projections for MVA type liquid crystal display devices; barrier ribs for cathodes of organic EL elements; be able to.

The negative photosensitive resin composition of the present disclosure, in addition to application to the above semiconductor devices, is also used for interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, etc. Useful.

EXAMPLES The embodiments of the present disclosure will be specifically described below with reference to Examples, but the present disclosure is not limited thereto. In Examples, Comparative Examples, and Production Examples, physical properties of polyimide precursors or negative photosensitive resin compositions were measured and evaluated according to the following methods.

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

(2) Preparation of a cured film on Cu On a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm), a sputtering device (L-440S-FHL type, manufactured by Canon Anelva) is used to make a thickness of 200 nm. of Ti and 400 nm thick Cu were sputtered in this order. Subsequently, on this wafer, a negative photosensitive resin composition prepared by the method described later was spin-coated using a coater developer (D-Spin60A type, manufactured by SOKUDO), and coated on a hot plate at 110° C. for 180 seconds. Pre-baking was performed to form a coating film. The obtained coating film is heated using a temperature-rising programmable curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.) under a nitrogen atmosphere at the temperatures shown in Tables 2 and 3 for 2 hours. A cured film of resin having a thickness of about 10 μm was obtained.

(3) Evaluation of copper adhesion A cured film obtained by treating a negative photosensitive resin composition prepared by the method described below was subjected to a copper substrate / Adhesive properties between cured resin coating films were evaluated based on the following criteria.
A: The lattice number of the cured resin coating adhered to the substrate is 80 or more and 100 or less B: The lattice number of the cured resin coating adhered to the substrate is 60 or more and less than 80 C: The cured resin adhered to the substrate Lattice number of the coating film is 40 or more and less than 60 D: The lattice number of the cured resin coating adhered to the substrate is less than 40

(4) Evaluation of residual film ratio after curing The residual film ratio of the cured film obtained in (2) was calculated according to the following definition.
Remaining film rate after curing [%] = (film thickness after curing [μm]) ÷ (film thickness before curing [μm]) × 100
The residual film ratio obtained by the above formula was evaluated according to the following criteria.
AA: Remaining film ratio after curing is 93% or more A: Remaining film ratio after curing is 90% or more and less than 93% B: Remaining film ratio after curing is 85% or more and less than 90% C: Remaining film ratio after curing is 80% or more less than 85%

The film thickness after curing and the film thickness before curing were measured using a stylus type profiler (trade name “P-17” manufactured by Tencor).

(5) Measurement of imidization rate The cured relief pattern resin part was measured using a Si prism with an ATR-FTIR measurement device (Nicolet Continuum, manufactured by Thermo Fisher Scientific), and the peak intensity at 1380 cm ^-1 was 1500 cm ^-1 . The value obtained by dividing by the peak intensity of the imidization index is obtained by dividing the imidization index of the film of each example and comparative example by the imidization index of the film obtained by curing the corresponding resin composition at 350 ° C. calculated as The imidization rate was evaluated based on the following criteria.
A: imidization rate is 95% or more B: imidization rate is 90% or more and less than 95% C: imidization rate is 80% or more and less than 90% D: imidization rate is 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) of triethylamine (TEA) were placed in a 100 mL three-necked flask, to which 3-mercaptotriazole 6 was added. .27 g (0.062 mol) was added dropwise and stirred overnight to obtain a γ-butyrolactone solution of heterocyclic compound 1. Heterocyclic compound 1 is a compound shown below. The heteroatom ratio of the heterocyclic compound 1 is such that the number of atoms excluding hydrogen atoms among the constituent atoms is 3 N atoms, 1 S atom, 3 O atoms, and 9 C atoms, so {( 3+1+3)/(3+1+3+9)}×100=44%. It is shown in Table 1 as "percentage of heteroatoms in side chain compounds". The same applies to other side chain compounds below.

((A) Synthesis of polymer A-1 as polyimide precursor)
31.0 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 1 L separable flask, and 40.0 g of γ-butyrolactone was added. 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. was added, and the mixture was stirred overnight at room temperature.

Next, while stirring the resulting reaction mixture, 30.0 g (0.20 mol) of 1-hydroxybenzoxazole (HOBt) was added, and then 40.4 g (0.20 mol) of dicyclohexylcarbodiimide (DCC) was added under ice cooling. in 40.0 g of γ-butyrolactone was added over 20 minutes, followed by 35.2 g (0.09 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP). A suspension in 35.0 g of gamma-butyrolactone was added over 20 minutes. After stirring at room temperature for 4 hours, 18 g of ethyl alcohol was added and the mixture was further stirred for 1 hour, then 140 g of γ-butyrolactone was added. The reaction mixture was filtered to remove the precipitate generated in the reaction system to obtain a reaction liquid.

The resulting reaction solution was added to 1.2 kg of ethyl alcohol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 300 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 2.0 kg of water to reprecipitate the polymer. The resulting reprecipitate was collected by filtration and dried in a vacuum to obtain a powdery polymer (polymer A-1). When the molecular weight of polymer A-1 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 15,000.

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

<Synthesis Example 3>
((A) Synthesis of polymer A-3 as polyimide precursor)
Instead of 31.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Synthesis Example 1, Synthesis Example 1 described above was used except that 21.8 g (0.1 mol) of pyrrolimethic anhydride (PMDA) was used. A polymer A-3 was obtained by carrying out the reaction in the same manner as described in . When the molecular weight of polymer A-3 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 16,000.

<Synthesis Example 4>
((A) Synthesis of polymer A-4 as polyimide precursor)
Instead of 31.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Synthesis Example 1, except that 29.4 g (0.1 mol) of 4-4'-biphthalic anhydride (hereinafter referred to as BPDA) was used. , and the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer A-4. When the molecular weight of polymer A-4 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 15,000.

<Synthesis Example 5>
((A) Synthesis of polymer A-5 as polyimide precursor)
In place of 31.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Synthesis Example 1, 52 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (hereinafter BisDA) was used. Except for using 0 g (0.1 mol), the reaction was carried out in the same manner as described in Synthesis Example 1 above to obtain polymer A-5. When the molecular weight of polymer A-5 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 18,000.

<Synthesis Example 6>
((A) Synthesis of polymer A-6 as polyimide precursor)
Except that 17.2 g (0.083 mol) of 4,4-diaminodiphenyl ether was used in place of 35.2 g of BAPP in Synthesis Example 1, the reaction was carried out in the same manner as in Synthesis Example 1 to give polymer A- got 6. When the molecular weight of polymer A-6 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 17,000.

<Synthesis Example 7>
((A) Synthesis of polymer A-7 as polyimide precursor)
Except for using 17.7 g (0.083 mol) of m-tolidine instead of 35.2 g of BAPP in Synthesis Example 1, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain polymer A-7. Ta. When the molecular weight of polymer A-7 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 17,000.

<Synthesis Example 8>
((A) Synthesis of polymer A-8 as polyimide precursor)
Except for using 9.0 g (0.083 mol) of p-phenylenediamine instead of 35.2 g of BAPP in Synthesis Example 1, the reaction was carried out in the same manner as in Synthesis Example 1 described above to give polymer A-8. Obtained. When the molecular weight of polymer A-8 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 18,000.

<Synthesis Example 9>
(Synthesis of heterocyclic compound 2)
8.81 g of GMA, 30.0 g of γ-butyrolactone and 0.63 g of triethylamine (TEA) were placed in a 100 mL three-necked flask, to which 7.20 g of 5-mercapto-1-methyltetrazole was added and stirred overnight to give a complex. A γ-butyrolactone solution of ring compound 2 was obtained. Heterocyclic compound 2 is a compound shown below.

((A) Synthesis of polymer A-9 as polyimide precursor)
Instead of 50.9 g of the γ-butyrolactone solution of the heterocyclic compound 1 in Synthesis Example 1, 51.8 g of the γ-butyrolactone solution of the heterocyclic compound 2 was used, and HOBt was changed to 0 g (not used). The reaction was carried out in the same manner as described in Synthesis Example 1 above to obtain polymer A-9. When the molecular weight of polymer A-9 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.

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

<Synthesis Example 11>
((A) Synthesis of polymer A-11 as polyimide precursor)
50.9 g of a γ-butyrolactone solution of heterocyclic compound 1 of Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) was added to N-(2-hydroxyethyl)phthalimide (NHPA, "heterocyclic compound 3" in the table).11. Polymer A-11 was obtained in the same manner as in Synthesis Example 1 except that HOBt was changed to 9 g (0.062 mol) and HOBt 30.0 g was changed to 0 g (not used). When the molecular weight of polymer A-11 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 18,000.

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

<Synthesis Example 13>
((A) Synthesis of polymer A-13 as polyimide precursor)
50.9 g of γ-butyrolactone solution of heterocyclic compound 1 of Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) was added to 6.08 g (0.062 mol) of 3-furan methanol (“heterocyclic compound 4” in the table). Polymer A-13 was obtained by carrying out the reaction in the same manner as in Synthesis Example 1, except that HOBt (30.0 g) was changed to 0 g (not used). When the molecular weight of polymer A-13 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 23,000.

<Synthesis Example 14>
((A) Synthesis of polymer A-14 as polyimide precursor)
50.9 g of a γ-butyrolactone solution of heterocyclic compound 1 of Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) was added to 7.70 g of 2,4-dimethyl-6-hydroxypyrimidine (“heterocyclic compound 5” in the table). (0.062 mol), and 30.0 g of HOBt was changed to 0 g (not used), but the reaction was carried out in the same manner as in Synthesis Example 1 to obtain polymer A-14. When the molecular weight of polymer A-14 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 15,000.

<Synthesis Example 15>
((A) Synthesis of polymer A-15 as polyimide precursor)
50.9 g of a γ-butyrolactone solution of heterocyclic compound 1 of Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) was added to 6.95 g of 2-hydroxymethyl-1-methylimidazole (“heterocyclic compound 6” in the table) ( 0.062 mol) and 30.0 g of HOBt was changed to 0 g (not used), but the reaction was carried out in the same manner as in Synthesis Example 1 to obtain polymer A-15. When the molecular weight of polymer A-15 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 24,000.

<Synthesis Example 16>
((A) Synthesis of polymer A-16 as polyimide precursor)
50.9 g of a γ-butyrolactone solution of heterocyclic compound 1 of Synthesis Example 1 (heterocyclic compound 1: 0.062 mol) was added to 11.7 g (0 .062 mol) and 30.0 g of HOBt was changed to 0 g (not used), but the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer A-16. When the molecular weight of polymer A-16 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 22,000.

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

Next, a solution of 40.4 g of DCC dissolved in 40 g of γ-butyrolactone was added over 40 minutes to the reaction mixture while stirring, and then 35.2 g (0.086 mol) of BAPP was added to the γ- A suspension in 35.0 g of butyrolactone was added over 20 minutes. After stirring at room temperature for 4 hours, 9.0 g of ethyl alcohol was added and the mixture was further stirred for 1 hour, then 140 g of γ-butyrolactone was added. The reaction mixture was filtered to remove the precipitate generated in the reaction system to obtain a reaction liquid.

The resulting reaction solution was added to 600 g of ethyl alcohol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 300 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 1 kg of water to reprecipitate the polymer. The resulting reprecipitate was collected by filtration and dried in a vacuum to obtain a powdery polymer (Polymer A-17). When the molecular weight of polymer A-17 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 25,000.

<Synthesis Example 18>
((A) Synthesis of polymer A-18 as polyimide precursor)
The reaction was carried out in the same manner as in Synthesis Example 1 above, except that 35.2 g (0.09 mol) of BAPP in Synthesis Example 1 was changed to 22.3 g (0.09 mol) of bis(3-aminophenyl)sulfone. to give polymer A-18. When the molecular weight of polymer A-18 was measured by gel permeation chromatography (converted to standard polystyrene), 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 placed in a 100 mL three-necked flask and cooled to 0°C. To this was added dropwise 15.5 g of Karenz MOI (trade name; Showa Denko KK) to obtain a γ-butyrolactone solution of urea compound 1. Urea compound 1 is a compound shown below.

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

Next, a solution of 40.7 g of dicyclohexylcarbodiimide (DCC) dissolved in 50 g of γ-butyrolactone was added to the reaction mixture under ice-cooling with stirring over 40 minutes, followed by 35.2 g of BAPP (0. 086 mol) in 150 g of γ-butyrolactone was added over 60 minutes. After stirring for 2 hours at room temperature, 9.0 g of ethyl alcohol was added and the mixture was further stirred for 1 hour, then 70 g of γ-butyrolactone was added. The reaction mixture was filtered to remove the precipitate generated in the reaction system to obtain a reaction liquid.

The resulting reaction solution was added to 1.2 kg of ethyl alcohol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 300 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 3.5 kg of water to reprecipitate the polymer. The resulting reprecipitate was collected by filtration and dried in a vacuum to obtain a powdery polymer (Polymer A-19). When the molecular weight of polymer A-19 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 29,000.

<Synthesis Example 20>
((A) Synthesis of polymer A-20 as polyimide precursor)
Except that 50.9 g of the γ-butyrolactone solution of heterocyclic compound 1 in Synthesis Example 1 was replaced with 10.80 g of 1-(4-aminobenzyl)-1,2,4-triazole (heterocyclic compound 1: 0.062 mol). was reacted in the same manner as described in Synthesis Example 1 above to obtain polymer A-20. When the molecular weight of polymer A-20 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 14,000.

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

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

<Example 3>
Using the polyimide precursor A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) A-1: 100 g as a polyimide precursor, (C) 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime as a photopolymerization initiator (hereinafter referred to as PDO, C -1): 3 g, (D) 20 g of pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd. A-TMMT) as a polymerizable monomer (D-1) is dissolved in γ-butyl lactone (hereinafter referred to as GBL): 100 g did. The viscosity of the resulting solution was adjusted to about 40 poise by further adding a small amount of GBL to prepare a negative photosensitive resin composition. The composition was evaluated according to the method described above.

<Examples 4 to 23, Comparative Examples 1 to 5>
Polymers, photoinitiators, polymerizable monomers, and solvents as shown in Tables 2 and 3 were used, but the same negative photosensitive resin compositions as in Examples 1 to 3 were prepared and evaluated according to the methods described above. .

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

C-1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (PDO)
D-1: pentaerythritol tetraacrylate D-2: 2-hydroxyethyl methacrylate D-3: tricyclodecane dimethanol diacrylate (Shin Nakamura Chemical Industry A-DCP)
D-4: Dipentaerythritol polyacrylate (Shin Nakamura Chemical Co., Ltd. A-DPH)
E-1: A compound represented by the following formula.

By using the negative photosensitive resin composition according to the present disclosure, it is possible to obtain a cured relief pattern with high adhesion to copper and little shrinkage of the film in the heating process after thermosetting. INDUSTRIAL APPLICABILITY The negative photosensitive resin composition of the present disclosure can be suitably used in the field of photosensitive materials useful for producing electric/electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (19)

(A) a polyimide precursor containing a structural unit represented by the following general formula (1); and (B) a negative photosensitive resin composition containing a solvent.
{In formula (1), X ₁ is a tetravalent organic group having 4 to 40 carbon atoms which may contain a heteroatom, and Y ₁ is a divalent organic group having 6 to 40 carbon atoms which may contain a heteroatom. and R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure One selected, provided that at least one of R ₁ and R ₂ is a monovalent organic group having a heterocyclic structure. } (A) a polyimide precursor containing a structural unit represented by the following general formula (1); and (B) a negative photosensitive resin composition containing a solvent.
{In formula (1), X ₁ is a tetravalent organic group having 4 to 40 carbon atoms which may contain a heteroatom, and Y ₁ is a divalent organic group having 6 to 40 carbon atoms which may contain a heteroatom. and R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure It is one selected type, provided that at least one of OR ₁ and OR ₂ is a monovalent organic group in which the number of heteroatoms accounts for 42% or more of the constituent atoms excluding hydrogen atoms. } 3. The negative photosensitive resin composition according to claim 1, further comprising (C) a photopolymerization initiator. The negative photosensitive resin composition according to claim ₁ or ₂ , wherein at least one of R1 and R2 is a monovalent organic group having a heterocyclic structure containing a nitrogen atom. The negative photosensitive resin composition according to claim ₁ or ₂ , wherein at least one of R1 and R2 is a monovalent organic group consisting of a 5-membered heterocyclic ring structure containing a nitrogen atom. The negative photosensitive resin composition according to claim ₁ or 2, wherein at least one of R1 and _R2 in all structural units of the (A) polyimide precursor has a (meth)acrylate group. In all structural units of the (A) polyimide precursor, R ₁ and R ₂ have a total of two or more (meth) acrylate groups, negative photosensitive resin composition according to claim 1 or 2 . The negative photosensitive resin composition according to claim ₁ or ₂ , wherein at least one of R1 and R2 is a group represented by the following general formula (3).
{In formula (3), Ar is the heterocyclic structure, the dashed line is a single bond bonding to the oxygen atom in formula (1), and 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 R ₆ and R ₇ are each independently a divalent organic group having 1 to 10 carbon atoms which may contain a heteroatom. } 3. The negative photosensitive resin composition according to claim 1, 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. . 3. The negative according to claim 1 or 2, wherein 10 mol% or more of the total R ₁ and R ₂ of the (A) polyimide precursor has the heterocyclic structure and/or the structure with a high proportion of heteroatoms. type photosensitive resin composition. 3. The negative photosensitive resin composition according to claim 1, further comprising (D) a monomer having a polymerizable functional group. 3. The negative photosensitive resin composition according to claim 1, wherein (D) the monomer having a polymerizable functional group has two or more polymerizable functional groups. 3. The negative photosensitive resin composition according to claim 1, wherein the (D) monomer having a polymerizable functional group has 3 or more polymerizable functional groups. 3. The negative photosensitive resin composition according to claim 1, wherein X ₁ contains at least one selected from the group consisting of the following general formulas (8) to (11).
3. The negative photosensitive resin composition according to claim 1, wherein Y ₁ contains at least one selected from the group consisting of the following general formulas (12) to (15).
{In the formula, each R ₁₁ is independently a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, and each a is independently an integer of 0 to 4. } 3. The negative photosensitive resin composition according to claim 1, further comprising (E) a thermal base generator of 0.1 parts by mass or more and 40 parts by mass or less relative to 100 parts by mass of the (A) polyimide precursor. . The following steps:
(1) a step of applying the negative photosensitive resin composition according to claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a hardened relief pattern, comprising the step of heat-treating the relief pattern to form a hardened relief pattern. A polyimide precursor comprising a structural unit represented by the following general formula (1).
{In formula (1), X ₁ is a tetravalent organic group having 4 to 40 carbon atoms which may contain a heteroatom, and Y ₁ is a divalent organic group having 6 to 40 carbon atoms which may contain a heteroatom. and R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure One selected, provided that at least one of R ₁ and R ₂ is a monovalent organic group having a heterocyclic structure. } A polyimide precursor comprising a structural unit represented by the following general formula (1).
{In formula (1), X ₁ is a tetravalent organic group having 4 to 40 carbon atoms which may contain a heteroatom, and Y ₁ is a divalent organic group having 6 to 40 carbon atoms which may contain a heteroatom. and R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms which may contain a heteroatom, and a monovalent organic group having a heterocyclic structure It is one selected type, provided that at least one of OR ₁ and OR ₂ is a monovalent organic group in which the number of heteroatoms accounts for 42% or more of the constituent atoms excluding hydrogen atoms. }