TW202413469A - Negative photosensitive resin composition and method for manufacturing hardened relief pattern - Google Patents

Abstract

The subject of the present invention is to provide a negative photosensitive resin composition having higher mechanical strength and showing better adhesion to aluminum, and a method for producing a hardened relief pattern using the photosensitive resin composition. The negative photosensitive resin composition of the present invention comprises: (A) having the following general formula (1): {wherein, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and at least one of _R1 and _R2 is a group having an ethylenically unsaturated bond}; (B) a plasticizer having a freezing point or a melting point of above -40°C and having 3 or more repeating units; and (C) a photopolymerization initiator.

Description

Negative photosensitive resin composition and method for producing hardened relief pattern

The present invention relates to a negative photosensitive resin composition and a method for producing a hardened relief pattern.

Previously, insulating materials for electronic parts, passivation films for semiconductor devices, surface protection films, interlayer insulation films, etc. used polyimide resins with excellent heat resistance, electrical properties, and mechanical properties. Among the polyimide resins, photosensitive polyimide precursors are provided, which can easily form heat-resistant embossed pattern films by coating, exposing, developing, and curing the precursors through thermal imidization treatment. Compared with previous non-photosensitive polyimides, this photosensitive polyimide precursor has the characteristic of greatly shortening the steps.

On the other hand, in recent years, the method of mounting semiconductor devices on printed wiring boards has also changed from the perspective of improving integration and functionality, and reducing chip size. The previous mounting method using metal pins and lead-tin eutectic soldering has shifted to a structure that uses a polyimide film to directly contact the solder bump, such as BGA (ball grid array) and CSP (chip size package) that can achieve higher density mounting. When forming this bump structure, the film is required to have higher heat resistance and chemical resistance.

Furthermore, as semiconductor devices become increasingly miniaturized, the problem of wiring delay becomes more and more prominent. As a method of improving the wiring resistance of semiconductor devices, the industry has adopted methods such as changing the gold or aluminum wiring that has been used so far to copper or copper alloy wiring with lower resistance, or preventing wiring delay by improving the insulation between wiring. In recent years, as a material with high insulation, low dielectric constant materials are generally used to constitute semiconductor devices. However, low dielectric constant materials are often brittle and easily damaged. Semiconductor devices containing low dielectric constant materials have the following problems: For example, when they are mounted on a substrate together with a semiconductor chip through a reflow soldering step, shrinkage caused by temperature changes will damage the low dielectric constant material part. Although protective film materials with high heat resistance and good mechanical properties have been developed to prevent this, there is a problem that the film becomes hard and the adhesion with aluminum used for wiring, terminals, pads, etc. deteriorates.

Patent document 1 discloses a photosensitive resin composition that obtains higher mechanical strength by using a specific polyimide precursor. However, in recent years, there has been a demand for photosensitive resin compositions with higher mechanical strength, and no mention is made of adhesion to aluminum, so there is still room for further improvement. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 2021-173787

[The problem the invention is trying to solve]

Therefore, the purpose of the present invention is to provide a negative photosensitive resin composition that has higher mechanical strength and exhibits better adhesion to aluminum, and a method for producing a hardened relief pattern using the photosensitive resin composition. [Technical means for solving the problem]

[Item 1] A negative photosensitive resin composition comprising: (A) having the following general formula (1): {wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are independently hydrogen atoms or monovalent organic groups with 1 to 40 carbon atoms, and at least one of R ₁ and R ₂ is a group having an ethylenically unsaturated bond}; (B) a plasticizer having a freezing point or a melting point of above -40°C and having 3 or more repeating units; and (C) a photopolymerization initiator. [Item 2] A negative photosensitive resin composition comprising: (A) having the following general formula (1): [Chemical 2] A polyimide precursor having a structure of {wherein, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and at least one of _R1 and _R2 is a group having an ethylenically unsaturated bond}; (B) the following general formula (3): [Chemical 3] (wherein _n2 is an integer of 6 to 45, a and b are independently an integer of 0 to 5; however, the sum of a and b is an integer of 1 to 5; and _R6 , _R7 , R6 _' , R7 _' , _R8 , _R9 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms); and (C) a photopolymerization initiator. [Item 3] A negative photosensitive resin composition as described in item 1 or 2, wherein _R1 and _R2 in the above general formula (1) are independently a hydrogen atom, or the following general formula (2): [Chemistry 4] (wherein R ₃ , R ₄ and R ₅ are independently hydrogen atoms or organic groups with 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10) a monovalent organic group represented by, or a saturated aliphatic group with 1 to 4 carbon atoms. [Item 4] A negative photosensitive resin composition as described in any one of items 1 to 3, wherein Y ₁ in the above general formula (1) comprises a structure represented by the following general formula (4). [Chemistry 5] (wherein, _R10 and _R11 independently represent an alkyl group having 1 to 4 carbon atoms, a fluorine atom, or a trifluoromethyl group) [Item 5] A negative photosensitive resin composition as described in any one of Items 1 to 4, wherein _X1 in the general formula (1) comprises at least one structure selected from the group consisting of the following general formulas (5), (6) and (7). [Chemistry 6] [Chemistry 7] [Chemistry 8] [Item 6] A negative photosensitive resin composition as described in any one of items 1 to 5, which comprises the above-mentioned (B) plasticizer having a structure represented by _n2 in the above-mentioned general formula (3) being an integer of 8 to 23. [Item 7] A negative photosensitive resin composition as described in any one of items 1 to 6, which comprises 5 to 30 parts by weight of the above-mentioned (B) plasticizer relative to 100 parts by weight of the above-mentioned (A) polyimide precursor. [Item 8] A negative photosensitive resin composition as described in any one of items 1 to 7, which comprises a free radical polymerizable compound (E). [Item 9] A negative photosensitive resin composition as described in any one of items 1 to 8, which is a negative photosensitive resin composition for forming a surface protective film, an interlayer insulating film, a protective film for redistribution, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure. [Item 10] A method for producing a hardened relief pattern, comprising: (1) forming a photosensitive resin layer on a substrate by applying a negative photosensitive resin composition as described in any one of items 1 to 9 onto the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) hardening the relief pattern by heating the relief pattern. [Effects of the Invention]

According to the present invention, a negative photosensitive resin composition showing high mechanical strength and adhesion to aluminum and capable of obtaining good resolution, a hardened relief pattern using the photosensitive resin composition, and a method for producing the same can be provided.

The following is a detailed description of the method for implementing the present invention (hereinafter referred to as "this embodiment"). Furthermore, the present invention is not limited to the following embodiment, and can be implemented in various ways within the scope of its main purpose. In addition, unless otherwise specified, the characteristic values recorded in this embodiment refer to the values measured by the method recorded in the item of [Example] or the method that the industry understands to be equivalent to it.

In the following description, the upper limit or lower limit in the numerical range recorded in the segment can be replaced by the upper limit or lower limit in the numerical range recorded in other segments. In addition, in the following description, the upper limit or lower limit in a numerical range can be replaced by the value recorded in the embodiment. Furthermore, for the term "step" in the following description, independent steps are undoubtedly included therein, and even if they cannot be clearly distinguished from other steps, as long as the function of the "step" is achieved, they can also be included in this term.

<Negative photosensitive resin composition> The negative photosensitive resin composition of the present embodiment (hereinafter referred to as the photosensitive resin composition of the present embodiment) comprises: (A) having the following general formula (1): [Chemical 9] {wherein, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and at least one of _R1 and _R2 is a group having an ethylenically unsaturated bond}; (B) a plasticizer having a freezing point or a melting point of above -40°C and having 3 or more repeating units or the following general formula (3): [Chemical 10] (wherein n ₂ is an integer of 6 to 45, a and b are independently integers of 0 to 5; the sum of a and b is an integer of 1 to 5; and R ₆ , R ₇ , R _6' , R _7' , R ₈ , and R ₉ are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms); and (C) a photopolymerization initiator.

<(A) Polyimide precursor> The (A) polyimide precursor used in this embodiment is described. The resin component in the photosensitive resin composition of this embodiment is a polyamide having a structural unit represented by the following general formula (1). The (A) polyimide precursor is converted into polyimide by applying a thermal cyclization treatment. [Chemical 11] {wherein, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and at least one of _R1 and _R2 is a group having an ethylenically unsaturated bond}

Furthermore, if _R1 and _R2 in the general formula (1) are independently hydrogen atoms, or the general formula (2): [Chemical 12] (wherein R ₃ , R ₄ and R ₅ are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10) or saturated aliphatic groups having 1 to 4 carbon atoms are more preferred from the viewpoint of resolution or compatibility. The group having an ethylenically unsaturated bond is preferably a monovalent organic group represented by the above general formula (2).

The ratio of _R1 and _R2 in the general formula (1) being hydrogen atoms is preferably 10% or less, more preferably 5% or less, and further preferably 1% or less, based on the total molar number of _R1 and _R2 . Furthermore, the ratio of _R1 and _R2 in the general formula (1) being monovalent organic groups represented by the above general formula (2) is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more, based on the total molar number of _R1 and _R2 . If the ratio of hydrogen atoms and the ratio of organic groups having the structure represented by the general formula (2) are within the above ranges, it is preferred from the viewpoint of photosensitivity and storage stability.

In the general formula (1), _n1 is not particularly limited and may be an integer of 2 to 150. From the viewpoint of the photosensitivity and mechanical properties of the negative photosensitive resin composition, n1 is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

In the general formula (1), from the viewpoint of achieving both heat resistance and photosensitivity, the tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms, and more preferably an aromatic group or alicyclic aliphatic group in which _-COOR1 and _-COOR2 are adjacent to -CONH-. The tetravalent organic group represented by _X1 can be specifically exemplified by an organic group having 6 to 40 carbon atoms and containing an aromatic ring. For example, the following general formula (9) can be exemplified: [Chemical 13] {wherein, R ₁₆ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent alkyl group, and a C1-C10 monovalent fluorine-containing alkyl 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}, but is not limited thereto. Furthermore, X ₁ may be selected from only one of the groups having the above structures, or may be selected from a combination of two or more. The X ₁ group having the structure represented by formula (9) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitivity.

If the negative photosensitive resin composition of the present embodiment comprises a structure represented by formula (9) which is particularly selected from the following general formulas (5), (6), and (7): [Chemistry 15] [Chemistry 16] At least one structure in the group is preferably used as the _X1 group from the viewpoints of the imidization rate when heated at low temperature, degassing property, adhesion, mechanical strength, chemical resistance, etc.

In general formula (1), from the viewpoint of achieving both heat resistance and photosensitivity, the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms, for example, formula (10): The structure represented by {wherein, R ₁₇ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent alkyl group, and a C1-C10 monovalent fluorine-containing alkyl group, and n is an integer selected from 0 to 4}, but is not limited thereto. In addition, Y ₁ may be selected from only one of the groups having the above structures, or may be selected from a combination of two or more. The Y ₁ group having the structure represented by formula (10) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitivity.

If the negative photosensitive resin composition of the present embodiment comprises the structure represented by formula (10), in particular, the following general formula (4): (wherein R ₁₀ and R ₁₁ independently represent an alkyl group having 1 to 4 carbon atoms, a fluorine atom, or a trifluoromethyl group) is preferably used as the Y ₁ group from the viewpoints of mechanical strength, chemical resistance, adhesion, etc.

In one embodiment, the polyimide precursor (A) preferably has the general formula (11): {wherein, R ₁ , R ₂ , and n ₁ have the same meanings as above}. More preferably, in general formula (11), at least one of R ₁ and R ₂ is a monovalent organic group represented by general formula (2). When (A) the polyimide precursor includes the polyimide precursor represented by general formula (11), the chemical resistance becomes particularly high.

In one embodiment, from the viewpoint of thermal properties, the polyimide precursor (A) preferably has the general formula (12): {wherein, R ₁ , R ₂ , and n ₁ have the same meanings as above}. More preferably, in the general formula (12), at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (2).

In one embodiment, from the viewpoint of thermal properties, the polyimide precursor (A) preferably has the general formula (13): {wherein, R ₁ , R ₂ , and n ₁ have the same meanings as above}. More preferably, in the general formula (13), at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (2).

In one embodiment, from the viewpoint of mechanical strength, the polyimide precursor (A) preferably has the general formula (14): {wherein, R ₁ , R ₂ , and n ₁ have the same meanings as above}. More preferably, in the general formula (14), at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (2).

In one embodiment, from the viewpoint of mechanical strength, the polyimide precursor (A) preferably has the general formula (15): {wherein, R ₁ , R ₂ , and n ₁ have the same meanings as above}. More preferably, in the general formula (15), at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (2).

From the viewpoint of resolution and mechanical strength, the polyimide precursor (A) preferably contains one or more different structural units represented by the general formula (1). In addition, the polyimide precursor (A) may also contain a mixture of polyimide precursors represented by the general formula (1) but having different structures. Here, different structural units represented by the same chemical formula refer to structural units having the same structure represented by the general formula (1) but having different structures due to different groups in the formula, or having different contents of the structural units. It is particularly preferred from the viewpoint of resolution and mechanical strength that the polyimide precursor (A) contains both structural units represented by the general formula (14) and structural units represented by the general formula (15). For example, (A) polyimide precursor may include a copolymer of a structural unit represented by general formula (14) and a structural unit represented by general formula (15), or may include a mixture of a polyimide precursor represented by general formula (14) and a polyimide precursor represented by general formula (15).

(A) Preparation method of polyimide precursor Regarding the (A) polyimide precursor, first, a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group _X1 is reacted with an alcohol having a photopolymerizable unsaturated double bond and an optional alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester). Thereafter, the (A) polyimide precursor is obtained by subjecting the partially esterified tetracarboxylic acid to amide polycondensation with a diamine containing the above-mentioned divalent organic group _Y1 .

(Preparation of Acid/Ester) In the present embodiment, a tetravalent organic group X is used to prepare (A) a polyimide precursor. Examples of the tetracarboxylic dianhydride of ₁ include the tetracarboxylic dianhydride represented by the above general formula (9), such as 4,4'-oxydiphthalic dianhydride (ODPA), pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (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. Preferred examples include, but are not limited to, 4,4'-oxydiphthalic dianhydride (ODPA), pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA). Of course, these may be used alone or in combination of two or more.

In the present embodiment, the photopolymerizable unsaturated double bond alcohols suitable for preparing the polyimide precursor (A) include, for example, 2-acryloxyethanol, 1-acryloxy-3-propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butyl acrylate, 2-hydroxy-3-meth ...tert-butyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butyl acrylate, 2-hydroxy-3-tert-butyl acrylate, 2-hydroxy-3-tert-butyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2- methacrylate, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc.

The above-mentioned alcohols having photopolymerizable unsaturated double bonds may be mixed with a portion of alcohols not having unsaturated double bonds, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, etc.

In addition, a non-photosensitive polyimide precursor prepared only from the above-mentioned alcohols without unsaturated double bonds can be mixed with a photosensitive polyimide precursor and used as a polyimide precursor. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by weight or less based on 100 parts by weight of the photosensitive polyimide precursor.

The above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohol can be mixed in the presence of an alkaline catalyst such as pyridine, dissolved by stirring at a temperature of 20-50° C. for 4-24 hours, thereby performing an esterification reaction of the anhydride to obtain the desired acid/ester.

(Preparation of polyimide precursor) A suitable dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc., can be added to the above-mentioned acid/ester body (representatively, a solution of the acid/ester body in the following solvent) under ice cooling and mixed to convert the acid/ester body into a polyanhydride, and then a diamine containing a divalent organic group _Y1 suitable for use in the present embodiment which is separately dissolved or dispersed in a solvent is added dropwise thereto to carry out amide condensation, thereby obtaining the target polyimide precursor. Alternatively, the target polyimide precursor can be obtained by acylating the acid/ester with thionyl chloride or the like and then reacting the resulting acid/ester with a diamine compound in the presence of a base such as pyridine.

Examples of diamines containing a divalent organic group _Y1 suitable for use in the present embodiment include diamines containing _Y1 having a structure represented by the above general formula (10), such as p-phenylenediamine (pPD), m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl 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'-diaminodiphenyl sulfone, Aminobenzophenone, 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]sulfonate, bis[4-(3-aminophenoxy)phenyl]sulfonate, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl] Ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine, 9,9-bis(4-aminophenyl)fluorene, and some of the hydrogen atoms on the benzene ring of the same are methyl, ethyl, hydroxymethyl , hydroxyethyl, halogen, etc., for example, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB: m-tolidine), 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof, but are not limited thereto. Preferred examples include p-phenylenediamine (pPD), 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB: m-tolidine), and 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB).

After the amide polycondensation reaction is completed, the water-absorbing byproduct of the dehydration condensation agent coexisting in the reaction solution is filtered and separated as needed, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component, and then the polymer is purified by repeatedly performing redissolution and reprecipitation operations. The purified polymer is vacuum dried to isolate the target polyimide precursor. In order to improve the degree of purification, the polymer solution can also be passed through a column filled with an anion and/or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

When the molecular weight of the polyimide precursor (A) is measured by the polystyrene conversion weight average molecular weight obtained by gel permeation chromatography, the molecular weight is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. When the weight average molecular weight of the polyimide precursor (A) is 8,000 or more, the mechanical properties are good. When the weight average molecular weight of the polyimide precursor (A) is 150,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. The developing solvent of the gel permeation chromatography is preferably tetrahydrofuran and N-methyl-2-pyrrolidone. In addition, the weight average molecular weight of the polyimide precursor (A) is obtained from a calibration curve made using standard monodisperse polystyrene. The standard monodisperse polystyrene is preferably the organic solvent system standard sample STANDARD SM-105 manufactured by Showa Denko K.K., but is not limited thereto.

<(B) Plasticizer> The (B) plasticizer used in the present embodiment is a compound having a freezing point or melting point of -40°C or higher and having 3 or more repeating units, and/or a compound represented by the following general formula (3). (wherein _n2 is an integer of 6 to 45, a and b are independently integers of 0 to 5, wherein the sum of a and b is an integer of 1 to 5, and _R6 , _R7 , R6 _' , R7 _' , _R8 , and _R9 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms)

By adding (B) plasticizer, the adhesion between the hardened relief pattern and aluminum, as well as the Young's modulus and resolution of the hardened relief pattern formed by the photosensitive resin composition of the present embodiment are improved. The reason is not clear, but the inventors of the present invention speculate as follows: the exposure film formed by the photosensitive resin composition of the present embodiment becomes soft due to the (B) plasticizer, and the tracking property to the substrate is improved, thereby obtaining good adhesion with aluminum. Furthermore, the inventors of the present invention believe that when the relief pattern formed by the photosensitive resin composition of the present embodiment is heat-cured, the (B) plasticizer can improve the fluidity of the polyimide after the heat cyclization of the (A) polyimide precursor through its plasticizing effect, and further, the filling property of the polymer can be improved by the volatility of the (B) plasticizer during heating, thereby improving the Young's modulus. Furthermore, the inventors of the present invention believe that since the polymer of the (A) polyimide precursor having the structure represented by the general formula (4) in which _Y1 in the general formula (1) comprises a high Young's modulus and strong absorption of i-rays, when the photosensitive resin composition using the same is exposed to i-rays, insufficient light reaches the bottom and insufficient hardening occurs, which often results in planing marks at the bottom of the formed relief pattern. By adding the (B) plasticizer thereto, other properties can be maintained, and the transparency of the photosensitive resin composition can be improved, and the bottom can also be sufficiently hardened, thereby improving the resolution. Furthermore, the inventors of the present invention believe that in order to exhibit such properties, the compatibility of (B) plasticizer with other composition components must also be good. Even if it is a commonly used plasticizer, if it is not the (B) plasticizer specified in this embodiment, it cannot fully exert the expected effect. The following describes the method for manufacturing a hardened relief pattern of this embodiment. In order for (B) plasticizer to exert the effects of various properties, it is more advantageous for (B) plasticizer to not volatilize and remain when the photosensitive resin composition is applied to the substrate and dried. Therefore, the freezing point or melting point of (B) plasticizer is preferably above -40°C. Furthermore, the inventors and others believe that in order to suppress the volatility caused by drying after the photosensitive resin composition of the present embodiment is applied to the substrate while the plasticizer (B) maintains compatibility and plasticization, the above effects can be advantageously obtained by having the plasticizer (B) have more than 3 repeating units. The above-mentioned (B) plasticizer is preferably a repeating unit having more than 3 continuous identical structures. Furthermore, considering volatility, compatibility, and plasticization, the (B) plasticizer can also be represented by the general formula (3), for example. The above-mentioned freezing point and melting point can be measured using known techniques. In one embodiment, the freezing point and melting point are, for example, values measured using a differential scanning calorimeter (DSC). The melting point can measure the temperature at which a solid melts and becomes a liquid, and the freezing point can measure the temperature at which a liquid solidifies and solidifies. From the viewpoint of non-volatility and plasticization, the freezing point or melting point of the plasticizer (B) is preferably above -40°C and below 60°C, and more preferably above -30°C and below 50°C. In addition, the lower limit of the freezing point or melting point of the plasticizer (B) is preferably above -40°C, or above -30°C, or above -10°C, or above 0°C, or above 5°C, or above 10°C. Furthermore, the upper limit of the freezing point or melting point of the plasticizer (B) is preferably below 60°C, or below 50°C, or below 40°C. In addition, the repeating units of the plasticizer (B) may be exemplified by oxyalkylene groups such as oxyethylene, oxypropylene, oxybutylene, oxypentylene, or the structural unit represented by the following formula obtained by ring-opening ε-caprolactone, but are not limited thereto. From the viewpoint of compatibility, aliphatic groups are preferred, and oxyalkylene groups are more preferred. [Chemistry 25]

In order to improve the aluminum adhesion, Young's modulus, plasticity and compatibility, it is more advantageous to improve the plasticity and compatibility, so the number of repetitions of the above-mentioned repeating structure units is preferably 3 or more and 45 or less, more preferably 4 or more and 45 or less, further preferably 6 or more and 45 or less, and most preferably 8 or more and 23 or less. In addition, the lower limit of the number of repetitions of the above-mentioned repeating structure units is preferably 3 or more, or 4 or more, or 6 or more, or 8 or more. Furthermore, the upper limit of the number of repetitions of the above-mentioned repeating structure units is preferably 45 or less, or 30 or less, or 23 or less, or 22 or less.

(B) Specific examples of plasticizers include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone glycol, or those modified with an alkyl group having 1 to 6 carbon atoms at one end, such as polyoxyethylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monopropyl ether, polyoxyethylene monobutyl ether, polyoxyethylene monopentyl ether, polyoxyethylene monohexyl ether, polyoxypropylene monomethyl ether, polyoxypropylene monoethyl ether, polyoxypropylene monopropyl ether, polyoxypropylene monobutyl ether, polyoxypropylene monopentyl ether, polyoxypropylene monohexyl ether, polyoxytetramethylene monomethyl ether, polyoxytetramethylene monopropyl ether, polyoxytetramethylene monobutyl ether, polyoxytetramethylene monopentyl ether, polyoxytetramethylene monohexyl ether, etc. Furthermore, examples thereof include polyoxyethylene dimethyl ether, polyoxyethylene diethyl ether, polyoxyethylene dipropyl ether, polyoxyethylene dibutyl ether, polyoxyethylene dipentyl ether, polyoxyethylene dihexyl ether, polyoxypropylene dimethyl ether, polyoxypropylene diethyl ether, polyoxypropylene dipropyl ether, polyoxypropylene dibutyl ether, polyoxypropylene dipentyl ether, polyoxypropylene dihexyl ether, polyoxytetramethylene dimethyl ether, polyoxytetramethylene dipropyl ether, polyoxytetramethylene dibutyl ether, polyoxytetramethylene dipentyl ether, polyoxytetramethylene dihexyl ether, etc., which are modified at both ends with an alkyl group having 1 to 6 carbon atoms.

Among the plasticizers (B), from the viewpoint of compatibility in the photosensitive resin composition of the present embodiment, adhesion between the cured film and aluminum, and Young's modulus, preferably, _n2 in the general formula (3) is an integer of 8 to 23.

From the viewpoint of compatibility or resolution in the photosensitive resin composition of the present embodiment, the sum of a and b is preferably an integer of 2 to 3. From the viewpoint of resolution of the photosensitive resin composition of the present embodiment or reliability of the cured film, _R8 and/or _R9 are preferably alkyl groups having 1 to 6 carbon atoms. Furthermore, from the viewpoint of compatibility in the photosensitive resin composition of the present embodiment, _R6 , _R7 , R6 _' and R7 _' are preferably hydrogen atoms or methyl groups.

(B) Commercially available plasticizers include PEG#300, PEG#400, PEG#600, PEG#1000, Uniox M-400, Uniox M-550, Uniox M-1000, Uniox M-2000, Uniox MM-400, Uniol D-400G, Uniol D-700, Uniol D-1000, Uniol D-1200, etc. manufactured by NOF Corporation. Also, PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, etc. manufactured by Mitsubishi Chemical Co., Ltd. Furthermore, Placcel 208, Placcel 210, Placcel 212, Placcel 210N, etc. manufactured by Daicel Corporation can be cited.

The content of the plasticizer (B) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more, based on 100 parts by mass of the polyimide precursor (A), from the viewpoint of adhesion to aluminum and Young's modulus. From the viewpoint of improving compatibility and resolution in the photosensitive resin composition, the content is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less.

＜(C) Photopolymerization initiator＞ The (C) photopolymerization initiator used in the present embodiment is described below. The photopolymerization initiator is preferably a photo-free radical polymerization initiator, preferably exemplified by: benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone and other acetophenone derivatives, 9-oxosulfuron , 2-methyl 9-oxosulfuron , 2-isopropyl 9-oxysulfide , diethyl 9-oxysulfide 9-Oxysulfuron derivatives, benzoyl, benzoyl dimethyl ketal, benzoyl-β-methoxyethyl acetal and other benzoyl derivatives, benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2 -(o-benzoyl) oxime, 1,3-diphenylpropane-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropane-2-(o-benzoyl) oxime and other oximes, N-arylglycine such as N-phenylglycine, peroxides such as perchlorinated benzoyl, aromatic biimidazoles, titanocene, α-(n-octylsulfonyloxyimino)-4-methoxyphenylacetonitrile and other photoacid generators, but not limited to them. Among the above-mentioned photopolymerization initiators, oximes are more preferred in terms of photosensitivity.

The content of the photopolymerization initiator (C) is preferably 0.1 to 20 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 1 to 5 parts by mass, based on 100 parts by mass of the polyimide precursor (A). The above content is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or resolution, and is preferably 20 parts by mass or less from the viewpoint of the physical properties of the cured film of the photosensitive resin composition.

<(D) Solvent> The negative photosensitive resin composition in this embodiment may also contain (D) solvent. Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. For example, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide (DMSO), 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 (GBL), 1,3-dimethyl-2-imidazolidinone (DMI), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylene glycol, tetrahydrofuran methanol, 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, etc. Among them, from the viewpoint of solubility and stability of the photosensitive resin composition and adhesion to the substrate, NMP, DMSO, tetramethyl urea, butyl acetate, ethyl lactate, GBL, DMI, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenylene glycol, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide and tetrahydrofuran methanol are preferred. Among such solvents, those that completely dissolve the polyimide precursor are particularly preferred, such as NMP, N,N-dimethylacetamide, N,N-dimethylformamide, DMSO, tetramethyl urea, GBL, DMI, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc. In particular, from the perspective of in-plane uniformity when the photosensitive resin composition is applied to a substrate, GBL, DMI, and 3-methoxy-N,N-dimethylpropionamide are preferred. (D) The solvent may be one or two or more solvents may be mixed and used. From the perspective of appropriately adjusting the stability of the photosensitive resin composition, a mixture of two or more solvents is preferred. In the case of containing two or more solvents, from the perspective of in-plane uniformity, 50% by weight or more of the solvent is preferably any one of GBL and 3-methoxy-N,N-dimethylpropionamide, and more preferably GBL.

In the photosensitive resin composition of the present embodiment, the content of the (D) solvent is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

<(E) Radical polymerizable compound> The negative photosensitive resin composition in this embodiment may also contain (E) a radical polymerizable compound. By containing (E) a radical polymerizable compound, the resolution can be improved. In order to obtain good resolution, it is preferred to contain 3 to 40 parts by mass of the (E) radical polymerizable compound relative to 100 parts by mass of the (A) polyimide precursor, more preferably 5 to 30 parts by mass, and further preferably 10 to 20 parts by mass.

The (E) radical polymerizable compound in this embodiment is not particularly limited as long as it is a compound that undergoes radical polymerization reaction by a photopolymerization initiator, and is preferably a (meth)acrylic acid compound, for example, preferably the following general formula (16): A compound represented by {wherein, X ₁₁ is an organic group, L ₁₁ , L ₁₂ and L ₁₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; n ₁₁ is an integer of 1 to 10}.

(E) Examples of free radical polymerizable compounds include: diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, mono- or di-acrylate and methacrylate of ethylene glycol or polyethylene glycol; mono- or di-acrylate and methacrylate of propylene glycol or polypropylene glycol; mono-, di- or tri-acrylate and methacrylate of glycerol; cyclohexane diacrylate and dimethacrylate; diacrylate and dimethacrylate of 1,4-butanediol; diacrylate and dimethacrylate of 1,6-hexanediol; diacrylate and dimethacrylate of neopentyl glycol; mono- or di-acrylate of bisphenol A; The present invention also includes compounds such as diacrylate and mono- or dimethacrylate of bisphenol A, benzyltrimethacrylate, isobutyl acrylate and isobutyl methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trihydroxymethylpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri- or tetraacrylate and methacrylate of pentaerythritol, tricyclodecane dimethanol diacrylate, tri-(2-acryloxyethyl) isocyanurate, and ethylene oxide or propylene oxide adducts of these compounds, but the present invention is not particularly limited to these examples.

More specifically, the following formula (17) can be cited as an example of the radical polymerizable compound (E): (wherein m is an integer greater than 1, and n is an integer greater than 1; wherein the sum of m and n is 30) is a compound represented by, but is not limited to, the above.

In the present invention, when the number of radical polymerizable groups in the (E) radical polymerizable compound is one, it is monofunctional. When the number of radical polymerizable groups is two or more, it is called x-functional group according to the number x of radical polymerizable groups, but there are also cases where two or more functional groups are collectively called polyfunctional. The (E) radical polymerizable compound may be monofunctional or may be two or more functional groups. From the viewpoint of resolution or mechanical strength of the cured film, the radical polymerizable compound is preferably two or more functional groups. In addition, the (E) radical polymerizable compound may be used alone or in combination of two or more functional groups.

The weight average molecular weight of the (E) radical polymerizable compound is preferably 100 or more, more preferably 200 or more, and more preferably 300 or more. The upper limit is preferably 2000 or less, and more preferably 1000 or less. By setting it within the above range, the resolution is improved.

<(F) Other additives> ・Silane coupling agent The negative photosensitive resin composition of this embodiment may also contain a silane coupling agent to improve the adhesion between the film formed using the negative photosensitive resin composition and the substrate. The silane coupling agent is not particularly limited, and examples thereof include: γ-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamide, benzophenone-3,3'-bis(N-[3-triethoxysilyl)propyl]phthalamide, 3-(Triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyl trimethoxysilane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-(Trialkoxysilyl)propyl succinic anhydride, γ-butylpropyl methyl dimethoxysilane, 3-butylpropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, Chisso Co., Ltd.: trade name Sila-Ace S810), 3-butylpropyl triethoxysilane (Azmax Co., Ltd.: trade name SIM6475.0), 3-butylpropyl methyl dimethoxysilane (Shin-Etsu Chemical Co., Ltd.: trade name LS1375, Azmax Co., Ltd.: trade name SIM6474.0), butyl methyl trimethoxy silane (Azmax Co., Ltd.: trade name SIM6473.5C), butyl methyl methyl dimethoxy silane (Azmax Co., Ltd.: trade name SIM6473.0), 3-butylpropyldiethoxymethoxysilane, 3-butylpropylethoxydimethoxysilane, 3-butylpropyltripropoxysilane, 3-butylpropyldiethoxypropoxysilane, 3-butylpropylethoxydipropoxysilane, 3-butylpropyldimethoxypropoxysilane, 3-butylpropylmethoxydipropoxysilane, 2-butylethyltrimethoxysilane, 2-butylethyldiethoxymethoxysilane, 2-butylethylethyl Oxydimethoxysilane, 2-butylethyltripropoxysilane, 2-butylethyltripropoxysilane, 2-butylethylethoxydipropoxysilane, 2-butylethyldimethoxypropoxysilane, 2-butylethylmethoxydipropoxysilane, 4-butyltrimethoxysilane, 4-butyltriethoxysilane, 4-butyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by 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-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl) Urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (Azmax Co., Ltd.: Trade name SLA0598.0), γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, m-aminophenyl trimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-aminophenyl trimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.1), aminophenyl trimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), etc.

Examples of the silane coupling agent include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-tert-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, tetra-isobutoxysilane, tetra-tert-butoxysilane, tetra(methoxyethoxysilane), tetra(methoxypropyl)-tert-butylcarbamate, bis(triethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-tert-butoxydiacetyloxy Silane, diisobutoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, trimethoxyphenylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, trimethoxy (p-tolyl) silane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethyl Phenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, t-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethyl-isopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, t-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, t-butyldiphenylsilanol, triphenylsilanol, etc., but are not limited thereto.

The silane coupling agents listed above may be used alone or in combination. Among the silane coupling agents listed above, preferred from the viewpoint of storage stability are phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following formula: [Chemical 28] Silane coupling agents of the structures shown.

When a silane coupling agent is used, the content is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor from the viewpoint of adhesion and compatibility with aluminum.

・Heterocyclic compounds The negative photosensitive resin composition of this embodiment may also contain a heterocyclic compound. By adding the heterocyclic compound, the adhesion between the cured film made from the photosensitive resin composition and aluminum can be improved. Examples of the heterocyclic compound include azole compounds or purine derivatives. Specific examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)] )phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole, 5-carboxyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8- Aminoadenine, 6-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 their derivatives.

Among the heterocyclic compounds, 5-amino-1H-tetrazole and 8-azaadenine are preferred from the viewpoint of adhesion. In addition, the heterocyclic compounds may be used alone or as a mixture of two or more. When the photosensitive resin composition contains a heterocyclic compound, the content thereof is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 5 parts by mass from the viewpoint of adhesion to aluminum.

・Thermoalkali generator The negative photosensitive resin composition of this embodiment may also contain a thermoalkali generator. A thermoalkali generator refers to a compound that generates a base by heating. By containing a thermoalkali generator, the imidization of the photosensitive resin composition can be further promoted. The thermoalkali generator is not particularly limited in type, and examples thereof include an amine compound protected by a tert-butoxycarbonyl group, or a thermoalkali generator disclosed in International Publication No. 2017/038598. However, it is not limited thereto, and other known thermoalkali generators may also be used.

Examples of the amine compound protected by the tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valine alcohol, and 3-amino-1,2-propanediol. , 2-amino-1,3-propanediol, tyramine, demethylephedrine, 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-pyrrolidone, 2-pyrrolidonemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidonemethanol, 3-piperidonemethanol, 2-piperidonemethanol, 4-piperidoneethanol, 2-piperidoneethanol, 2-(4-piperidone)-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-tetraoxotetradecane, 1-aza-15-crown-5, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or a compound in which the amino group of an amino acid and its derivatives are protected by a tert-butoxycarbonyl group, but the present invention is not limited thereto.

The content of the hot alkali generator is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the polyimide precursor (A). The above-mentioned amount is preferably 0.1 parts by mass or more from the viewpoint of promoting the imidization effect, and is preferably 30 parts by mass or less from the viewpoint of improving the physical properties of the photosensitive resin layer after the negative photosensitive resin composition is cured.

・Hindered phenol compound The negative photosensitive resin composition of this embodiment may also optionally contain a hindered phenol compound to suppress discoloration on the surface of the substrate. The hindered phenol compound is not limited, and examples thereof include: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], 2,2-thio-diethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-phenylpropionamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris-(3,5-di-tert-butyl-4-hydroxyphenyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, etc.

Examples of hindered phenol compounds include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-(1-ethylpropyl)-3-hydroxy-2 ,6-dimethylbenzyl]-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)- The present invention also includes, but is not limited to, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione.

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

The content of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the content of the hindered phenol compound is 0.1 parts by mass or more relative to 100 parts by mass of the polyimide precursor (A), for example, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy as a substrate, discoloration and corrosion of the copper or the copper alloy can be prevented. On the other hand, when the content is 20 parts by mass or less, the photosensitivity is excellent.

・Organic titanium compound The negative photosensitive resin composition of this embodiment may also contain an organic titanium compound. By containing the organic titanium compound, a photosensitive resin layer with excellent chemical resistance can be formed even when curing at a low temperature.

Usable organic titanium compounds include organic chemical substances bonded to titanium atoms via covalent bonds or ionic bonds.

Specific examples of organic titanium compounds are shown in the following I) to VII): I) Titanium chelate compounds: Among titanium chelate compounds, titanium chelate compounds having two or more alkoxy groups are more preferred because they can obtain the storage stability of the negative photosensitive resin composition and a good relief pattern. Specific examples are titanium bis(triethanolamine) diisopropyl alcohol, titanium bis(2,4-pentanedioic acid) di-n-butanol, titanium bis(2,4-pentanedioic acid) diisopropyl alcohol, titanium bis(tetramethylpimelic acid) diisopropyl alcohol, titanium diisopropyl alcohol bis(ethyl acetylacetate), etc.

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

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

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

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

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

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

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

The content of the organic titanium compound is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the polyimide precursor (A). When the content is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when the content is 10 parts by mass or less, excellent storage stability is achieved.

・Sensitizer The negative photosensitive resin composition of this embodiment may also contain a sensitizer to increase the photosensitivity. Examples of the sensitizer include: michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzene. Allylene dihydroindanone, p-dimethylaminobenzylidene dihydroindanone, 2-(p-dimethylaminophenylbenzene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylamino)acetone 3-Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4- Benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-benzimidazole, 1-phenyl-5-benzyltetrazol, 2-benzylthiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminophenylvinyl)styrene, etc. These can be used alone or in combination of 2 to 5 types.

When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the content of the sensitizer is preferably 0.1 to 25 parts by weight relative to 100 parts by weight of the (A) polyimide precursor.

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

・Thermal crosslinking agent The negative photosensitive resin composition of this embodiment may also contain a thermal crosslinking agent arbitrarily to improve the heat resistance of the cured film. Regarding the thermal crosslinking agent, for example, those having one thermal crosslinking group include: ML-26X, ML-24X, ML-236TMP, 4-Methylol 3M6C, ML-MC, ML-TBC (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), P-a type Benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), etc. Examples of the compounds having two thermally crosslinkable groups include DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (these are trade names, manufactured by Asahi Chemical Industries, Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, Dimethylol-Bis-C, Dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (these are trade names, manufactured by Honshu Chemical Industries, Ltd.), NIKALAC MX-290 (trade name, manufactured by SANWA CHEMICAL (manufactured by Shikoku Chemical Co., Ltd.), B-a type Benzoxazine, B-m type Benzoxazine (the above are trade names, manufactured by Shikoku Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, etc. Those with three thermal crosslinking groups include TriML-P, TriML-35XL, TriML-TrisCR-HAP (the above are trade names, manufactured by Honshu Chemical Co., Ltd.), etc. Examples of compounds having four thermally crosslinkable groups include TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (the above are trade names, manufactured by Honshu Chemical Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270 (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), etc. Examples of compounds having six thermally crosslinkable groups include HML-TPPHBA, HML-TPHAP (the above are trade names, manufactured by Honshu Chemical Co., Ltd.), NIKALAC MW-390, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.). Among them, in the present embodiment, those containing at least two thermally crosslinkable groups are preferred, and more preferred are 46DMOC, 46DMOEP (the above are trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by SANWA CHEMICAL Co., Ltd.), B-a type Benzoxazine, B-m type Benzoxazine (the above are trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, etc., TriML-P, TriML-35XL (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), etc., TM-BIP-A (the above are trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270 (the above are trade names, manufactured by SANWA CHEMICAL (Co., Ltd.), HML-TPPHBA, HML-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry (Co., Ltd.)), etc. Further preferred examples include: NIKALAC MX-290, NIKALAC MX-280, NIKALAC MX-270 (the above are trade names, manufactured by SANWA CHEMICAL (Co., Ltd.)), B-a type Benzoxazine, B-m type Benzoxazine (the above are trade names, manufactured by Shikoku Chemical Industry (Co., Ltd.)), NIKALAC MW-390, NIKALAC MW-100LM (the above are trade names, manufactured by SANWA CHEMICAL (Co., Ltd.)), etc. In order to improve the heat resistance of the cured film, the content of the heat crosslinking agent is preferably 0.5 to 20 parts by mass, and more preferably 2 to 10 parts by mass relative to 100 parts by mass of the (A) polyimide precursor. When the content is 0.5 parts by mass or more, good heat resistance is exhibited. On the other hand, when the content is 20 parts by mass or less, excellent storage stability is achieved.

<Method for manufacturing hardened relief pattern and semiconductor device> The method for manufacturing hardened relief pattern of the present embodiment comprises: (1) forming a photosensitive resin layer on a substrate by applying the negative photosensitive resin composition of the present embodiment to the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) hardening the relief pattern by heating the relief pattern.

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

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

(3) Relief pattern forming step In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from previously known photoresist developing methods such as a rotary spray method, a liquid coating method, and an immersion method accompanied by ultrasonic treatment. In addition, after development, for the purpose of adjusting the shape of the relief pattern, post-development baking can be performed according to any combination of temperature and time as needed.

The developer used for development is preferably a good solvent of the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent. The good solvent is preferably NMP, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. The poor solvent is preferably toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, and water, etc. When a good solvent and a poor solvent are mixed and used, it is preferred to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Furthermore, two or more solvents, for example, several solvents, may be used in combination.

(4) Relief pattern hardening step In this step, the relief pattern obtained by the above-mentioned development is subjected to heat treatment to dilute the photosensitive component, and the (A) polyimide precursor is imidized, thereby hardening the relief pattern and converting it into a hardened relief pattern containing polyimide. As a method of heat treatment, various methods can be selected, such as a method using a heating plate, a method using an oven, and a method using a temperature-raising oven with a settable temperature program. The heat treatment can be performed, for example, at 160°C to 350°C and for 30 minutes to 5 hours. The temperature of the heat treatment is preferably above 200°C and below 280°C. The time of the heat treatment is preferably above 0.5 hours and below 10 hours. The atmosphere gas during heat curing can be air, or inert gases such as nitrogen and argon.

<Semiconductor device> In this embodiment, a semiconductor device having a hardened relief pattern obtained by the above-mentioned method for manufacturing a hardened relief pattern is also provided. Therefore, a semiconductor device having a substrate as a semiconductor element and a hardened relief pattern of polyimide formed on the substrate by the above-mentioned method for manufacturing a hardened relief pattern can be provided. In addition, it can also be applied to a method for manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-mentioned method for manufacturing a hardened relief pattern of the present embodiment as a part of the steps. The semiconductor device can be manufactured by forming the hardened relief pattern formed by the manufacturing method of the hardened relief pattern of the present embodiment into a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip chip device, or a protective film for a semiconductor device with a bump structure, and combining it with a known manufacturing method of a semiconductor device. The negative photosensitive resin composition of the present embodiment can be preferably used as a negative photosensitive resin composition for forming a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip chip device, or a protective film for a semiconductor device with a bump structure.

<Display device> In this embodiment, a display device can be provided, which has a display element and a cured film disposed on the upper part of the display element, and the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern can be directly laminated in contact with the display element, or can be laminated through other layers. For example, the cured film can be exemplified as a surface protection film, an insulating film, and a flattening film of a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a spacer for a cathode of an organic EL element.

The negative photosensitive resin composition of the present embodiment is preferably used for forming an insulating member or an interlayer insulating film. In addition to being applied to semiconductor devices as described above, the negative photosensitive resin composition of the present embodiment can also be used for interlayer insulating films of multilayer circuits, surface coatings of flexible copper foils, solder resist films, and liquid crystal alignment films. [Example]

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

(1) Weight average molecular weight The weight average molecular weight (Mw) of each photosensitive resin composition was measured using gel permeation chromatography (standard polystyrene conversion) under the following conditions.

Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: 2 Shodex KD-806M manufactured by Showa Denko (Co., Ltd.) in series, or Shodex 805M/806M manufactured by Showa Denko (Co., Ltd.) in series Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko (Co., Ltd.) Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL/min.

(2) Evaluation of Resolution of Hardened Relief Pattern (Polyimide Coating) The photosensitive resin composition was spin-coated onto a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm) using a coating developer (D-Spin 60A model, manufactured by SOKUDO) to a film thickness of about 10 μm, and pre-baked at 110°C for 240 seconds using a hot plate to form a coating. The coating was exposed to i-rays at a step of 50 mJ/ ^cm2 from an exposure amount of 400 mJ/ ^cm2 to 700 mJ/ ^cm2 using a stepper NSR2005i11A (manufactured by Nikon) having an exposure wavelength of i-rays (365 nm) through a multiplying mask with a test pattern attached. Next, a coating developer (D-Spin 60A, manufactured by SOKUDO) was used to perform rotary spray development at 23°C using cyclopentanone as a developer for 1.4 times the time required for the unexposed portion to completely dissolve and disappear, followed by rotary spray washing with propylene glycol monomethyl ether acetate for 10 seconds to obtain a relief pattern including a resin film. Subsequently, a vertical curing furnace VF200B (manufactured by Koyo Thermo Systems) was used to perform curing at 280°C for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern.

For each pattern obtained, observe the shape of the pattern or the width of the pattern portion under an optical microscope, and find the resolution. Regarding the resolution, a pattern with a plurality of openings of different areas is formed by exposing through a multiplied mask with a test pattern attached in the same manner as above. If the area of the opening of the obtained pattern is more than 1/2 of the opening area of the corresponding pattern mask, it is considered to be resolved, and the length of the opening edge of the mask corresponding to the opening with the smallest area among the resolved openings is taken as the resolution. The exposure amount with the best resolution among the irradiated exposure amounts is set as the optimal exposure amount, and the pattern accuracy is evaluated based on the following criteria. If the evaluation is A to C, it can be preferably used as a hardened relief pattern suitable for semiconductors.

A: The pattern cross section is not wavy, there is no planing mark, swelling or bridging at the bottom, and the resolution is 9 μm or less. B: The pattern cross section is not wavy, there is no planing mark, swelling or bridging at the bottom, and the resolution is 10 μm or less. C: The pattern cross section is not wavy, there is no planing mark, swelling or bridging at the bottom, and the resolution is 12 μm or less. D: None of the above conditions A to C are met.

(3) Evaluation of Young's modulus of hardened relief pattern (polyimide coating) The photosensitive resin composition was spin-coated onto a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm) using a coating developer (D-Spin 60A, manufactured by SOKUDO) to a film thickness of about 10 μm, and pre-baked at 110°C for 240 seconds using a hot plate to form a coating. Afterwards, the entire surface was exposed to 800 mJ/ ^cm2 using a parallel light mask alignment exposure machine (PLA-501FA, manufactured by Canon), and heated at 280°C for 2 hours in a nitrogen atmosphere using a temperature-controlled curing furnace (VF-2000, manufactured by Koyo Lindberg) to obtain a hardened relief pattern (thermally cured polyimide coating). The obtained polyimide coating was cut into short strips with a width of 3 mm using a dicing machine (DAD3350, manufactured by DISCO), and then peeled from the silicon wafer using 46% hydrofluoric acid to obtain a polyimide tape. The Young's modulus of the obtained polyimide tape was measured using a tensile tester (UTM-II-20, manufactured by Orientec) in accordance with ASTM D882-09 and evaluated according to the following criteria. If the evaluation is A to C, it can be preferably used as a hardening film for semiconductors.

A: Young's modulus is 6.5 GPa or more B: Young's modulus is 6.0 GPa or more but less than 6.5 GPa C: Young's modulus is 5.0 GPa or more but less than 6.0 GPa D: Young's modulus is less than 5.0 GPa

(4) Evaluation of adhesion with aluminum A 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm) was sputter-coated with aluminum (Al) with a thickness of 100 nm using a sputtering device (L-440S-FHL, manufactured by Canon Anelva). Then, a photosensitive resin composition was spin-coated onto the wafer using a coating developer (D-Spin60A, manufactured by SOKUDO) to a film thickness of approximately 10 μm, and pre-baked at 110°C for 240 seconds using a heating plate to form a coating film. Afterwards, the entire surface was exposed and heated at 280°C for 2 hours in a nitrogen atmosphere using a temperature-controlled curing furnace (VF-2000, manufactured by Koyo Lindberg) to obtain a hardened relief pattern (thermohardened polyimide coating). The heat-treated film was evaluated for the bonding properties between the aluminum substrate and the hardened resin coating based on the following criteria in accordance with the cross-cut method of the JIS K 5600-5-6 standard. If the evaluation is A to B, it can be preferably used as a hardened film suitable for semiconductors.

A: The number of grids of the hardened resin coating on the substrate is 80 or more to 100 B: The number of grids of the hardened resin coating on the substrate is 40 or more and less than 80 C: The number of grids of the hardened resin coating on the substrate is less than 40

<Production Example 1> Synthesis of polymer A1 as a precursor of (A) polyimide 155 g (0.5 mol) of 4,4'-oxydiphthalic anhydride (ODPA) was placed in a 2-liter separable flask, 135 g (0.2 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 79.1 g of pyridine was added while stirring. After stirring for 16 hours, a reaction mixture was prepared.

Next, under ice cooling, a solution prepared by dissolving 203 g of dicyclohexylcarbodiimide (DCC) in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, and then a solution prepared by suspending 48 g (0.44 mol) of p-phenylenediamine (pPD) in 280 ml of γ-butyrolactone was added over 60 minutes while stirring. The mixture was further stirred at room temperature for 4 hours, and then 40 ml of ethanol was added and stirred for 1 hour, and then 1 liter of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 4 liters of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was separated by filtration and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 30 liters of water to precipitate the polymer. The obtained precipitate was separated by filtration and then vacuum dried to obtain a powdered polymer (polymer A1). The molecular weight of polymer A1 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 18,000.

<Production Example 2> Synthesis of polymer A2 as a precursor of (A) polyimide Except for using 94 g (0.44 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB: m-tolidine) instead of 48 g (0.44 mol) of p-phenylenediamine (pPD) in Production Example 1, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A2. The molecular weight of polymer A2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 24,000.

<Production Example 3> Synthesis of polymer A3 as a precursor of (A) polyimide 108 g (0.5 mol) of pyromellitic dianhydride (PMDA) was used instead of 155 g (0.5 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1, and 94 g (0.44 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB: m-tolidine) was used instead of 48 g (0.44 mol) of p-phenylenediamine (pPD). The reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A3. The molecular weight of polymer A3 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000.

<Production Example 4> Synthesis of polymer A4 as a precursor of (A) polyimide Except for using 140 g (0.44 mol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) instead of 48 g (0.44 mol) of p-phenylenediamine (pPD) in Production Example 1, the reaction was carried out in the same manner as described in the above Production Example 1 to obtain polymer A4. The molecular weight of polymer A4 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 24,000.

<Production Example 5> Synthesis of polymer A5 as a precursor of polyimide (A) Except that 147 g (0.5 mol) of 3,3'-,4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155 g (0.5 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 4, the reaction was carried out in the same manner as described in the above Production Example 4 to obtain polymer A5. The molecular weight of polymer A5 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 24,000.

<Preparation of photosensitive resin composition> Each compound was weighed according to the mixing ratio listed in Table 1 and dissolved in a (D) solvent prepared by mixing GBL (D1) and DMSO (D2) at a weight ratio of 80:20 to obtain a solution. The viscosity of the obtained solution was adjusted to about 40 poise by adding a necessary amount of (D) solvent of GBL (D1): DMSO (D2) = 80:20 to prepare a photosensitive resin composition. The composition was evaluated according to the above method and the results are shown in Table 1. The values listed in Table 1 are weight parts. In addition, for the names of each compound (A) to (F) listed in Table 1, the freezing point or melting point of a part of the compound (B) plasticizer and (F) other additives and the number of repetitions of the unit structure are listed in Table 2. Furthermore, the substituents and other structures of the plasticizer (B) represented by formula (3) are recorded in Table 3. Furthermore, F4 and F5 as (F) other additives in Table 2 are common plasticizers that do not conform to the plasticizer (B) of this embodiment. Moreover, although F6 to F8 do not conform to the plasticizer (B) of this embodiment, they are compounds having a structure similar to the plasticizer (B) of this embodiment in terms of having a compound or repeating unit represented by general formula (3).

[Table 1-A] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 (A) Polyimide Precursor A1 100 100 A2 100 100 100 100 100 100 100 100 100 100 A3 A4 A5 (B) Plasticizer B1 15 B2 15 15 3 30 10 10 B3 5 B4 B5 15 B6 5 B7 10 B8 10 (C) Photopolymerization initiator C1 5 5 5 5 5 5 5 5 5 5 5 5 (D) Solvent D1 100 100 100 100 100 100 100 100 100 100 100 100 D2 25 25 25 25 25 25 25 25 25 25 25 25 (E) Radical polymerizable compound E1 5 E2 E3 E4 (F) Other additives F1 10 10 10 10 10 10 10 10 10 10 10 10 F2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 F3 5 5 5 5 5 5 5 5 5 5 5 5 F4 F5 F6 F7 F8 Evaluation results Aluminum tightness A A A B A B B B A A A A Young's modulus C C B C B B C C B B B B Resolution B A B B C B B C C B B A

[Table 1-B] Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Comparative Example 6 Comparison Example 7 (A) Polyimide Precursor A1 100 100 100 100 100 A2 100 100 100 A3 100 100 100 100 100 A4 100 A5 100 (B) Plasticizer B1 B2 15 40 10 10 10 B3 5 10 B4 15 B5 B6 B7 B8 (C) Photopolymerization initiator C1 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 (D) Solvent D1 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 D2 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 (E) Radical polymerizable compound E1 15 E2 5 E3 5 E4 5 (F) Other additives F1 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 F2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 F3 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 F4 15 F5 15 F6 15 F7 15 F8 15 Evaluation results Aluminum tightness B B A A B A A A C B C B C C C Young's modulus A C C C B B B B D D C D B B B Resolution C B C C C A A A B D D C D D D

[Table 2] Freezing point(℃) Melting point(℃) Number of repetitions of unit structure (A) Polyimide Precursor A1 Preparation of the polyimide precursor described in Example 1 - - - A2 Preparation of the polyimide precursor described in Example 2 - - - A3 Preparation of the polyimide precursor described in Example 3 - - - A4 Preparation of the polyimide precursor described in Example 4 - - - A5 Preparation of the polyimide precursor described in Example 5 - - - (B) Plasticizer B1 Polyoxyethylene monomethyl ether, Mw 400 (Trade name: Uniox M-400, manufactured by NOF Corporation) 0 - 8 B2 Polyoxyethylene dimethyl ether, Mw 400 (Trade name: Uniox MM-400, manufactured by NOF Corporation) 5 - 8 B3 Polyoxyethylene monomethyl ether, Mw 1000 (Trade name: Uniox M-1000, manufactured by NOF Corporation) 40 - twenty two B4 Polyethylene glycol, Mw 400 (trade name: PEG#400, manufactured by NOF Corporation) 6 - 9 B5 Polyethylene glycol, Mw 300 (trade name: PEG#300, manufactured by NOF Corporation) -8 - 6 B6 Polyoxyethylene monomethyl ether, Mw 2000 (Trade name: Uniox M-2000, manufactured by NOF Corporation) 50 - 45 B7 Polytetramethylene glycol, Mw 650 (trade name: PTMG650, manufactured by Mitsubishi Chemical Co., Ltd.) 11 - 9 B8 Polypropylene glycol, Mw 400 (Trade name: Uniol D-400G, manufactured by NOF Corporation) -31 -31 7 (C) Photopolymerization initiator C1 2-[[(Ethoxycarbonyl)oxy]imino]-1-phenylpropane-1-one (trade name: Speed Cure PDO, manufactured by LAMBSON) - - - (D) Solvent D1 γ-Butyrolactone (Mitsubishi Chemical) - - - D2 Dimethyl sulfoxide (manufactured by Toray Fine Chemicals) - - - (E) Radical polymerizable compound E1 Tetraethylene glycol dimethacrylate (trade name: NK Ester 4G, manufactured by Shin-Nakamura Chemical Industries, Ltd.) - - - E2 Tricyclodecanedimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Industries, Ltd.) - - - E3 Ethoxylated bisphenol A dimethacrylate (trade name: NK Ester BPE-500, manufactured by Shin-Nakamura Chemical Industries, Ltd.) - - - E4 Tris-(2-acryloyloxyethyl) isocyanurate (trade name: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Industries, Ltd.) - - - (F) Other additives F1 N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) - - - F2 N-[3-(Triethoxysilyl)propyl]phthalamide - - - F3 Methylated urea resin (trade name: NIKALAC MX-290, manufactured by SANWA CHEMICAL Co., Ltd.) - - - F4 Di-2-ethylhexyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) -50 -50 1 F5 Dicyclohexyl phthalate - 66 1 F6 Dipropylene glycol methyl ether acetate - -25 2 F7 Tripropylene glycol methyl ether -78 -78 3 F8 Tripropylene glycol butyl ether -75 -75 3

[table 3] General formula (3) a+b n ₂ R ₆ R ₇ R _6' R _7' R ₈ R ₉ B1 2 8 H H H H CH ₃ H B2 2 8 H H H H CH ₃ CH ₃ B3 2 twenty two H H H H CH ₃ H B4 2 9 H H H H H H B5 2 6 H H H H H H B6 2 45 H H H H CH ₃ H B7 4 9 H H H H H H B8 2 (a＝1，b＝1) 7 CH ₃ H H H H H

From the evaluation results in Table 1, it can be seen that Comparative Examples 1 to 7, which do not meet the requirements of this embodiment, cannot achieve good performance in terms of adhesion to aluminum, Young's modulus, and resolution in a balanced manner. On the other hand, Examples 1 to 20 all show excellent performance in terms of adhesion to aluminum, Young's modulus, and resolution. By comparing Comparative Examples 1, 2, and 4 with Example 2, and by comparing Comparative Examples 3, 5, 6, and 7 with Example 13, it can be seen that by using the (B) plasticizer, which is a requirement of this embodiment, adhesion to aluminum, Young's modulus, and resolution are improved. In Comparative Example 2 or Comparative Examples 4 to 7, a compound generally referred to as a plasticizer or a compound having a structure similar to the plasticizer (B) of this embodiment is contained. However, it is speculated that because the freezing point or melting point specified in this embodiment, or the number of repetitions of the unit structure or the structure represented by the general formula (3) is not satisfied, sufficient plasticizing effect or compatibility with other composition components is not obtained, and the effect of improving the adhesion with aluminum, Young's modulus and resolution is not obtained.

When comparing Example 2 with Example 3, Example 3 using (A) a polyimide precursor in which _Y1 comprises A2 of the general formula (4) is superior in Young's modulus. When comparing Example 11 with Example 12 and Examples 18 to 20, Example 12 and Examples 18 to 20 comprising (E) a radical polymerizable compound have good resolution. The detailed structures of (B) plasticizers are compared. Comparing Example 1, Example 2 and Example 15, it can be seen that Example 1 and Example 2, in which the (B) plasticizer is a (B) plasticizer with a structure represented by the general formula (3) and R ₈ and/or R ₉ is an alkyl group, have good resolution, and Example 2, in which both R ₈ and R ₉ are alkyl groups, has even better resolution. In addition, comparing Example 9 with Example 10 and Example 11, it can be seen that Example 10 and Example 11, in which the (B) plasticizer is a (B) plasticizer with a structure represented by the general formula (3) and a total of a and b is 2 to 3, have good resolution. It is speculated that this is because the compatibility of the (B) plasticizer in the photosensitive resin composition is better, so the resolution is improved. If Example 3 is compared with Example 7, and Example 6 with Example 8, Example 3 (n2 is 8) and Example 6 ( _{n2 is 22), wherein the plasticizer (B) is a plasticizer having a structural formula represented by the general formula (3) and n2 is} 8 to 23, are superior in terms of performance balance. The reason is not certain, but it is believed that if the value of _n2 is larger, such as Example 8 ( _n2 is 45) _, the effect of promoting the filling of the polymer during the compatibility or heat treatment is reduced, and the help to improve the resolution or Young's modulus is often reduced. In addition, it is speculated that even if the value of _n2 is smaller, such as Example 7 ( _n2 is 6), a sufficient plasticizing effect is not obtained, and the effect of improving the adhesion with aluminum or the Young's modulus becomes smaller (Example 7). In addition, regarding (B) plasticizer, if it contains 5 parts by mass or more relative to 100 parts by mass of (A) polyimide precursor, it is particularly effective in improving the adhesion with aluminum or Young's modulus (based on the comparison between Example 3 and Example 4). Furthermore, if more than 30 parts by mass of (B) plasticizer is contained relative to 100 parts by mass of (A) polyimide precursor, the resolution deteriorates, so it is more preferable to contain 5 to 30 parts by mass of (B) plasticizer (based on the comparison between Example 2 and Example 16). [Industrial Applicability]

By using the photosensitive resin composition of the present invention, a hardened relief pattern with high mechanical strength (Young's modulus), excellent adhesion to aluminum and excellent resolution can be obtained. The present invention can be preferably used in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multi-layer wiring substrates.

Claims (10)

A negative photosensitive resin composition comprising: (A) having the following general formula (1): {wherein, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and at least one of _R1 and _R2 is a group having an ethylenically unsaturated bond}; (B) a plasticizer having a freezing point or a melting point of above -40°C and having 3 or more repeating units; and (C) a photopolymerization initiator. A negative photosensitive resin composition comprising: (A) having the following general formula (1): A polyimide precursor having a structure of {wherein, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and at least one of _R1 and _R2 is a group having an ethylenically unsaturated bond}; (B) the following general formula (3): [Chemical 3] (wherein _n2 is an integer of 6 to 45, a and b are each independently an integer of 0 to 5; but the sum of a and b is an integer of 1 to 5; and _R6 , _R7 , R6 _' , _R7' , _R8 , _R9 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms); and (C) a photopolymerization initiator. The negative photosensitive resin composition of claim 1 or 2, wherein _R1 and _R2 in the above general formula (1) are independently hydrogen atoms, or the following general formula (2): [Chemical 4] (wherein R ₃ , R ₄ and R ₅ are independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer from 2 to 10) a monovalent organic group represented by, or a saturated aliphatic group having 1 to 4 carbon atoms. The negative photosensitive resin composition of claim 1 or 2, wherein _Y1 in the above general formula (1) comprises a structure represented by the following general formula (4), [Chemical 5] (wherein, _R10 and _R11 each independently represent an alkyl group having 1 to 4 carbon atoms, a fluorine atom, or a trifluoromethyl group). The negative photosensitive resin composition of claim 1 or 2, wherein _X1 in the general formula (1) comprises at least one structure selected from the group consisting of the following general formulas (5), (6) and (7), [Chemical 6] [Chemistry 7] [Chemistry 8] . The negative photosensitive resin composition of claim 1 or 2 comprises the plasticizer (B) having a structure represented by _n2 in the general formula (3) being an integer of 8 to 23. The negative photosensitive resin composition of claim 1 or 2 contains 5 to 30 parts by weight of the plasticizer (B) relative to 100 parts by weight of the polyimide precursor (A). The negative photosensitive resin composition of claim 1 or 2, comprising a free radical polymerizable compound (E). The negative photosensitive resin composition of claim 1 or 2 is a negative photosensitive resin composition for forming a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure. A method for producing a hardened relief pattern, comprising: (1) forming a photosensitive resin layer on a substrate by applying a negative photosensitive resin composition as claimed in claim 1 or 2 to the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) hardening the relief pattern by heating the relief pattern.