KR20200119202A - Negative photosensitive resin composition, method of producing polyimide and method of producing cured relief pattern - Google Patents

Abstract

The present invention relates to a negative photosensitive resin composition capable of obtaining high chemical resistance and resolution, and suppressing the generation of voids at the interface of a Cu layer in contact with a resin layer after a high temperature storage test. The negative photosensitive resin composition comprises: (A) a polyimide precursor; (B) a photoinitiator; (C) a silane coupling agent represented by chemical formula (1); and (D) an organic solvent including at least one selected from the group consisting of gamma-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, imethyl succinate, dimethyl malonate, and epsilon-caprolactone. In the chemical formula, a is an integer of 1 to 3, n is an integer of 1 to 6, R21 is each independently an alkyl group having 1 to 4 carbon atoms, R22 is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R20 is at least one selected from the group consisting of a substituent including an epoxy group, a phenylamino group, a ureide group, and an isocyanate group.

Description

TECHNICAL FIELD The manufacturing method of a negative photosensitive resin composition, a polyimide, and a curing relief pattern TECHNICAL FIELD [NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION, METHOD OF PRODUCING POLYIMIDE AND METHOD OF PRODUCING CURED RELIEF PATTERN}

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

BACKGROUND ART Conventionally, polyimide resins, polybenzoxazole resins, phenol resins, etc., which have excellent heat resistance, electrical properties, and mechanical properties, have been used for insulating materials for electronic components and for passivation films, surface protective films, and interlayer insulating films for semiconductor devices. . Among these resins, those provided in the form of a photosensitive resin composition can easily form a heat-resistant relief pattern film by application of the composition, exposure, development, and thermal imidization treatment by curing. Such a photosensitive resin composition has the characteristic that it enables a significant process reduction compared with the conventional non-photosensitive material.

By the way, a semiconductor device (hereinafter, also referred to as a "element") is mounted on a printed circuit board in various ways according to the purpose. Conventional elements are generally manufactured by a wire bonding method in which a thin wire is connected from an external terminal (pad) of the element to a lead frame. However, today, when the speed of the device has advanced and the operating frequency has reached GHz, the difference in wiring lengths of each terminal in the mounting has reached the point where it affects the operation of the device. For this reason, in mounting a device for high-end use, it is necessary to accurately control the length of the mounting wiring, and it has become difficult to satisfy the demand by wire bonding.

Therefore, flip chip mounting has been proposed in which a redistribution layer is formed on the surface of a semiconductor chip, and a bump (electrode) is formed thereon, and then the chip is turned over and directly mounted on a printed circuit board (for example, Patent Document 1 Reference). In this flip-chip mounting, since the wiring distance can be accurately controlled, it is employed in devices for high-end applications that handle high-speed signals, or in mobile phones because of its small mounting size, and demand is rapidly expanding. When a material such as polyimide, polybenzoxazole, or phenol resin is used for flip chip mounting, a metal wiring layer forming step is performed after the pattern of the resin layer is formed. In general, the metal wiring layer is subjected to plasma etching on the surface of the resin layer to roughen the surface, and then a metal layer serving as a seed layer for plating is formed by sputtering to a thickness of 1 μm or less, and then the metal layer is used as an electrode. Thus, it is formed by electrolytic plating. At this time, in general, titanium (Ti) is used as the metal used as the seed layer, and copper (Cu) is used as the metal in the redistribution layer formed by electrolytic plating.

In addition, recently, fan-out semiconductor packages are attracting attention. In a fan-out type semiconductor package, a chip encapsulant larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with an encapsulant (resin layer). In addition, a redistribution layer extending to the semiconductor chip and the encapsulant region is formed. The redistribution layer is formed with a thin film thickness. Moreover, since the rewiring layer can be formed up to the region of the sealing material, the number of external connection terminals can be increased.

With respect to such a metal rewiring layer, it is required to have high adhesion between the rewired metal layer and the resin layer after the reliability test. In particular, in recent years, the temperature at which the redistribution layer is heated and cured is required to be lower. Examples of the reliability test include a high-temperature storage test, which is stored in air at a high temperature of 125°C or higher for 100 hours or longer; A high-temperature operation test in which the operation under storage for 100 hours or more in air at a temperature of about 125°C while applying a voltage by attaching wiring is confirmed; A temperature cycle test in which a low temperature state of about -65°C to -40°C and a high temperature state of about 125°C to 150°C are reciprocated in air in a cycle; A high-temperature, high-humidity storage test that is stored in a vapor atmosphere of 85% or more of humidity at a temperature of 85°C or higher; High-temperature, high-humidity bias test in which a test similar to the high-temperature, high-humidity storage test is carried out while applying a voltage by attaching a wire; And a solder reflow test in which a 260 degreeC solder reflono is passed multiple times in air or under nitrogen, etc. are mentioned.

Japanese Laid-Open Patent Publication No. 2001-338947

However, among the above reliability tests, in the case of the high-temperature storage test, there is a problem that voids occur at the interface of the rewired Cu layer after the test in contact with the resin layer. In particular, when the temperature to be cured by heating is low, there is a tendency to become more remarkable. When a void occurs at the interface between the Cu layer and the resin layer, the adhesiveness between the two is deteriorated.

Moreover, in addition to the problem of voids, the metal rewiring layer is required to have chemical resistance, and the demand for miniaturization is also increasing. For this reason, in particular, the photosensitive resin composition used for formation of a rewiring layer of a semiconductor is required to suppress generation of voids and exhibit high chemical resistance and resolution.

The present invention was devised in view of such a conventional situation, and high chemical resistance and resolution are obtained, and after a high temperature storage test, the occurrence of voids at the interface of the Cu layer in contact with the resin layer is prevented. An object thereof is to provide a negative photosensitive resin composition that can be suppressed (hereinafter, also simply referred to as "photosensitive resin composition" in the present specification). Moreover, it is also one object to provide a method for forming a cured relief pattern using the negative photosensitive resin composition of the present invention.

The inventors of the present invention have found that the above problems can be solved by combining a specific polyimide precursor, a silane coupling agent having a specific structure, and a specific organic solvent, and have come to complete the present invention. That is, the present invention is as follows.

[One]

The following ingredients:

(A) polyimide precursor;

(B) photoinitiator;

(C) the following general formula (1):

[Formula 1]

{In the formula, a is an integer of 1 to 3, n is an integer of 1 to 6, R ₂₁ is each independently an alkyl group having 1 to 4 carbon atoms, and R ₂₂ is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, And R ₂₀ is at least one member selected from the group consisting of an epoxy group, a phenylamino group, a ureide group, and a substituent including an isocyanate group.}

Silane coupling agent represented by; And

(D) an organic solvent containing at least one selected from the group consisting of γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone ;

A negative photosensitive resin composition containing a.

[2]

The negative photosensitive resin composition according to [1], wherein in the general formula (1), R ₂₀ is at least one selected from the group consisting of a phenylamino group and a substituent including a ureide group.

[3]

The negative photosensitive resin composition according to [1] or [2], wherein in the general formula (1), R ₂₀ is a substituent containing a phenylamino group.

[4]

(E) The negative photosensitive resin composition according to any one of [1] to [3], further comprising a hot base generator.

[5]

The (D) organic solvent is at least two selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone. The negative photosensitive resin composition according to any one of [1] to [4] to be contained.

[6]

The (A) polyimide precursor is the following general formula (2):

[Formula 2]

{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 each independently a hydrogen atom or a monovalent oil It is a device, and at least one of R ₁ and R ₂ is a monovalent organic group.}

The negative photosensitive resin composition according to any one of [1] to [5], which has a structural unit represented by.

[7]

In the general formula (2), at least one of R ₁ and R ₂ is the following general formula (3):

[Formula 3]

{In the formula, L ₁ , L _2, and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10.}

The negative photosensitive resin composition according to [6], which is a monovalent organic group represented by.

[8]

In the general formula (2), X ₁ is the following general formula (20a):

[Formula 4]

The negative photosensitive resin composition according to [6] or [7], which has a structure represented by.

[9]

In the general formula (2), X ₁ is the following general formula (20b):

[Formula 5]

The negative photosensitive resin composition according to [6] or [7], which has a structure represented by.

[10]

In the general formula (2), X ₁ is the following general formula (20c):

[Formula 6]

The negative photosensitive resin composition according to [6] or [7], which has a structure represented by.

[11]

In the general formula (2), Y ₁ is the following general formula (21b):

[Formula 7]

The negative photosensitive resin composition in any one of [6]-[10] containing the structure represented by.

[12]

In the general formula (2), Y ₁ is the following general formula (21c):

[Formula 8]

{In the formula, R ₆ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and n is from 0 to 4 It is an integer selected.}

The negative photosensitive resin composition in any one of [6]-[10] containing the structure represented by.

[13]

The (A) polyimide precursor is the following general formula (4):

[Formula 9]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 .}

The negative photosensitive resin composition according to [6] or [7], which has a structural unit represented by.

[14]

The (A) polyimide precursor is the following general formula (5):

[Formula 10]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 .}

The negative photosensitive resin composition according to [6] or [7], which has a structural unit represented by.

[15]

The (A) polyimide precursor is the following general formula (4):

[Formula 11]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 The structural unit represented by .}, and

The following general formula (5):

[Formula 12]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 . These may be the same as or different from R ₁ , R ₂ , and n ₁ in General Formula (4).}

The negative photosensitive resin composition according to [6] or [7], which simultaneously contains the structural unit represented by.

[16]

The negative photosensitive resin composition according to [15], wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5).

[17]

The (A) polyimide precursor is the following general formula (6):

[Formula 13]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 .}

The negative photosensitive resin composition according to [6] or [7], which has a structural unit represented by.

[18]

100 parts by mass of the (A) polyimide precursor,

0.1 to 20 parts by mass of the (B) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor,

0.1 to 20 parts by mass of the (C) silane coupling agent based on 100 parts by mass of the (A) polyimide precursor

The negative photosensitive resin composition in any one of [1]-[17] containing.

[19]

A polyimide production method including a step of converting the negative photosensitive resin composition according to any one of [1] to [18] to a polyimide.

[20]

The following process:

(1) A step of applying the negative photosensitive resin composition according to any one of [1] to [18] on a substrate to form a photosensitive resin layer on the substrate;

(2) Step of exposing the photosensitive resin layer;

(3) Step of developing the photosensitive resin layer after exposure to form a relief pattern; And,

(4) Step of heat-treating the relief pattern to form a cured relief pattern;

Containing, the method for producing a cured relief pattern.

According to the present invention, high chemical resistance and resolution are obtained, and after a high temperature storage test, the production of a negative photosensitive resin composition and polyimide that suppresses the occurrence of voids at the interface of the Cu layer in contact with the resin layer A method can be provided, and a method for forming a cured relief pattern using the negative photosensitive resin composition can be provided.

Hereinafter, an embodiment for carrying out the present invention (hereinafter, abbreviated as "embodiment") will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

In addition, throughout this specification, when a plurality of structures represented by the same reference numerals in the general formula are present in a molecule, they may be the same or different from each other.

<Negative photosensitive resin composition>

The negative photosensitive resin composition according to the present embodiment includes the following components:

(A) polyimide precursor;

(B) photoinitiator;

(C) a silane coupling agent having a specific structure; And

(D) specific organic solvent;

Includes.

From the viewpoint of obtaining high resolution, the negative photosensitive resin composition includes 0.1 to 20 parts by mass based on 100 parts by mass of (A) polyimide precursor, and (A) 100 parts by mass of polyimide precursor (B) photoinitiator and , (A) 0.1 to 20 parts by mass based on 100 parts by mass of the polyimide precursor (C) It is preferable to contain a silane coupling agent having a specific structure.

(A) polyimide precursor

The (A) polyimide precursor in this embodiment is a resin component contained in the negative photosensitive resin composition, and is converted into polyimide by performing heat cyclization treatment.

The polyimide precursor is the following general formula (2):

[Formula 14]

{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 each independently a hydrogen atom or a monovalent oil It's a device.}

It is preferably a polyamide having a structural unit represented by.

At least one of R ₁ and R ₂ is preferably, the following general formula (3):

[Formula 15]

{In the formula, L ₁ , L _2, and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10.}

It is a monovalent organic group represented by.

Although n ₁ in General Formula (2) is not limited as long as it is an integer of 2 to 150, an integer of 3 to 100 is preferable, and an integer of 5 to 70 from the viewpoint of photosensitive properties and mechanical properties of the negative photosensitive resin composition. An integer is more preferable.

In the general formula (2), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably -COOR ₁ group and -COOR from the viewpoint of achieving both heat resistance and photosensitive properties. _{The 2} group and the -CONH- group are an aromatic group or an alicyclic aliphatic group in an ortho position to each other. As the tetravalent organic group represented by X ₁ , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (20):

[Formula 16]

{In the formula, R ₆ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and l is selected from 0 to 2 And m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4. A group having a structure represented by} is mentioned, but is not limited thereto. In addition, the structure of X ₁ may be one or a combination of two or more. The X ₁ group having a structure represented by the above formula (20) is preferable from the viewpoint of making both heat resistance and photosensitive properties compatible.

As the X ₁ group, among the structures represented by the above formula (20), the following formula (20A), (20B), or (20C):

[Formula 17]

[Formula 18]

[Formula 19]

The structure represented by is more preferable from the viewpoint of chemical resistance, resolution, and void suppression after a high temperature storage test, and the following formulas (20a), (20b) or (20c):

[Formula 20]

[Formula 21]

[Formula 22]

The structure represented by is particularly preferred.

In the general formula (2), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties, for example, the following formula (21):

[Formula 23]

{In the formula, R ₆ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and n is from 0 to 4 It is an integer selected.}

Although the structure represented by is mentioned, it is not limited to these. In addition, the structure of Y ₁ may be one or a combination of two or more. The Y ₁ group having a structure represented by the above formula (21) is preferable from the viewpoint of achieving both heat resistance and photosensitive properties.

As the Y ₁ group, among the structures represented by the above formula (21), the following formula (21A), (21B) or (21C):

[Formula 24]

[Formula 25]

[Formula 26]

The structure represented by is preferable from the viewpoint of chemical resistance, resolution, and void suppression after a high temperature storage test, and the following formula (21b) or (21c):

[Formula 27]

[Formula 28]

The structure represented by is particularly preferred.

In the general formula (3), L ₁ is preferably a hydrogen atom or a methyl group, and L ₂ and L ₃ are preferably a hydrogen atom from the viewpoint of photosensitive properties. Moreover, m ₁ is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive properties.

In one embodiment, the (A) polyimide precursor is the following general formula (4):

[Chemical Formula 29]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 .}

It is preferable that it is a polyimide precursor which has a structural unit represented by.

In general formula (4), it is more preferable that at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (3). When the (A) polyimide precursor contains the polyimide precursor represented by the general formula (4), the effect of resolving property becomes particularly high.

In one embodiment, the (A) polyimide precursor is the following general formula (5):

[Formula 30]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 .}

It is preferable that it is a polyimide precursor which has a structural unit represented by.

In general formula (5), it is more preferable that at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (3). When the (A) polyimide precursor contains the polyimide precursor represented by the general formula (5) in addition to the polyimide precursor represented by the general formula (4), the effect of resolving property is particularly enhanced.

Among these, the (A) polyimide precursor contains the structural units represented by the general formulas (4) and (5) at the same time, or is a copolymer of the structural units represented by the general formulas (4) and (5). , From the viewpoint of chemical resistance, resolution, and suppression of voids after a high temperature storage test. (A) In the case where the polyimide precursor is a copolymer of structural units represented by general formulas (4) and (5), R ₁ , R ₂ , and n ₁ in one formula are, respectively, R ₁ in the other formula, R ₂ and n ₁ may be the same as or different from each other.

In one embodiment, the (A) polyimide precursor is the following general formula (6):

[Formula 31]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 .}

It is preferable that it is a polyimide precursor which has a structural unit represented by.

In general formula (6), it is more preferable that at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (3). When the (A) polyimide precursor contains the polyimide precursor represented by General Formula (6), the effect of chemical resistance in particular increases.

(A) Method for preparing a polyimide precursor

(A) The polyimide precursor includes a tetracarboxylic dianhydride containing a tetravalent organic group X ₁ in the aforementioned general formula (2), alcohols having a photopolymerizable unsaturated double bond, and optionally an unsaturated double bond. After preparing a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester body) by reacting alcohols that do not have, this and the divalent organic group Y ₁ in the aforementioned general formula (2) are included. It is obtained by amide polycondensation of diamines.

(Preparation of acid/ester body)

In this embodiment, as the tetracarboxylic dianhydride containing a tetravalent organic group X ₁ which is preferably used to prepare a polyimide precursor (A), tetracarboxylic dianhydride having a structure represented by the general formula (20) Including carboxylic dianhydride, for example, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4' -Tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, di Phenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1 ,1,1,3,3,3-hexafluoropropane, etc., preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone- 3,3',4,4'-tetracarboxylic dianhydride and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited thereto. In addition, these may be used alone, as well as a mixture of two or more.

In this embodiment, as alcohols having a photopolymerizable unsaturated double bond, which are preferably used in order to prepare a polyimide precursor (A), for example, 2-acryloyloxyethyl alcohol, 1-acrylo Iloxy-3-propyl alcohol, 2-acrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxy Propylacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-hydroxy-3-butoxypropylacrylate, 2-hydroxy-3-t-butoxypropylacrylate, 2-hydroxy- 3-cyclohexyloxypropylacrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl Vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy- 3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc. are mentioned.

To the alcohols having a photopolymerizable unsaturated double bond, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-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 mono Some alcohols that do not have an unsaturated double bond, such as ethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol, may be mixed and used.

Further, as a polyimide precursor, a non-photosensitive polyimide precursor prepared only from alcohols having no unsaturated double bond may be mixed with a photosensitive polyimide precursor to be used. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

Acid anhydride by stirring and dissolving the preferred tetracarboxylic dianhydride and the alcohols in a solvent as described later in the presence of a basic catalyst such as pyridine at a temperature of 20 to 50° C. for 4 to 10 hours and mixing The esterification reaction proceeds, and a desired acid/ester body can be obtained.

(Preparation of polyimide precursor)

To the acid/ester body (typically a solution in a solvent described later), under ice-cooling, a suitable dehydration condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. are added and mixed to form an acid/ester form of polyacid anhydride. After setting it as, diamines containing a divalent organic group Y ₁ preferably used in the present embodiment are added dropwise to the solution or dispersed in a separate solvent, and amide polycondensation is performed to obtain the target polyimide precursor. Can be obtained. In general, the above-described acid/ester body is acid-chlorinated using a thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine, whereby the target polyimide precursor can be obtained.

Diamines containing a divalent organic group Y ₁ preferably used in the present embodiment include diamines having a structure represented by the general formula (21), for example, p-phenylenediamine, m-phenyl Rendiamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4 '-Diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diamino Diphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-dia Minobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4 -Bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis(4-(4-aminophenoxy) Phenyl] sulfone, bis [4-(3-aminophenoxy) phenyl] sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis [4-(4-aminophenoxy)phenyl] ether, bis [4-(3-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, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and some of the hydrogen atoms on the benzene ring thereof, are methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc. Substituted, for example 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4, 4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof, etc. are mentioned, but the present invention is not limited thereto.

After completion of the amide polycondensation reaction, the absorption by-products of the dehydration condensation agent coexisting in the reaction solution are separated by filtration as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component. Then, the polymer component is precipitated, and the polymer is purified by repeating re-dissolution and reprecipitation operations, etc., and vacuum drying to isolate the target polyimide precursor. In order to improve the degree of purification, ionic impurities may be removed by passing a solution of this polymer through a column filled with an anion and/or a cation exchange resin swelled with an appropriate organic solvent.

When the molecular weight of the polyimide precursor (A) is measured by a weight average molecular weight in terms of polystyrene by gel permeation chromatography, it is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in a developer is good, and the resolution performance of the relief pattern is good. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. Moreover, the weight average molecular weight is calculated|required from the calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the standard sample STANDARD SM-105 manufactured by Showa Electric Corporation.

(B) photoinitiator

The photoinitiator (B) used in this embodiment will be described. As a photoinitiator, it is preferable that it is a photoradical polymerization initiator, and benzophenone derivatives, such as benzophenone, o-methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2, Acetophenone derivatives such as 2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methyloxanthone, 2-isopropylthioc Thioxanthone derivatives such as santon and diethyl thioxanthone, benzyl derivatives such as benzyl, benzyldimethylketal, and benzyl-β-methoxyethylacetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl- 1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2- Propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o- Oxime such as ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl) oxime, N-arylglycines such as N-phenylglycine, peroxidation of benzoyl perchloride, etc. Distribution, aromatic biimidazoles, titanocenes, and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide, etc. are preferably mentioned, but the present invention is not limited thereto. Among the photoinitiators, oximes are more preferable, particularly from the viewpoint of light sensitivity.

The blending amount of the photopolymerization initiator (B) in the negative photosensitive resin composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass, based on 100 parts by mass of the (A) polyimide precursor. It is not more than parts by mass. The blending amount is 0.1 parts by mass or more from the viewpoint of light sensitivity or patterning property, and 20 parts by mass or less from the viewpoint of physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

(C) a silane coupling agent having a specific structure

A silane coupling agent having a specific structure (C) used in the present embodiment will be described.

The silane coupling agent having a specific structure (C) according to the present embodiment has a structure represented by the following general formula (1).

[Formula 32]

{In the formula, a is an integer of 1 to 3, n is an integer of 1 to 6, R ₂₁ is each independently an alkyl group having 1 to 4 carbon atoms, and R ₂₂ is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, And R ₂₀ is at least one species selected from the group consisting of an epoxy group, a phenylamino group, and a substituent including a ureide group.}

In General Formula (1), a is not limited as long as it is an integer of 1 to 3, but 2 or 3 is preferable, and 3 is more preferable from the viewpoint of adhesion to the metal rewiring layer.

Although n is not limited as long as it is an integer of 1 to 6, 1 or more and 4 or less are preferable from the viewpoint of adhesion to the metal rewiring layer. From the viewpoint of developability, 2 or more and 5 or less are preferable.

R ₂₁ is not limited as long as it is an alkyl group having 1 to 4 carbon atoms. A methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, etc. can be illustrated.

R ₂₂ is not limited as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. The alkyl group having from 1 to 4 carbon atoms, there can be mentioned the same alkyl groups as R _21.

R ₂₀ is not limited as long as it is a substituent including an epoxy group, a phenylamino group, a ureide group, and an isocyanate group. Among these, from the viewpoint of developability and adhesiveness of the metal redistribution layer, it is preferable that it is at least one selected from the group consisting of a substituent containing a phenylamino group and a substituent containing a ureide group, and the substituent containing a phenylamino group is more desirable.

As the silane coupling agent containing an epoxy group, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. can be illustrated.

As a silane coupling agent containing a phenylamino group, N-phenyl-3-aminopropyltrimethoxysilane can be illustrated.

As a silane coupling agent containing a ureide group, 3-ureidopropyl trialkoxysilane can be illustrated.

As the silane coupling agent containing an isocyanate group, 3-isocyanate propyltriethoxysilane can be illustrated.

(D) an organic solvent with a specific structure

The organic solvent according to the present embodiment is at least one selected from the group consisting of γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone. It is not limited if it contains. By including the organic solvent, the adhesion to the sealing material can be sufficiently expressed. Among them, (A) from the viewpoint of the solubility of the polyimide precursor, γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, and ε-caprolactone are preferable, and from the viewpoint of suppressing copper surface voids It is more preferable to contain at least two types of organic solvents selected from the group.

The reason why the organic solvent having a specific structure according to the present embodiment has good adhesion to the sealing material is not clear, but the present inventors estimate as follows.

Conventionally, as an organic solvent for dissolving a photosensitive resin composition containing a polyimide precursor, an amide solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide is used. Has been. These solvents have very high solubility of the polyimide precursor, but in the case where the recently required heat-curing temperature is low (for example, less than 200°C), they have high affinity with the resulting polyimide. There is a tendency to remain. Therefore, the performance is deteriorated due to interaction with the silane coupling agent having a specific structure (C). On the other hand, by including the solvent, even when the heat curing temperature becomes low, since the solvent remaining in the film after heat curing can be sufficiently reduced, there is a tendency for good adhesion to the sealing material.

In the negative photosensitive resin composition of the present embodiment, the amount of the organic solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, based on 100 parts by mass of the (A) polyimide precursor. , More preferably from 125 to 500 parts by mass.

(E) Hot base generator

The negative photosensitive resin composition of this embodiment may further contain components other than the said (A)-(D) components. In particular, in order to cope with the lowering of the heating and curing temperature, it is more preferable to include (E) a hot base generator.

The hot base generator refers to a compound that generates a base by heating. By containing the hot base generator, the imidization of the photosensitive resin composition can be further promoted.

The type of the hot base generator is not particularly determined, but an amine compound protected by a tert-butoxycarbonyl group, a hot base generator disclosed in International Publication No. 2017/038598, and the like can be mentioned. However, it is not limited to these, and other known hot base generators can be used.

As an amine compound protected by a tert-butoxycarbonyl group, 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, ballinol, 3-amino-1, 2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-Aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanol Amine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypi Peridine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinmethanol, 3-piperidinmethanol, 2-piperidinmethanol, 4 -Piperidineethanol, 2-piperidinethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ether, 1,2-bis(2-amino Ethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene Glycolbis (3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of amino acids and derivatives thereof is protected by a tert-butoxycarbonyl group. However, it is not limited to these.

(E) The blending amount of the hot base generator is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. The blending amount is preferably 0.1 parts by mass or more from the viewpoint of the imidization promoting effect, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

The negative photosensitive resin composition of this embodiment may further contain components other than the said (A)-(E) components.

Components other than components (A) to (E) are not limited, but include nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, sensitizers, photopolymerizable unsaturated monomers, thermal polymerization inhibitors, etc. have.

<Nitrogen-containing heterocyclic compound>

In the case of forming a cured film on a substrate made of copper or a copper alloy using the negative photosensitive resin composition of the present embodiment, in order to suppress discoloration of the copper phase, the negative photosensitive resin composition optionally contains a nitrogen-containing heterocyclic compound. You may include it. Specifically, an azole compound, a purine derivative, etc. are mentioned.

As an azole compound, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4- t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl) triazole Sol, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl- 2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl -2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2- Hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H- Tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. are mentioned.

Especially preferably, tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole are mentioned. In addition, these azole compounds may be used alone or in a mixture of two or more.

Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2 -Methyl adenine, 1-methyl adenine, N-methyl adenine, N,N-dimethyl adenine, 2-fluoroadenine, 9-(2-hydroxyethyl) adenine, guanine oxime, N-(2-hydroxyethyl) Adenine, 8-aminoadenin, 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-azac And xanthine, 8-azahypoxanthine, and the like, and derivatives thereof.

When the negative photosensitive resin composition contains the azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor (A), and 0.5 to 5 from the viewpoint of light sensitivity characteristics. The mass part is more preferable. When the blending amount of the azole compound with respect to 100 parts by mass of the polyimide precursor (A) is 0.1 parts by mass or more, when the negative photosensitive resin composition of the present embodiment is formed on copper or copper alloy, discoloration of the surface of copper or copper alloy On the other hand, when it is 20 parts by mass or less, the light sensitivity is excellent.

<hindered phenol compound>

Moreover, in order to suppress the discoloration on the copper surface, the negative photosensitive resin composition may contain a hindered phenol compound arbitrarily. As a hindered phenol compound, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di -t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol) , Triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t -Butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N, N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2, 2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t- Butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6 -(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2, 4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1, 3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione , 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4, 6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1 ,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy -2-Methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hyde Roxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3- Hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl -5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc. are mentioned, but limited to this It does not become. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trione and the like are particularly preferred.

The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics, based on 100 parts by mass of the polyimide precursor (A). When the compounding amount of the hindered phenol compound to 100 parts by mass of the polyimide precursor (A) is 0.1 parts by mass or more, for example, when the negative photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, copper or Discoloration and corrosion of the copper alloy are prevented, and on the other hand, the light sensitivity is excellent in the case of 20 parts by mass or less.

<Organic titanium compound>

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

Examples of usable organic titanium compounds include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of the organic titanium compound are shown in the following I) to VII):

I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable from the viewpoint of obtaining storage stability and a good pattern of the negative photosensitive resin composition. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium di (n-butoxide) bis (2,4-pentanedionate, titanium diisopropoxide bis (2,4-pentanedionate) , Titanium diisopropoxide bis (tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate), and the like.

II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium Tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonyl oxide), titanium tetra (n-propoxide), titanium tetrastearyl oxide, titanium tetrakis[bis{2] ,2-(allyloxymethyl)butoxide}].

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

IV) Monoalkoxy titanium compounds: For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, and the like.

V) Titanium oxide compounds: For example, titanium oxide bis (pentanedionate), titanium oxide bis (tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.

VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate and the like.

VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, the organic titanium compound is at least one compound selected from the group consisting of I) a titanium chelate compound, II) a tetraalkoxy titanium compound, and III) a titanocene compound from the viewpoint of exhibiting better chemical resistance. Titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-di Particularly preferred is fluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyimide precursor (A). When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, and on the other hand, when it is 10 parts by mass or less, storage stability is excellent.

<Sensitizer>

The negative photosensitive resin composition of this embodiment may optionally contain a sensitizer in order to improve the light sensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis( 4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4' -Bis(diethylamino)chalcone, p-dimethylamino cinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p- Dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-) Diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3- Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 2-mercaptobenzimidazole , 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2-(p-dimethylaminobenzoyl) styrene, etc. are mentioned. These can be used individually or in combination of 2-5 types, for example.

When the negative photosensitive resin composition contains a sensitizer for improving light sensitivity, it is preferable that the blending amount is 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

<Photopolymerizable unsaturated monomer>

The negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. As such a monomer, a (meth)acrylic compound which undergoes radical polymerization reaction with a photoinitiator is preferable, and is not particularly limited to the following, but such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, Mono or diacrylate and methacrylate of ethylene glycol or polyethylene glycol, mono or diacrylate and methacrylate of propylene glycol or polypropylene glycol, mono, di or triacrylate and methacrylate of glycerol, cyclohexanedi Acrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacryl of neopentyl glycol Rate, mono or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate And methacrylate, di or triacrylate and methacrylate of glycerol, di, tri, or tetraacrylate and methacrylate of pentaerythritol, and compounds such as ethylene oxide or propylene oxide adducts of these compounds. I can.

When the photosensitive resin composition contains the monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is (A) 100 parts by mass of the polyimide precursor. It is preferable that it is 1-50 mass parts.

<Thermal polymerization inhibitor>

Further, the negative photosensitive resin composition of the present embodiment may optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and light sensitivity of the negative photosensitive resin composition, especially when stored in a solution state containing a solvent. do. As a thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine 4 acetic acid, 1,2-cyclohexane Diamine 4 acetic acid, glycol etherdiamine 4 acetic 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)hydro A hydroxylamine ammonium salt or the like is used.

<Method of manufacturing cured relief pattern and semiconductor device>

In addition, the present invention provides a step of (1) applying the negative photosensitive resin composition of the present embodiment described above on a substrate to form a photosensitive resin layer on the substrate, and (2) exposing the photosensitive resin layer. And (3) developing the photosensitive resin layer after exposure to form a relief pattern, and (4) heating the relief pattern to form a cured relief pattern. Provides a manufacturing method.

(1) Photosensitive resin layer formation process

In this step, the negative photosensitive resin composition of the present invention is applied onto a substrate and, if necessary, dried thereafter to form a photosensitive resin layer. As an application method, a method conventionally used for application of a photosensitive resin composition, for example, a method of applying with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc., a method of spraying with a spray coater, etc. You can use

If necessary, the coating film containing the negative photosensitive resin composition can be dried. As a drying method, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. Specifically, when performing air drying or heat drying, drying can be performed at 20°C to 140°C under the conditions of 1 minute to 1 hour. As described above, a photosensitive resin layer (negative photosensitive resin layer) can be formed on the substrate.

(2) Exposure process

In this step, the negative photosensitive resin layer formed above is exposed using an exposure apparatus such as a contact aligner, mirror projection, or stepper, through a photomask or reticle having a pattern, or directly, with an ultraviolet light source or the like. .

Thereafter, for the purpose of improving light sensitivity or the like, post-exposure baking (PEB) and/or pre-development baking may be performed according to an arbitrary combination of temperature and time, if necessary. As for the range of the baking conditions, the temperature is preferably from 40° C. to 120° C., and the time is preferably from 10 seconds to 240 seconds, but is limited to this range unless it impairs the properties of the negative photosensitive resin composition of the present invention. It doesn't work.

(3) Relief pattern formation process

In this step, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), an arbitrary method is selected from a conventionally known photoresist developing method, for example, a rotary spray method, a puddle method, an immersion method with ultrasonic treatment, etc. Can be used. Further, for the purpose of adjusting the shape of the relief pattern after development, or the like, if necessary, baking may be performed after development by any combination of temperature and time.

As a developer used for development, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and the poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyro Lactone, α-acetyl-γ-butyrolactone, and the like are preferable. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent by the solubility of the polymer in the negative photosensitive resin composition. Moreover, each solvent can also be used in combination of 2 or more types, for example, several types.

(4) Curing relief pattern formation process

In this step, while heating the relief pattern obtained by the above development to dilute the photosensitive component, (A) the polyimide precursor is imidized to convert it into a cured relief pattern made of polyimide. As a method of heat hardening, various methods can be selected, such as using a hot plate, using an oven, or using a temperature-rising oven capable of setting a temperature program. Heating can be performed, for example, at 170°C to 400°C under the conditions of 30 minutes to 5 hours. Air may be used as the atmosphere gas during heat curing, or an inert gas such as nitrogen or argon may be used.

<Polyimide>

The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (8).

[Formula 33]

{, X ¹ and Y ¹ in the formula is the formula (2) in X ₁ and the same and, m is a positive integer and Y _1.}

Preferred X ₁ and Y ₁ in the general formula (2) are also preferable in the polyimide of the general formula (8) for the same reason. The number of repeating units m of the general formula (8) may be a positive integer and is not particularly limited, but may be an integer of 2 to 150 or an integer of 3 to 140.

In addition, a method for producing a polyimide including a step of converting the negative photosensitive resin composition described above into a polyimide is also an aspect of the present invention.

<Semiconductor device>

In this embodiment, a semiconductor device having a cured relief pattern obtained by the method for producing a cured relief pattern described above is also provided. Accordingly, a semiconductor device having a substrate as a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the method for producing a cured relief pattern described above can be provided. In addition, the present invention can also be applied to a method for manufacturing a semiconductor device in which a semiconductor element is used as a base material and the method for manufacturing a cured relief pattern described above is included as part of the process. In the semiconductor device of the present invention, a cured relief pattern formed by the above cured relief pattern manufacturing method is formed as 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 of a semiconductor device having a bump structure. , It can be manufactured by combining it with a known manufacturing method of a semiconductor device.

<Display device>

In this embodiment, as a display device including a display element and a cured film formed on the upper portion of the display element, a display device in which the cured film is the above-described cured relief pattern is provided. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated through another layer. For example, as the cured film, a surface protective film, an insulating film, and a planarization film of a thin film transistor (TFT) liquid crystal display element and a color filter element, a projection for a multi-domain vertical alignment (MVA) type liquid crystal display device, and an organic electroluminescence And partition walls for negative electrode (EL) element cathodes.

The negative photosensitive resin composition of the present invention is useful in applications such as interlayer insulation of multilayer circuits, cover coats of flexible copper clad plates, solder resist films, and liquid crystal alignment films, in addition to applications to the above-described semiconductor devices.

Example

Hereinafter, although this embodiment is demonstrated concretely with an Example, this invention is not limited to this. In Examples, Comparative Examples, and Production Examples, the physical properties of the polymer or negative photosensitive resin composition were measured and evaluated according to the following method.

<Measurement and evaluation method>

(1) weight average molecular weight

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

Pump: JASCO PU-980

Detector: JASCO RI-930

Column oven: JASCO CO-965 40°C

Column: Showa Electric Co., Ltd. Shodex KD-806M 2 in series, or

Shodex 805M/806M serial manufactured by Showa Electric Co., Ltd.

Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Electric Works Co., Ltd.

Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP)

Flow rate: 1 mL/min.

(2) Preparation of cured relief pattern on Cu

200 nm-thick Ti and 400 nm-thick Cu using a sputtering device (L-440S-FHL type, manufactured by Canon Anelbas) on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) It sputtered in this order. Subsequently, on this wafer, the negative photosensitive resin composition prepared by the method described later was applied by rotation using a coater developer (D-Spin60A type, manufactured by SOKUDO), and prebaked with a hot plate at 110°C for 180 seconds. Then, a coating film having a thickness of about 7 μm was formed. An energy of 500 mJ/cm 2 was irradiated on this coating film by Prisma GHI (manufactured by Ultratech) using a mask with a test pattern formed thereon. Subsequently, this coating film was spray-developed with a coater developer (D-Spin60A type, manufactured by SOKUDO) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu.

The wafer on which the relief pattern was formed on Cu was heat-treated for 2 hours at the curing temperature shown in Table 1 in a nitrogen atmosphere using a temperature-rising programmable curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.). On the top, a cured relief pattern made of a resin having a thickness of about 4 to 5 µm was obtained.

(3) Evaluation of the resolution of the cured relief pattern on Cu

The cured relief pattern obtained by the above method was observed under an optical microscope, and the size of the minimum opening pattern was determined. At this time, if the area of the opening of the obtained pattern is 1/2 or more of the corresponding pattern mask opening area, it is regarded as resolved, and the length of the mask opening side corresponding to the one having the smallest area among the resolved openings is taken as the resolution.

Those having a resolution of less than 10 µm were set as "excellent", those having a resolution of 10 µm or more and less than 14 µm were set as "good", those having a resolution of 14 µm or more and less than 18 µm were set as "possible", and those having a resolution of 18 µm or more were set as "impossible".

(4) High temperature storage test of cured relief pattern on Cu and evaluation of void area thereafter

The wafer in which the cured relief pattern was formed on Cu was heated in air at 150° C. for 168 hours using a temperature-rising programmable cure furnace (VF-2000 type, manufactured by Koyo Lindbergh). Subsequently, all the Cu-phase resin layers were removed by plasma etching using a plasma surface treatment apparatus (EXAM type, manufactured by Shinko Seiki Co., Ltd.). Plasma etching conditions are as follows.

Power: 133 W

Gas type/flow rate: O ₂ : 40 mL/min + CF ₄ : 1 mL/min

Gas pressure: 50 Pa

Mode: Hard Mode

Etching time: 1800 seconds

The Cu surface from which all the resin layers were removed was observed with FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and using image analysis software (A phase group, manufactured by Asahi Chemical Corporation), on the surface of the Cu layer The area of the void occupied was calculated. When the total area of the voids when evaluating the photosensitive resin composition described in Comparative Example 1 is 100%, those with a total area ratio of voids less than 50% are "excellent", and those with 50% or more and less than 75% are "good", 75 What was more than% and less than 100% was judged as "possible", and what was 100% or more was judged as "impossible".

(5) Evaluation of chemical resistance of cured relief pattern (polyimide coating film)

The cured relief pattern formed on Cu was applied with a resist stripper {manufactured by ATMI, product name ST-44, main component: 2-(2-aminoethoxy)ethanol, and 1-cyclohexyl-2-pyrrolidone} It was immersed in the thing heated at 50 degreeC for 5 minutes, washed with running water for 1 minute, and air-dried. Thereafter, the film surface was visually observed with an optical microscope, and chemical resistance was evaluated based on the presence or absence of damage due to chemicals such as cracks, and/or the rate of change in the film thickness after treatment with the chemicals. As an evaluation criterion, if damage such as cracks does not occur and the film thickness change rate is within 10% based on the film thickness before chemical immersion, "Excellent", 10 to 15% is "Good", and 15 to 20%. The thing was set as "possible", and the thing in which a crack occurred or the thing with a film thickness change rate exceeding 20% was set as "impossible".

(6) Adhesion test with encapsulant

As an epoxy-based encapsulant, R4000 series manufactured by Nagase Chemtex was prepared.

Subsequently, on the silicon wafer sputtered with aluminum, the sealing material was spin-coated to a thickness of about 150 microns, followed by heat curing at 130°C to cure the epoxy-based sealing material. The photosensitive resin composition prepared in Examples and Comparative Examples was applied on the epoxy-based cured film so that the final film thickness was 10 microns. After exposing the entire surface of the applied photosensitive resin composition under exposure conditions of 500 mJ/cm 2, it was thermosetted at 180° C. for 2 hours to prepare a first layer cured film having a thickness of 10 microns.

The photosensitive resin composition used in the formation of the first layer cured film was applied on the first layer cured film, and the entire surface was exposed under the same conditions as in the production of the first layer cured film, followed by thermal curing, and 2 having a thickness of 10 microns. A layer cured film was produced.

An epoxy resin was applied on the photosensitive resin cured film of the sample, and a pin was then set up, and an adhesion test was performed using a take-up tester (manufactured by Quad Group Corporation, Sebastian 5 type). It evaluated according to the following criteria.

Evaluation: adhesive strength 70 MPa or more: excellent adhesion

More than 50 MPa-Less than 70 MPa: Good adhesion

More than 30 MPa-Less than 50 MPa: Adhesion is possible

Less than 30 MPa: No adhesion

Production Example 1: (A) Synthesis of Polymer A-1 as a polyimide precursor

Put 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) into a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone at room temperature. Under stirring, pyridine 81.5 g was added while stirring to obtain a reaction mixture. After completion of the exotherm due to the reaction, the reaction mixture was allowed to stand to cool to room temperature and allowed to stand for 16 hours.

Next, under ice-cooling, a solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, followed by 4,4'-oxy Cydianillin (ODA) 93.0 g was suspended in 350 mL of γ-butyrolactone and added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 L of ethyl alcohol to produce a precipitate composed of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration, followed by vacuum drying to obtain a powdery polymer (Polymer A-1). When the molecular weight of the polymer (A-1) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.

Production Example 2: (A) Synthesis of Polymer A-2 as a polyimide precursor

In place of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) of Production Example 1, except for using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), The reaction was carried out in the same manner as in the method described in Production Example 1 above to obtain a polymer (A-2). When the molecular weight of the polymer (A-2) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

Production Example 3: (A) Synthesis of Polymer A-3 as a polyimide precursor

In place of 93.0 g of 4,4'-oxydianiline (ODA) of Production Example 1, except for using 50.2 g of p-phenylenediamine, the reaction was carried out in the same manner as in Production Example 1 described above, and a polymer ( A-3) was obtained. When the molecular weight of the polymer (A-3) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 19,000.

Production Example 4: (A) Synthesis of Polymer A-4 as a polyimide precursor

4,4'-oxydiphthalic dianhydride of Preparation Example 1 fluorenic dianhydride (229.2 g), 4,4'-oxydianiline 2,2'-bis (trifluoromethyl) benzidine (TFMB) Except having changed to (148.5 g), it carried out similarly to the method described in Production Example 1 mentioned above, and carried out reaction, and the polymer (A-4) was obtained. When the molecular weight of the polymer (A-4) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 12,000.

Production Example 5: (A) Synthesis of Polymer A-5 as a polyimide precursor

In place of 93.0 g of 4,4'-oxydianiline (ODA) of Preparation Example 1, except for using 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB), the above preparation It reacted like the method described in Example 1, and obtained the polymer (A-5). When the molecular weight of the polymer (A-5) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

Production Example 6: (E) Synthesis of hot base generator E-1

To a 1 L nass-shaped flask, 100 g of diethylene glycol bis(3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol were added, mixed with a stirrer and stirred to obtain a homogeneous solution. It cooled to below °C. To this, 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 120 g of ethanol and added dropwise by a dropping funnel. At this time, dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50°C or less. 2 hours after the dropwise addition, the reaction solution was concentrated under reduced pressure at 50° C. for 3 hours to obtain the target compound E-1.

<Example 1>

Using polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) Polymer A-1 as a polyimide precursor: 100 g, (B) 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (photo polymerization initiator B) as a photopolymerization initiator Equivalent to -1): 3 g was dissolved in (C) KBM-403 (1.5 g) (D) organic solvent γ-butyllactone (hereinafter referred to as GBL): 150 g. The viscosity of the obtained solution was adjusted to about 30 poise by additionally adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the method described above. Table 1 shows the results.

<Examples 2 to 13, Comparative Examples 1 to 3>

The negative photosensitive resin composition similar to Example 1 was prepared except having prepared by the component and the compounding ratio shown in Table 1, and the same evaluation as Example 1 was performed. The results are shown in Table 1. The compounds described in Table 1 are as follows, respectively.

B-1: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

C-1: 3-glycidoxypropyltrimethoxysilane (KBM-403)

C-2: N-phenyl-3-aminopropyltrimethoxysilane (KBM-573)

C-3: 3-ureidopropyltriethoxysilane (KBE-585)

C-4: 3-isocyanate propyltriethoxysilane (KBE-9007)

C-5: 3-aminopropyltrimethoxysilane (KBM-903)

D-1: γ-butyllactone (hereinafter referred to as GBL)

D-2: dimethyl sulfoxide (DMSO)

E-1: Compound represented by Production Example 5

E-2: 1-(tert-butoxycarbonyl)-4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)

As is clear from Table 1, in Examples 1 to 13 containing the silane coupling agent (C) having a specific structure represented by the general formula (1), (C) having a specific structure represented by the general formula (1) Compared with Comparative Examples 1-3 which do not contain a silane coupling agent, high chemical resistance and resolution were obtained. In addition, after the high-temperature storage test, the generation of voids at the interface in contact with the resin layer of the Cu layer was also suppressed, and the adhesion to the sealing material was also good.

By using the negative photosensitive resin composition according to the present invention, a cured relief pattern having high chemical resistance and resolution can be obtained, and the generation of voids on the Cu surface can be suppressed. The present invention can be suitably used in the field of photosensitive materials useful for manufacturing electric/electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (20)

The following ingredients:
(A) polyimide precursor;
(B) photoinitiator;
(C) the following general formula (1):

{In the formula, a is an integer of 1 to 3, n is an integer of 1 to 6, R ₂₁ is each independently an alkyl group having 1 to 4 carbon atoms, and R ₂₂ is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, And R ₂₀ is at least one member selected from the group consisting of an epoxy group, a phenylamino group, a ureide group, and a substituent including an isocyanate group.}
Silane coupling agent represented by; And
(D) an organic solvent containing at least one selected from the group consisting of γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone ;
A negative photosensitive resin composition containing a. The method of claim 1,
In the general formula (1), R ₂₀ is at least one selected from the group consisting of a phenylamino group and a substituent containing a ureide group, the negative photosensitive resin composition. The method according to claim 1 or 2,
In the above general formula (1), R ₂₀ is a substituent containing a phenylamino group, the negative photosensitive resin composition. The method according to any one of claims 1 to 3,
(E) A negative photosensitive resin composition further containing a hot base generator. The method according to any one of claims 1 to 4,
The (D) organic solvent is at least two selected from the group consisting of γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone. To contain, the negative photosensitive resin composition. The method according to any one of claims 1 to 5,
The (A) polyimide precursor is the following general formula (2):

{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 each independently a hydrogen atom or a monovalent oil It is a device, and at least one of R ₁ and R ₂ is a monovalent organic group.}
A negative photosensitive resin composition having a structural unit represented by. The method of claim 6,
In the general formula (2), at least one of R ₁ and R ₂ is the following general formula (3):

{In the formula, L ₁ , L _2, and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10.}
The negative photosensitive resin composition which is a monovalent organic group represented by. The method according to claim 6 or 7,
In the general formula (2), X ₁ is the following general formula (20a):

A negative photosensitive resin composition having a structure represented by. The method according to claim 6 or 7,
In the general formula (2), X ₁ is the following general formula (20b):

A negative photosensitive resin composition having a structure represented by. The method according to claim 6 or 7,
In the general formula (2), X ₁ is the following general formula (20c):

A negative photosensitive resin composition having a structure represented by. The method according to any one of claims 6 to 10,
In the general formula (2), Y ₁ is the following general formula (21b):

The negative photosensitive resin composition containing the structure represented by. The method according to any one of claims 6 to 10,
In the general formula (2), Y ₁ is the following general formula (21c):

{In the formula, R ₆ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and n is from 0 to 4 It is an integer selected.}
The negative photosensitive resin composition containing the structure represented by. The method according to claim 6 or 7,
The (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 .}
A negative photosensitive resin composition having a structural unit represented by. The method according to claim 6 or 7,
The (A) polyimide precursor is the following general formula (5):

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 .}
A negative photosensitive resin composition having a structural unit represented by. The method according to claim 6 or 7,
The (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 The structural unit represented by .}, and
The following general formula (5):

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 . These may be the same as or different from R ₁ , R ₂ , and n ₁ in General Formula (4).}
The negative photosensitive resin composition containing the structural unit represented by at the same time. The method of claim 15,
The negative photosensitive resin composition, wherein the (A) polyimide precursor is a copolymer of the structural units represented by the general formulas (4) and (5). The method according to claim 6 or 7,
The (A) polyimide precursor is the following general formula (6):

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150 .}
A negative photosensitive resin composition having a structural unit represented by. The method according to any one of claims 1 to 17,
100 parts by mass of the (A) polyimide precursor,
0.1 to 20 parts by mass of the (B) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor,
0.1 to 20 parts by mass of the (C) silane coupling agent based on 100 parts by mass of the (A) polyimide precursor
A negative photosensitive resin composition containing a. A method for producing a polyimide, comprising a step of converting the negative photosensitive resin composition according to any one of claims 1 to 18 into polyimide. The following process:
(1) A step of applying the negative photosensitive resin composition according to any one of claims 1 to 18 on a substrate to form a photosensitive resin layer on the substrate;
(2) Step of exposing the photosensitive resin layer;
(3) Step of developing the photosensitive resin layer after exposure to form a relief pattern; And,
(4) Step of heat-treating the relief pattern to form a cured relief pattern;
Containing, the method for producing a cured relief pattern.