JP5657414B2 - Negative photosensitive resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

Description

  The present invention relates to, for example, an insulating material for an electronic component, a photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, and a method for producing a cured relief pattern using the same. And a semiconductor device.

  Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been used for insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by thermal imidization treatment by applying the precursor, exposing, developing, and curing. be able to. Such a photosensitive polyimide precursor has a feature that enables significant process shortening compared to a conventional non-photosensitive polyimide.

  On the other hand, in recent years, a method for mounting a semiconductor device on a printed wiring board has also changed from the viewpoint of improvement in integration degree and function, and reduction in chip size. There is a structure in which polyimide film such as BGA (Ball Griped Array), CSP (Chip Size Packaging), etc. that can be mounted with higher density than the conventional metal pin and lead-tin eutectic solder is in direct contact with the solder bump. It has come to be used. When forming such a bump structure, the film is required to have high heat resistance and chemical resistance. A method for improving the heat resistance of a polyimide film or a polybenzoxazole film by adding a thermal crosslinking agent to a composition containing a polyimide precursor or a polybenzoxazole precursor has been disclosed (see Patent Document 1).

  Furthermore, with the progress of miniaturization of semiconductor devices, the wiring resistance of semiconductor devices cannot be ignored. Therefore, the gold or aluminum wiring used so far has been changed to a copper or copper alloy wiring having a lower resistance.

JP 2003-287889 A

  However, when pattern formation is performed on a substrate made of copper or a copper alloy using the photosensitive resin composition disclosed in Patent Document 1, when the pattern is cured at a low temperature of about 250 ° C., the cured product and the substrate The inventor has recognized that there is a problem that the adhesiveness does not reach the use level, and as a result of intensive studies, the present invention has been made.

  The present invention relates to a negative photosensitive resin composition that gives a cured film having excellent adhesion to a substrate after low-temperature curing, a method for producing a cured relief pattern that forms a polyimide pattern using the photosensitive resin composition, and a semiconductor device The purpose is to provide.

  The present inventors use a compound having a specific structure, so that even when copper or a copper alloy is used as a substrate, a negative photosensitive resin composition that provides a cured film having excellent adhesion to the substrate after low-temperature curing. Has been found, and the present invention has been completed. That is, the present invention is as follows.

｛式中、Ｘ₁は、４価の有機基であり、Ｙ₁は、２価の有機基であり、ｎは、２〜１５０の整数であり、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、又は下記一般式（２）：

（式中、Ｒ₃、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍは、２〜１０の整数である。）で表される１価の有機基、又は炭素数１〜４の飽和脂肪族基である。但し、Ｒ₁及びＲ₂の両者が同時に水素原子であることはない。｝で表される構造を有するポリイミド前駆体：１００質量部、
（Ｂ）光重合開始剤：１〜２０質量部、並びに
（Ｃ）ヒドロキシル基、エーテル基及びエステル基からなる群より選ばれる官能基を１つ以上有する炭素数２〜３０のモノカルボン酸化合物：０．０１〜１０質量部、
を含有する、ネガ型感光性樹脂組成物。
［２］ 上記（Ｃ）のモノカルボン酸化合物が、下記一般式（３）：

｛式中、Ｒ₆は、水素原子又は炭素数１〜３の有機基であり、Ｒ₇は、水素原子、炭素数１〜３のアルキル基又はＲ₈であり、ここでＲ₈は下記一般式：

（式中、Ｚ₁は、水酸基又は炭素数１〜３のアルコキシ基であり、ｊは、０〜５の整数であり、そしてＺ₁は、複数存在する場合には互いに同一であっても異なっていてもよい。）で表される基であり、Ｒ₉は、水素原子、炭素数１〜３のアルキル基又は炭素数１〜３のアルキルカルボニル基である。｝
で表される化合物からなる群より選ばれる少なくとも１種のモノカルボン酸化合物である、上記［１］に記載のネガ型感光性樹脂組成物。
［３］ 上記（Ｃ）のモノカルボン酸化合物が、下記一般式（４）：

｛式中、Ｒ₁₀は、水素原子又は炭素数１〜３の有機基であり、Ｒ₁₁は、水素原子、炭素数１〜３のアルキル基又はＲ₁₂であり、ここでＲ₁₂は下記一般式：

（式中、Ｚ₂は、水酸基又は炭素数１〜３のアルコキシ基であり、ｋは、０〜５の整数であり、そしてＺ₂は、複数存在する場合には互いに同一であっても異なっていてもよい。）で表される基である。｝
で表される化合物からなる群より選ばれる少なくとも１種のモノカルボン酸化合物である、上記［１］又は［２］に記載のネガ型感光性樹脂組成物。
［４］ （Ｄ）有機チタン化合物：０．０５〜１０質量部をさらに含有する、上記［１］〜［３］のいずれかに記載のネガ型感光性樹脂組成物。
［５］ 上記（Ｄ）有機チタン化合物が、チタンキレート化合物、テトラアルコキシチタン化合物、及びチタノセン化合物からなる群から選ばれる少なくとも１種の化合物である、上記［４］に記載のネガ型感光性樹脂組成物。
［６］ 以下の：
（１）上記［１］〜［５］のいずれかに記載のネガ型感光性樹脂組成物を基板上に塗布することによって感光性樹脂層を該基板上に形成する工程と、
（２）該感光性樹脂層を露光する工程と、
（３）該露光後の感光性樹脂層を現像してレリーフパターンを形成する工程と、
（４）該レリーフパターンを加熱処理することによって硬化レリーフパターンを形成する工程と
を含む、硬化レリーフパターンの製造方法。
［７］ 上記［６］に記載の製造方法により得られる硬化レリーフパターンを有してなる、半導体装置。 [1] The following:
(A) The following general formula (1):

{Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently A hydrogen atom or the following general formula (2):

(Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R ₁ and R ₂ are not simultaneously hydrogen atoms. } Polyimide precursor having a structure represented by: 100 parts by mass,
(B) Photopolymerization initiator: 1 to 20 parts by mass, and (C) a monocarboxylic acid compound having 2 to 30 carbon atoms having at least one functional group selected from the group consisting of a hydroxyl group, an ether group and an ester group: 0.01 to 10 parts by mass,
A negative photosensitive resin composition comprising:
[2] The monocarboxylic acid compound of the above (C) is represented by the following general formula (3):

{Wherein, R ₆ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₇ is a hydrogen atom, an alkyl group or R ₈ having 1 to 3 carbon atoms, wherein R ₈ is represented by the following general formula:

(In the formula, Z ₁ is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, j is an integer of 0 to 5, and when a plurality of Z ₁ are present, they may be the same as or different from each other. R ₉ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkylcarbonyl group having 1 to 3 carbon atoms. }
The negative photosensitive resin composition according to the above [1], which is at least one monocarboxylic acid compound selected from the group consisting of compounds represented by:
[3] The monocarboxylic acid compound of the above (C) is represented by the following general formula (4):

{Wherein, R ₁₀ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₁₁ is a hydrogen atom, an alkyl group or R ₁₂ having 1 to 3 carbon atoms, wherein R ₁₂ is represented by the following general formula:

(In the formula, Z ₂ is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, k is an integer of 0 to 5, and Z ₂ may be the same as or different from each other when a plurality of Z ₂ exist. It is a group represented by. }
The negative photosensitive resin composition according to the above [1] or [2], which is at least one monocarboxylic acid compound selected from the group consisting of compounds represented by:
[4] (D) Organic titanium compound: The negative photosensitive resin composition according to any one of [1] to [3], further containing 0.05 to 10 parts by mass.
[5] The negative photosensitive resin according to [4], wherein the (D) organic titanium compound is at least one compound selected from the group consisting of a titanium chelate compound, a tetraalkoxytitanium compound, and a titanocene compound. Composition.
[6] The following:
(1) forming a photosensitive resin layer on the substrate by applying the negative photosensitive resin composition according to any one of [1] to [5] on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing a photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of forming a cured relief pattern by heat-treating the relief pattern.
[7] A semiconductor device having a cured relief pattern obtained by the production method according to [6].

  According to the present invention, by incorporating a compound having a specific structure into a negative photosensitive resin composition, a negative photosensitive resin that can give a cured film excellent in adhesion to a substrate after curing even by low-temperature curing. A photosensitive resin composition can be obtained, and a method for producing a cured relief pattern that forms a polyimide pattern using the photosensitive resin composition and a semiconductor device can be provided.

  The present invention will be specifically described below. Throughout the present specification, structures represented by the same reference numerals in the general formula may be the same or different from each other when there are a plurality of structures in the molecule.

｛式中、Ｘ₁は、４価の有機基であり、Ｙ₁は、２価の有機基であり、ｎは、２〜１５０の整数であり、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、又は下記一般式（２）：

（式中、Ｒ₃、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍは、２〜１０の整数である。）で表される１価の有機基、又は炭素数１〜４の飽和脂肪族基である。但し、Ｒ₁及びＲ₂の両者が同時に水素原子であることはない。｝で表される構造を有するポリイミド前駆体（以下、（Ａ）ポリイミド前駆体ともいう）：１００質量部、（Ｂ）光重合開始剤：１〜２０質量部、並びに（Ｃ）ヒドロキシル基、エーテル基及びエステル基からなる群より選ばれる官能基を１つ以上有する炭素数２〜３０のモノカルボン酸化合物（以下、（Ｃ）モノカルボン酸化合物ともいう）：０．０１〜１０質量部、を含有する、ネガ型感光性樹脂組成物を提供する。すなわち、本発明のネガ型感光性樹脂組成物は、（Ａ）ポリイミド前駆体：１００質量部、（Ｂ）光重合開始剤１〜２０質量部、及び（Ｃ）モノカルボン酸化合物：０．０１〜１０質量部を必須成分とする。 <Negative photosensitive resin composition>
The present invention provides (A) the following general formula (1):

{Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently A hydrogen atom or the following general formula (2):

(Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R ₁ and R ₂ are not simultaneously hydrogen atoms. } Polyimide precursor (hereinafter also referred to as (A) polyimide precursor): 100 parts by mass, (B) photopolymerization initiator: 1 to 20 parts by mass, and (C) hydroxyl group, ether A C2-C30 monocarboxylic acid compound having one or more functional groups selected from the group consisting of a group and an ester group (hereinafter also referred to as (C) monocarboxylic acid compound): 0.01 to 10 parts by mass A negative photosensitive resin composition is provided. That is, the negative photosensitive resin composition of the present invention comprises (A) polyimide precursor: 100 parts by mass, (B) 1-20 parts by mass of a photopolymerization initiator, and (C) monocarboxylic acid compound: 0.01. -10 mass parts is an essential component.

(A) Polyimide precursor (A) The polyimide precursor used for this invention is demonstrated. (A) A polyimide precursor is a resin component in the negative photosensitive resin composition of the present invention, and is a polyamide having a structure represented by the general formula (1). (A) A polyimide precursor is converted into a polyimide by performing a cyclization treatment (for example, 200 ° C. or higher).

In the general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably, from the viewpoint of achieving both heat resistance and photosensitive characteristics. , -COOR ₁ group, -COOR ₂ group and -CONH- group are each an aromatic group or an alicyclic aliphatic group in the ortho position. The tetravalent organic group represented by X ₁ is more preferably the following formula (5):

Although the structure represented by these is mentioned, it is not limited to these. The structure of X ₁ may be one type or a combination of two or more types. The X ₁ group having the structure represented by the above formula (5) is preferable in terms of achieving both heat resistance and photosensitive characteristics.

In the general formula (1), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive characteristics. Following formula (6):

And a structure represented by the following formula (7):

{In the formula, A represents a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a propyl group (—C ₃ H ₇ ), or a butyl group (—C ₄ H ₉ ). }
Although the structure represented by these is mentioned, it is not limited to these. The structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having the structure represented by the above formulas (6) and (7) is preferable in terms of achieving both heat resistance and photosensitive characteristics.

Regarding R ₁ and R ₂ , R ₃ in the general formula (2) is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably a hydrogen atom from the viewpoint of photosensitive properties. M is from 2 to 10, preferably from 2 to 4, from the viewpoint of photosensitive properties.

[(A) Preparation Method of Polyimide Precursor]
(A) In the polyimide precursor, the structure represented by the general formula (1) includes, for example, the above-described tetracarboxylic dianhydride containing the tetravalent organic group X ₁ and photopolymerizable unsaturation. After preparing a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester) by reacting an alcohol having a double bond and optionally a saturated aliphatic alcohol having 1 to 4 carbon atoms. This can be obtained by amide polycondensation of the diamine with the divalent organic group Y ₁ described above.

(Preparation of acid / ester)
In the present invention, tetracarboxylic dianhydride containing a tetravalent organic group X ₁ which is suitably used for preparing (A) a polyimide precursor, for example, pyromellitic anhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride , Diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, 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, but are not limited thereto It is not a thing. These may be used alone or in combination of two or more.

  Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used for preparing the polyimide precursor (A) in the present invention include 2-acryloyloxyethyl alcohol, 1-acryloyloxy- 3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl Acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2- Examples thereof include hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

  For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, and the like can be partially mixed and used as the saturated aliphatic alcohol having 1 to 4 carbon atoms.

  In the presence of a basic catalyst such as pyridine, the tetracarboxylic dianhydride suitable for the present invention described above and the above alcohol are stirred and dissolved in a suitable reaction solvent at a temperature of 20 to 50 ° C. for 4 to 10 hours. By mixing, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester body can be obtained.

  The reaction solvent is preferably a solvent that completely dissolves an acid / ester and a polyimide precursor that is an amide polycondensation product of this with a diamine component. For example, N-methyl-2-pyrrolidone, N, N -Dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone and the like.

  Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate. Diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like. These may be used alone or in admixture of two or more as required.

(Preparation of polyimide precursor)
To the acid / ester (typically, a solution in the reaction solvent) under ice-cooling, an appropriate dehydration condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N′-disuccinimidyl carbonate and the like are added and mixed to form an acid / ester body as a polyanhydride. A target polyimide precursor can be obtained by adding dropwise a solution obtained by dissolving or dispersing a diamine containing a divalent organic group Y ₁ suitably used in the present invention in a solvent, followed by amide polycondensation. it can.

Examples of diamines containing a divalent organic group Y ₁ that are preferably used in the present invention include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone 3,3′-diaminodiphenyl sulfone, 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-diaminodipheni Methane, 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-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 these In which part of the hydrogen atoms on the benzene ring is substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, etc., such as 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 2,2′-di Examples include til-4,4′-diaminodiphenylmethane, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, and mixtures thereof. It is not limited to.

  In addition, for the purpose of improving the adhesion between the photosensitive resin layer formed on the substrate and various substrates by applying the negative photosensitive resin composition of the present invention on the substrate, (A) the polyimide precursor In preparation, diaminosiloxanes such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane can be copolymerized.

  After completion of the amide polycondensation reaction, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off if necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is removed. The polymer component is added to the polymer component, and the polymer component is precipitated. Further, the polymer is purified by repeating redissolution, reprecipitation and the like, and vacuum drying is performed to obtain the target polyimide precursor. Isolate. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

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

(B) Photopolymerization initiator (B) The photopolymerization initiator used in the present invention will be described. (B) As a photoinitiator, the compound conventionally used as a photoinitiator for UV hardening can be selected arbitrarily. (B) Examples of a compound that can be suitably used as a photopolymerization initiator include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, and fluorenone. Acetophenone derivatives such as 2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Benzyl derivatives such as benzyldimethyl ketal and benzyl-β-methoxyethyl acetal, 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-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione- Preferred examples include oximes such as 2- (o-benzoyl) oxime, N-aryl glycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, and the like. Is not to be done. Moreover, in using these, 1 type or a 2 or more types of mixture may be sufficient. Among the above photopolymerization initiators, oximes are more preferable particularly from the viewpoint of photosensitivity.

  (B) The compounding quantity of a photoinitiator is 1-20 mass parts with respect to 100 mass parts of (A) polyimide precursor, and 2-15 mass parts is preferable from a viewpoint of a photosensitivity characteristic. (B) A photoinitiator is excellent in photosensitivity by mix | blending 1 mass part or more with respect to 100 mass parts of (A) polyimide precursor, and it is excellent in thick film curability by mix | blending 20 mass parts or less.

(C) Monocarboxylic acid compound (C) The monocarboxylic acid compound used in the present invention will be described. (C) The monocarboxylic acid compound has only one carboxyl group in the molecule and has at least one functional group selected from the group consisting of a hydroxyl group, an ether group, and an ester group. 30 carboxylic acid compounds. (C) By using a monocarboxylic acid compound, good adhesion between the cured substrate (especially copper or copper alloy) and the polyimide resin formed from the (A) polyimide precursor is obtained even by low-temperature curing. It is done. Although the chemical mechanism of obtaining good adhesion even by low-temperature curing is not clear, only one carboxyl group in the molecule interacts with, for example, copper on the substrate, and hydroxyl group, ether group and ester group The functional group selected from the group consisting of (A) the distance between the substrate and the resin is constant by interacting with the carbonyl group of the polyimide precursor or the carbonyl group of the polyimide cyclized by heating through a hydrogen bond or the like. It can be presumed that the adhesion is improved. (C) Carbon number of a monocarboxylic acid compound is 2 or more and 30 or less from a viewpoint of the adhesive improvement of the hardened | cured material after hardening of a negative photosensitive resin composition, and a board | substrate (especially copper or copper alloy). This carbon number becomes like this. Preferably it is the range of 2-20, More preferably, it is the range of 2-15.

  Specific examples of (C) monocarboxylic acid compounds include hydroxyacetic acid, methoxyacetic acid, ethoxyacetic acid, isopropoxyacetic acid, lactic acid, 2-methoxypropionic acid, 2-hydroxyisobutyric acid, benzylidenelactic acid, 4-hydroxyphenyllactic acid, 4 -Hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-hydroxy-3-phenylpropionic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, Examples include atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, 3-hydroxybutyric acid, 4-hydroxypentanoic acid, 4-methoxybutyric acid, and 3-methoxypropionic acid. Among these, from the viewpoint of obtaining the above-mentioned adhesion more favorably, the monocarboxylic acid compound having 2 to 30 carbon atoms having at least one functional group selected from the group consisting of a hydroxyl group, an ether group and an ester group at the α-position of the carboxyl group Is preferred.

  Furthermore, (C) the monocarboxylic acid compound is represented by the following general formula (3):

（式中、Ｚ₁は、水酸基又は炭素数１〜３のアルコキシ基であり、ｊは、０〜５の整数であり、そしてＺ₁は、複数存在する場合には互いに同一であっても異なっていてもよい。）で表される基であり、Ｒ₉は、水素原子、炭素数１〜３のアルキル基又は炭素数１〜３のアルキルカルボニル基である。｝
で表される化合物からなる群より選ばれる少なくとも１種のモノカルボン酸化合物であることが、接着性向上の観点からより好ましい。 {Wherein, R ₆ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₇ is a hydrogen atom, an alkyl group or R ₈ having 1 to 3 carbon atoms, wherein R ₈ is represented by the following general formula:

(In the formula, Z ₁ is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, j is an integer of 0 to 5, and when a plurality of Z ₁ are present, they may be the same as or different from each other. R ₉ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkylcarbonyl group having 1 to 3 carbon atoms. }
It is more preferable from a viewpoint of an adhesive improvement that it is at least 1 sort (s) of monocarboxylic acid compound chosen from the group which consists of a compound represented by these.

  Specific examples of the compound represented by the general formula (3) include hydroxyacetic acid, methoxyacetic acid, ethoxyacetic acid, isopropoxyacetic acid, lactic acid, 2-methoxypropionic acid, 2-hydroxyisobutyric acid, and 4-hydroxymandel. Examples include acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid and α-methoxyphenylacetic acid.

  Among them, the following general formula (4):

（式中、Ｚ₂は、水酸基又は炭素数１〜３のアルコキシ基であり、ｋは、０〜５の整数であり、そしてＺ₂は、複数存在する場合には互いに同一であっても異なっていてもよい。）で表される基である。｝
で表される化合物からなる群より選ばれる少なくとも１種のモノカルボン酸化合物は、接着性が特に良好である点でさらに好ましい。上記一般式（４）で表される化合物として、具体的には、ヒドロキシ酢酸、乳酸、２‐ヒドロキシイソ酪酸、４−ヒドロキシマンデル酸、３，４−ジヒドロキシマンデル酸、４−ヒドロキシ−３−メトキシマンデル酸、マンデル酸等が挙げられる。 {Wherein, R ₁₀ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₁₁ is a hydrogen atom, an alkyl group or R ₁₂ having 1 to 3 carbon atoms, wherein R ₁₂ is represented by the following general formula:

(In the formula, Z ₂ is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, k is an integer of 0 to 5, and Z ₂ may be the same as or different from each other when a plurality of Z ₂ exist. It is a group represented by. }
At least one monocarboxylic acid compound selected from the group consisting of the compounds represented by formula (1) is more preferable in that the adhesiveness is particularly good. Specific examples of the compound represented by the general formula (4) include hydroxyacetic acid, lactic acid, 2-hydroxyisobutyric acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxy. Examples include mandelic acid and mandelic acid.

R ₆ in the general formula (3) and R ₁₀ in the general formula (4) are each a hydrogen atom or an organic group having 1 to 3 carbon atoms from the viewpoint of photosensitive properties. In addition, R ₇ in the general formula (3) is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or the above R ₈ from the viewpoint of photosensitive characteristics, and R ₁₁ in the general formula (4) is the same as the above R ₇ . For the same reason, they are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or the above R ₁₂ . R ₉ in the general formula (3) is a hydrogen atom or a carbon number of 1 to 3 from the viewpoint of improving the adhesion between the cured product of the negative photosensitive resin composition and the substrate (particularly copper or copper alloy). An alkyl group or an alkylcarbonyl group having 1 to 3 carbon atoms.

  (C) The compounding quantity of a monocarboxylic acid compound is 0.01-10 mass parts with respect to 100 mass parts of (A) polyimide precursor, Preferably it is 0.05-2 mass parts. When the blending amount is 0.01 parts by mass or more, good adhesiveness is expressed, while when it is 10 parts by mass or less, the negative photosensitive resin composition of the present invention on a copper or copper alloy substrate. When the photosensitive resin layer is formed using, the color change suppression effect on copper or copper alloy is excellent.

(D) Organic Titanium Compound The negative photosensitive resin composition of the present invention may contain (D) an organic titanium compound. (D) By containing an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of 250 ° C. In particular, by including both (C) the monocarboxylic acid compound and (D) the organic titanium compound in the negative photosensitive resin composition, the cured photosensitive resin layer is resistant to the substrate adhesion in addition to the substrate adhesion. The effect is excellent in chemical properties.

  (D) Examples of the organic titanium compound that can be used as the organic titanium compound include those in which an organic chemical substance is bonded to a titanium atom through a covalent bond or an ionic bond.

Specific examples of (D) organotitanium compounds 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 because it provides storage stability and a good pattern of the negative photosensitive resin composition, and a specific example is titanium bis (Triethanolamine) diisopropoxide, titanium di (n-butoxide) bis (2,4-pentanedionate, titanium diisopropoxide bis (2,4-pentanedionate), titanium diisopropoxide bis ( Tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate) and the like.

  II) Tetraalkoxytitanium compounds: for example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , Titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonyloxide), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis [bis {2,2- (allyloxymethyl) Butoxide}] and the like.

III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluorophenyl) titanium, bis (η ⁵ − 2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.

IV) Monoalkoxytitanium compounds: for example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanedionate), titanium oxide bis (tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate.
VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate.

  Among them, (D) the organotitanium compound is at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. It is preferable from the viewpoint of exhibiting sex.

  (D) It is preferable that the compounding quantity in the case of mix | blending an organic titanium compound is 0.05-10 mass parts with respect to 100 mass parts of (A) polyimide precursor, More preferably, it is 0.1-2 mass parts. It is. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are expressed, and when it is 10 parts by mass or less, the storage stability is excellent.

(E) Other components The negative photosensitive resin composition of this invention may further contain components other than the said (A)-(D) component. The negative photosensitive resin composition of the present invention is typically used as a negative photosensitive resin composition in which the above components and optional components further used as necessary are dissolved in a solvent to form a varnish. Therefore, a solvent can be mentioned as (E) other components. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the (A) polyimide precursor. Specifically, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α -Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like can be mentioned, and these can be used alone or in combination of two or more.

  The said solvent is the range of 30-1500 mass parts with respect to 100 mass parts of (A) polyimide precursor according to the desired coating film thickness and viscosity of a negative photosensitive resin composition, Preferably it is 100-1000 masses. It can be used within the range of parts.

  Furthermore, from the viewpoint of improving the storage stability of the negative photosensitive resin composition, a solvent containing alcohols is preferable. Alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond, and specific examples include methyl alcohol, ethyl alcohol, n- Alkyl alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, lactic acid esters such as ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol Propylene glycol monoalkyl ethers such as -1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- (n-propyl) ether Le, ethylene glycol methyl ether, ethylene glycol ethyl ether, mono-alcohols such as ethylene glycol -n- propyl ether, 2-hydroxyisobutyric acid esters, ethylene glycol, and can be given dialcohols such as propylene glycol. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable, and particularly ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, And propylene glycol-1- (n-propyl) ether is more preferred.

  When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the entire solvent is preferably 5 to 50% by mass, more Preferably it is 10-30 mass%. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the negative photosensitive resin composition is improved. When the content is 50% by mass or less, (A) a polyimide precursor The solubility of is improved.

  The negative photosensitive resin composition of the present invention may further contain a resin component other than the above-described (A) polyimide precursor. Examples of the resin component that can be contained include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of (A) polyimide precursor.

  Moreover, in order to improve photosensitivity, the sensitizer can be arbitrarily mix | blended with the negative photosensitive resin composition of this invention. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4′-diethylaminobenzal) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene 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-ethoxy Carbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N′-ethylethanolamine N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) ) Naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. These can be used alone or in combination of, for example, 2 to 5 kinds.

  When the negative photosensitive resin composition contains a sensitizer for improving the photosensitivity, the blending amount may be 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. preferable.

  Moreover, in order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily blended. Such a monomer is preferably a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, but includes ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Polyethylene glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol di Acrylate and dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate, neopentyl glycol Acrylate and dimethacrylate, 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 tri of glycerol Mention may be made of compounds such as acrylates and methacrylates, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

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

  In addition, an adhesion aid can be optionally blended for improving the adhesion between the film formed using the negative photosensitive resin composition of the present invention and the substrate. Adhesion aids include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3′-bis (N- [3-triethoxysilyl] propylamide) -4,4′-dicarboxylic acid, benzene-1, 4-bis (N- [3-trie Toxisilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, silane coupling agents such as N-phenylaminopropyltrimethoxysilane, and aluminum tris (ethyl acetoacetate), Examples thereof include aluminum adhesion assistants such as aluminum tris (acetylacetonate) and ethyl acetoacetate aluminum diisopropylate.

  Among these adhesion assistants, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. The blending amount when the negative photosensitive resin composition contains an adhesion aid is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

  In addition, a thermal polymerization inhibitor can be optionally blended in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition during storage, particularly in a solution containing a solvent. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6 -Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N- Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

  As a compounding quantity of the thermal-polymerization inhibitor in the case of mix | blending with a negative photosensitive resin composition, the range of 0.005-12 mass parts is preferable with respect to 100 mass parts of (A) polyimide precursor.

  Moreover, a crosslinking agent can be arbitrarily mix | blended. When the relief pattern formed using the negative photosensitive resin composition of the present invention is heat-cured, the crosslinking agent can (A) crosslink the polyimide precursor, or the crosslinking agent itself forms a crosslinked network. Can be a cross-linking agent. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the negative photosensitive resin composition. As the crosslinking agent, amino resins and derivatives thereof are preferably used, and among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are preferably used. Particularly preferred are alkoxymethylated urea compounds and alkoxymethylated melamine compounds, for example, MX-290 (manufactured by Nippon Carbide), UFR-65 (manufactured by Nippon Cytec), and MW-390 (manufactured by Nippon Carbide). ).

  In consideration of various performances other than heat resistance and chemical resistance, the compounding amount when the negative photosensitive resin composition contains a crosslinking agent is 0.5 to 100 parts by mass of (A) polyimide precursor. It is preferable that it is 20 mass parts, More preferably, it is 2-10 mass parts. When the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are expressed, and when it is 20 parts by mass or less, the storage stability is excellent.

  Moreover, when using the board | substrate which consists of copper or a copper alloy, for example, in order to suppress board | substrate discoloration, an azole compound can be arbitrarily mix | blended. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, and 4-t-butyl-5. -Phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyl Triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (α, α-dimethylben Dil) 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-tetra Lumpur, 1-methyl -1H- tetrazole, and the like. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in a mixture of two or more.

  When the negative photosensitive resin composition contains the azole compound, the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. From 0.5 to 5 parts by mass is more preferable. When the compounding quantity with respect to 100 mass parts of (A) polyimide precursor of an azole compound is 0.1 mass part or more, when forming the negative photosensitive resin composition of this invention on copper or a copper alloy, copper Or the discoloration of the copper alloy surface is suppressed, and on the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent.

  Moreover, in order to suppress discoloration on copper, a hindered phenol compound can be arbitrarily mix | blended. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and 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-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphene) ) 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-tert-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanate Nurate, 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-ethyl Propyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4-triethyl Methyl-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-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5 Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1 , 3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -tri 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-tert-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H , 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H , 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-5-ethyl-3) Hydroxy-2-methylbenzyl) -1,3,5-triazine -2,4,6- (1H, 3H, 5H) - but trione, etc., but is not limited thereto. 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.

  It is preferable that the compounding quantity of a hindered phenol compound is 0.1-20 mass parts with respect to 100 mass parts of (A) polyimide precursors, and it is 0.5-10 mass parts from a viewpoint of a photosensitivity characteristic. Is more preferable. When the compounding quantity with respect to 100 mass parts of (A) polyimide precursor of a hindered phenol compound is 0.1 mass part or more, For example, when forming the negative photosensitive resin composition of this invention on copper or a copper alloy Further, discoloration / corrosion of copper or copper alloy is prevented, and on the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent.

<Method for producing cured relief pattern>
The present invention also includes (1) a step of forming a photosensitive resin layer on the substrate by applying the above-described negative photosensitive resin composition of the present invention onto the substrate, and (2) the photosensitive resin layer. (3) a step of developing the exposed photosensitive resin layer to form a relief pattern, and (4) a step of forming a cured relief pattern by heat-treating the relief pattern. A method for producing a cured relief pattern is provided. Hereinafter, typical aspects of each process will be described.

(1) The process of forming a photosensitive resin layer on this board | substrate by apply | coating a negative photosensitive resin composition on a board | substrate In this process, the negative photosensitive resin composition of this invention is apply | coated on a base material. Then, if necessary, it is then dried to form a photosensitive resin layer. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., spray coating with a spray coater A method or the like can be used.

  If necessary, the coating film made of 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. Moreover, it is desirable to perform drying of a coating film on the conditions that the imidation of the (A) polyimide precursor in a negative photosensitive resin composition does not occur. Specifically, when performing air drying or heat drying, drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. Thus, a photosensitive resin layer can be formed on the substrate.

(2) Step of exposing photosensitive resin layer In this step, the photosensitive resin layer formed as described above is exposed through a photomask or reticle having a pattern using an exposure apparatus such as a contact aligner, mirror projection, or stepper. Alternatively, direct exposure is performed with an ultraviolet light source or the like.

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

(3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the photosensitive resin layer after the exposure (irradiation), a conventionally known photoresist developing method, for example, a rotary spray method, a paddle method, an immersion method with ultrasonic treatment, or the like can be used. A method can be selected and used. Further, after development, for the purpose of adjusting the shape of the relief pattern, post-development baking at any combination of temperature and time may be performed as necessary.

  The developer used for development is preferably a good solvent for the negative photosensitive resin composition or a combination of the good solvent and the poor solvent. As the good solvent, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable and poor. As the solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When mixing and using a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative photosensitive resin composition. Also, two or more of each solvent, for example, several types may be used in combination.

(4) Step of forming a cured relief pattern by heat-treating the relief pattern In this step, the relief pattern obtained by the above development is heated to diffuse the photosensitive component, and (A) the polyimide precursor is imidized. By converting it into a cured relief pattern made of polyimide. As a method of heat curing, various methods such as a method using a hot plate, a method using an oven, a method using a temperature rising type oven capable of setting a temperature program can be selected. Heating can be performed, for example, at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, and an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
The present invention also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention. The present invention also provides a semiconductor device having a substrate which is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described cured relief pattern manufacturing method. The present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern as part of the process. The semiconductor device of the present invention is a semiconductor device having a surface relief film, an interlayer insulation film, a rewiring insulation film, a flip chip device protection film, or a bump structure as a cured relief pattern formed by the above-described cured relief pattern production method. And can be manufactured by combining with a known method for manufacturing a semiconductor device.

  The negative photosensitive resin composition of the present invention is used for applications such as the above-mentioned semiconductor devices as well as interlayer insulation of multilayer circuits, cover coats of flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Is also useful.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In Examples, Comparative Examples, and Production Examples, the physical properties of negative photosensitive resin compositions were measured and evaluated according to the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) of each polyimide precursor was measured by the gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement is a trade name Shodex 805M / 806M series manufactured by Showa Denko KK, the standard monodisperse polystyrene is Shodex STANDARD SM-105 manufactured by Showa Denko KK, and the developing solvent is N-methyl-2-pyrrolidone The detector used was a trade name Shodex RI-930 manufactured by Showa Denko.

(2) Adhesion test A negative photosensitive resin composition was spin-coated on a copper substrate, dried to form a 17 μm-thick coating film as a photosensitive resin layer, and then a temperature-programmed curing furnace (VF-2000) 10 μm-thick polyimide coating film was obtained by heat treatment (curing) at 200 ° C. for 1 hour and then at 250 ° C. for 2 hours in a nitrogen atmosphere using a mold, manufactured by Koyo Lindberg, Japan. The film thickness was measured using a Tencor P-15 type step gauge (manufactured by KLA Tencor). According to the cross cut method of JIS K 5600-5-6 standard, the adhesive properties between the metal material (copper substrate) / heat-resistant resin (polyimide coating film) were evaluated on the cured film based on the following criteria.
“Best”: The number of lattices of the polyimide coating film adhered to the substrate is 100.
“Good”: The number of lattices of the polyimide coating film adhered to the substrate is 80 to 99.
“Slightly good”: The polyimide coating film adhered to the substrate has a lattice number of 50 to 79.
“Slightly bad”: The number of lattices of the polyimide coating film adhered to the substrate is 20 to 49.
“Bad”: The number of lattices of the polyimide coating film adhered to the substrate is less than 20.

(3) Chemical resistance test A 6-inch nitride-coated silicon wafer (manufactured by Kyodo International Co., Ltd.) was spin-coated and dried to form a 17 μm thick coating film as a photosensitive resin layer. This coating film was exposed by irradiating energy at 200 mJ / cm ² using a reticle with a test pattern by a ghi stepper (Prisma-ghi, manufactured by Ultratech). Next, the coating film formed on the wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and uncoated. The exposed portion was developed and removed to obtain a relief pattern of the polyimide precursor. The wafer on which the relief pattern is formed is heat-treated in a nitrogen atmosphere at 200 ° C. for 1 hour and then at 250 ° C. for 2 hours using a temperature-programmed curing furnace (VF-2000, manufactured by Koyo Lindberg, Japan). As a result, a cured relief pattern of polyimide having a thickness of 10 μm was obtained on a silicon wafer with a nitride film.

  The obtained polyimide pattern was immersed in a solution consisting of 1 wt% potassium hydroxide, 39 wt% 3-methoxy-3-methyl-1-butanol and 60 wt% dimethyl sulfoxide at 100 ° C. for 1 hour. After washing with water and air drying, the polyimide coating film was evaluated by film thickness measurement and observation under an optical microscope. Regarding the coating film after immersion, the film thickness variation with respect to the film before immersion is within ± 1% and no crack is generated. The case where it did not occur was evaluated as “good”, and the case where the film thickness variation exceeded ± 3% or a crack occurred was evaluated as “bad”.

<Production Example 1> ((A) Synthesis of Polymer A as Polyimide Precursor)
Place 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 liter separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stir at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours.

  Next, under ice cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4′-diaminodiphenyl ether (DADPE). A suspension of 93.0 g in γ-butyrolactone 350 ml was added over 60 minutes with stirring. After further stirring for 2 hours at room temperature, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml 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 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polymer A). When the molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20000.

<Production Example 2> ((A) Synthesis of polymer B as polyimide precursor)
The above-mentioned production except that 147.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4′-oxydiphthalic dianhydride of Production Example 1. Reaction was carried out in the same manner as in the method described in Example 1 to obtain polymer B. When the molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Example 1>
Using the polymers A and B, negative photosensitive resin compositions were prepared by the following method, and the prepared compositions were evaluated. Polymer A 50 g and B 50 g ((A) polyimide precursor), which are polyimide precursors, were converted into 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime ((B) photopolymerization initiator) 4 g. , 0.2 g of mandelic acid ((C) monocarboxylic acid compound), 0.15 g of benzotriazole, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1, 3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 1.5 g, N-phenyldiethanolamine 10 g, methoxymethylated urea resin (MX-290) 4 g, tetraethylene glycol dimethacrylate 8 g, Along with 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid and 0.05 g of 2-nitroso-1-naphthol, - (hereinafter referred to as NMP) methyl-2-pyrrolidone was dissolved in a mixed solvent consisting of 80g ethyl lactate 20g. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a negative photosensitive resin composition.

  The composition was evaluated according to the above-described method. As a result, even when it was cured at low temperature, the evaluation of adhesiveness was 100, “best”, and the evaluation of chemical resistance was “good”.

<Examples 2 and 3>
A negative photosensitive resin composition was prepared by changing the amount of mandelic acid as the monocarboxylic acid compound (C) in Example 1 of Example 1 to the composition shown in Table 1, and the same as in Example 1 Was evaluated. In any case, evaluation was performed in the same manner as in Example 1, and the evaluation results were the same as in Example 1.

<Example 4>
A negative photosensitive resin composition was prepared by changing the blending amount of mandelic acid as the monocarboxylic acid compound (C) in Example 1 of Example 1 into the composition shown in Table 1, and the same as in Example 1 Evaluation was performed. As a result of evaluating the adhesiveness, it was 80, which was “good”. The evaluation results of chemical resistance were the same as in Example 1.

<Example 5>
A negative photosensitive resin composition was prepared by changing the blending amount of mandelic acid as the monocarboxylic acid compound (C) in Example 1 of Example 1 into the composition shown in Table 1, and the same as in Example 1 Evaluation was performed. The evaluation results were the same as in Example 1.

<Example 6>
A negative photosensitive resin composition was prepared by using 2-hydroxyisobutyric acid in the composition shown in Table 1 instead of mandelic acid as the monocarboxylic acid compound (C) in Example 1 of the present invention, and carried out. Evaluation similar to Example 1 was performed. The evaluation results were the same as in Example 1.

<Example 7>
A negative photosensitive resin composition was prepared using lactic acid in the composition shown in Table 1 in place of mandelic acid as the monocarboxylic acid compound (C) in the present invention in Example 1, and the same as in Example 1. Was evaluated. As a result of evaluating the adhesiveness, it was 85 and “good”. The evaluation results of chemical resistance were the same as in Example 1.

<Example 8>
A negative photosensitive resin composition was prepared by using methoxyphenylacetic acid in the composition shown in Table 1 instead of mandelic acid as the monocarboxylic acid compound (C) in Example 1 of the present invention. The same evaluation was performed. As a result of evaluating the adhesiveness, it was 60, which was “slightly good”. The evaluation results of chemical resistance were the same as in Example 1.

<Example 9>
Negative photosensitive resin composition as in Example 1 except that 0.1 g of titanium diisopropoxide bis (ethylacetoacetate) (D1) as an organic titanium compound was further added to the composition of Example 1. A product was prepared. As a result of evaluating the chemical resistance, the film thickness variation was within ± 1%, and no crack was observed, and the film was “best”. The evaluation result of adhesiveness was the same as that of Example 1.

<Example 10>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.1 g of titanium tetra (n-butoxide) (D2) (D) as an organic titanium compound was further added to the composition of Example 1. . As a result of evaluating the chemical resistance, the film thickness variation was within ± 1%, and no crack was observed, and the film was “best”. The evaluation result of adhesiveness was the same as that of Example 1.

<Example 11>
In addition to the composition of Example 1, (D) bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) as an organotitanium compound A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.1 g of phenyl) titanium (D3) was added. As a result of evaluating the chemical resistance, the film thickness variation was within ± 1%, and no crack was observed, and the film was “best”. The evaluation result of adhesiveness was the same as that of Example 1.

<Example 12>
A negative photosensitive resin composition was prepared in the same manner as in Example 9, except that 100 g of polymer A was used instead of 50 g of polymer A and 50 g of polymer B as the polyimide precursor (A) in the present invention. The same evaluation was performed. The evaluation results were the same as in Example 9.

<Comparative Example 1>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that mandelic acid was omitted from the composition of Example 1, and the same evaluation as in Example 1 was performed. The polyimide coating film obtained by application, drying, exposure, development, and heat treatment on a silicon wafer and a copper substrate according to the above-described method was evaluated as “good” in chemical resistance. C) Since the monocarboxylic acid compound was not included, the adhesiveness was 40, which was “slightly poor”.

<Comparative example 2>
Negative photosensitive resin composition in the same manner as in Comparative Example 1 except that 0.1 g of titanium diisopropoxide bis (ethylacetoacetate) (D1) as an organic titanium compound was added to the composition of Comparative Example 1. Were prepared and evaluated in the same manner as in Example 1. The polyimide coating film obtained by applying, drying, exposing, developing, and heat-treating on a silicon wafer and a copper substrate according to the above-mentioned method was evaluated as “best” in chemical resistance. C) Since the monocarboxylic acid compound was not contained, the adhesiveness was 0, which was “poor”.

  The negative photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (7)

below:
(A) The following general formula (1):

{Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently A hydrogen atom or the following general formula (2):

(Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R ₁ and R ₂ are not simultaneously hydrogen atoms. } Polyimide precursor having a structure represented by: 100 parts by mass,
(B) Photopolymerization initiator: 1 to 20 parts by mass, and (C) a monocarboxylic acid compound having 2 to 30 carbon atoms having at least one functional group selected from the group consisting of a hydroxyl group, an ether group and an ester group: 0.01 to 10 parts by mass,
A negative photosensitive resin composition comprising: The monocarboxylic acid compound (C) is represented by the following general formula (3):

{Wherein, R ₆ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₇ is a hydrogen atom, an alkyl group or R ₈ having 1 to 3 carbon atoms, wherein R ₈ is represented by the following general formula:

(In the formula, Z ₁ is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, j is an integer of 0 to 5, and when a plurality of Z ₁ are present, they may be the same as or different from each other. R ₉ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkylcarbonyl group having 1 to 3 carbon atoms. }
The negative photosensitive resin composition of Claim 1 which is the at least 1 sort (s) of monocarboxylic acid compound chosen from the group which consists of a compound represented by these. The monocarboxylic acid compound (C) is represented by the following general formula (4):

{Wherein, R ₁₀ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₁₁ is a hydrogen atom, an alkyl group or R ₁₂ having 1 to 3 carbon atoms, wherein R ₁₂ is represented by the following general formula:

(In the formula, Z ₂ is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, k is an integer of 0 to 5, and Z ₂ may be the same as or different from each other when a plurality of Z ₂ exist. It is a group represented by. }
The negative photosensitive resin composition of Claim 1 or 2 which is at least 1 sort (s) of monocarboxylic acid compound chosen from the group which consists of a compound represented by these.   (D) Organic titanium compound: The negative photosensitive resin composition of any one of Claims 1-3 which further contains 0.05-10 mass parts.   The negative photosensitive resin composition of Claim 4 whose said (D) organic titanium compound is at least 1 sort (s) of compound chosen from the group which consists of a titanium chelate compound, a tetraalkoxy titanium compound, and a titanocene compound. below:
(1) A step of forming a photosensitive resin layer on the substrate by coating the negative photosensitive resin composition according to any one of claims 1 to 5 on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing a photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of forming a cured relief pattern by heat-treating the relief pattern.   The semiconductor device which has a hardening relief pattern obtained by the manufacturing method of Claim 6.