JP2016167036A - Photosensitive resin composition, production method of cured relief pattern, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition exhibiting no changes in adhesion between a cured film thereof and copper or a copper alloy even when the film is exposed to a high temperature environment for a long time.SOLUTION: The negative photosensitive resin composition comprises: (A) a resin containing at least a polyamide acid, a polyamide acid ester or a polyamide acid salt as a precursor of polyimide, or polyamide; (B) a photosensitive agent; and (C) a compound containing two or more alcoholic hydroxyl groups, in which at least one alcoholic hydroxyl group is a primary hydroxyl group.SELECTED DRAWING: None

Description

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

  Polyimide resins have excellent heat resistance, electrical characteristics, and chemical resistance, and are therefore used as insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, interlayer insulating films, and the like. The photosensitive polyimide provided with photosensitivity to the polyimide resin is provided in the form of a varnish comprising a polyimide precursor and a photosensitizer, and a polyimide relief pattern is obtained by applying a varnish, exposing, developing, and curing by thermal imidization. Can be formed. In order to form a relief pattern of non-photosensitive polyimide, it is necessary to apply and peel off a resist material, whereas such a photosensitive polyimide precursor has a feature that it can greatly shorten the process.

  In recent years, with the progress of miniaturization of semiconductor devices, the wiring resistance of semiconductor devices cannot be ignored. Therefore, the gold or aluminum wiring that has been used so far is changed to a copper or copper alloy wiring having a lower resistance. However, the conventional photosensitive resin composition has a problem in that discoloration of copper or copper alloy occurs because the compound in the composition easily reacts with copper or copper alloy.

  As a means for solving the above, a method for suppressing discoloration and corrosion occurring in copper or a copper alloy by adding tetrazole to a composition containing a polyimide precursor has been disclosed (see Patent Document 1).

  Furthermore, in recent years, semiconductor devices have been remarkably used in automobile applications or mobile phone applications, and semiconductor devices in this field are required to have high reliability, and operation stability tests are performed in a high temperature environment. For this reason, the photosensitive polyimide used as a protective film of a semiconductor device is also required to have no change in physical properties even when exposed to a high temperature environment for a long time.

  For example, Patent Document 2 discloses a photosensitive polybenzoxazole that does not change its adhesion and chemical resistance performance even in an environment of high temperature and high humidity.

JP 2005-99661 A International Publication No. 12/172793

  However, in the compositions described in Patent Documents 1 and 2, when a varnish is applied to a copper substrate to form a pattern and exposed for a long time in a high temperature environment, oxygen transmitted through the polyimide film oxidizes copper, resulting in polyimide. There was a problem that the adhesion between the film and the copper substrate was lowered.

  By adding a compound having two or more alcoholic hydroxyl groups to the photosensitive resin composition, the present inventors do not change the adhesion between copper or a copper alloy and a cured film even when exposed for a long time in a high temperature environment. The inventors have found that a photosensitive resin composition can be obtained, and have completed the present invention. 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、ｎ₁は、２〜１５０の整数であり、そしてＲ₁及びＲ₂は、それぞれ独立に、水素原子、炭素数１〜３０の飽和脂肪族基、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ｍ₁は、２〜１０の整数である。）で表される１価の有機基、
又は下記一般式（３）：

（式中、Ｒ₆、Ｒ₇及びＲ₈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ｍ₂は、２〜１０の整数である。）で表される一価のアンモニウムイオン｝
で表されるポリイミドの前駆体であるポリアミド酸、ポリアミド酸エステル又はポリアミド酸塩、
あるいは下記一般式（４）：

｛式中、Ｘ₂は、炭素数６〜１５の３価の有機基であり、Ｙ₂は、炭素数６〜３５の２価の有機基であり、Ｒ₉は、炭素数３〜２０のラジカル重合性の不飽和結合基を少なくとも一つ有する有機基であり、そしてｎ₂は、１〜１０００の整数である。但し、複数あるＸ₂とＹ₂はそれぞれ異なる構造を有していてよい。｝
で表される構造を有するポリアミドを少なくとも含む樹脂；
（Ｂ）感光材；並びに
（Ｃ）アルコール性水酸基を２つ以上含む化合物、を含むネガ型感光性樹脂組成物である。
「２」
前記（Ｃ）アルコール性水酸基を２つ以上含む化合物が、前記（Ａ）の樹脂１００質量部に対して、１〜５０質量部である、「１」に記載のネガ型感光性樹脂組成物である。
「３」
前記（Ｃ）アルコール性水酸基を２つ以上含む化合物、その内少なくとも１つのアルコール性水酸基が下記一般式（５）：

｛式中、Ｚは、置換基を有してもよい水素原子、炭素原子、及び酸素原子から構成される炭素数１〜３０の脂肪族又は脂環式構造である。｝で表される構造を有する１級水酸基
である「１」又は「２」に記載のネガ型感光性樹脂組成物。
「４」
前記（Ｃ）アルコール性水酸基を２つ以上含む化合物が、３つ以上のアルコール性水酸基を持つ、「１」〜「３」のいずれか一項に記載のネガ型感光性樹脂組成物である。
「５」
前記（Ｃ）アルコール性水酸基を２つ以上含む化合物が、１級水酸基と２級水酸基をそれぞれ１つ以上持つ、「１」〜「４」のいずれか一項に記載のネガ型感光性樹脂組成物である。
「６」
前記（Ｃ）アルコール性水酸基を２つ以上含む化合物が、アルドース、ケトース、ピラノース、フラノース、及びアルジトールからなる群から選ばれる「１」〜「５」のいずれか一項に記載のネガ型感光性樹脂組成物である。
「７」
（Ｄ）含窒素複素環式化合物をさらに含む、「１」〜「６」いずれか一項に記載のネガ型感光性樹脂組成物である。
「８」
前記ネガ型感光性樹脂組成物から形成されたレリーフパターンを加熱処理することにより得られる硬化レリーフパターンを、大気圧空気雰囲気下、１５０℃で５００時間及び１０００時間の高温環境下保持後に、ＪＩＳ Ｋ ５６００−５−６規格のクロスカット法に準じて評価したとき、硬化レリーフパターンの基板に接着している格子数が５０以上である、「１」〜「７」のいずれか一項に記載のネガ型感光性樹脂組成物である。
「９」
（１）「１」〜「８」のいずれか一項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前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）前記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）前記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
を含む、硬化レリーフパターンの製造方法である。
「１０」
前記基板が、銅又は銅合金から形成されている、「９」に記載の方法である。
「１１」
「９」又は「１０」に記載の方法により得られる硬化レリーフパターンである。
「１２」
「１１」に記載の硬化レリーフパターンを含む半導体装置である。 "1"
(A) The following general formula (1):

{Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently And a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, 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 ₁ is an integer of 2 to 10). A monovalent organic group,
Or the following general formula (3):

(Wherein R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10). Monovalent ammonium ion}
A polyamic acid, a polyamic acid ester or a polyamic acid salt, which is a polyimide precursor represented by:
Or the following general formula (4):

{Wherein X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and R ₉ is a carbon group having 3 to 20 carbon atoms. It is an organic group having at least one radical-polymerizable unsaturated bond group, and n ₂ is an integer of 1 to 1000. However, the plurality of X ₂ and Y ₂ may have different structures. }
A resin containing at least a polyamide having a structure represented by:
A negative photosensitive resin composition comprising (B) a photosensitive material; and (C) a compound containing two or more alcoholic hydroxyl groups.
“2”
(C) The negative photosensitive resin composition as described in "1" whose compound which contains two or more alcoholic hydroxyl groups is 1-50 mass parts with respect to 100 mass parts of resin of the said (A). is there.
“3”
The compound (C) containing two or more alcoholic hydroxyl groups, of which at least one alcoholic hydroxyl group is represented by the following general formula (5):

{In formula, Z is a C1-C30 aliphatic or alicyclic structure comprised from the hydrogen atom which may have a substituent, a carbon atom, and an oxygen atom. } The negative photosensitive resin composition as described in "1" or "2" which is the primary hydroxyl group which has a structure represented by these.
“4”
(C) The negative photosensitive resin composition according to any one of “1” to “3”, wherein the compound containing two or more alcoholic hydroxyl groups has three or more alcoholic hydroxyl groups.
“5”
The negative photosensitive resin composition according to any one of “1” to “4”, wherein the compound (C) having two or more alcoholic hydroxyl groups has one or more primary hydroxyl groups and one or more secondary hydroxyl groups, respectively. It is a thing.
“6”
The negative photosensitivity according to any one of “1” to “5”, wherein the compound (C) containing two or more alcoholic hydroxyl groups is selected from the group consisting of aldose, ketose, pyranose, furanose, and alditol. It is a resin composition.
“7”
(D) The negative photosensitive resin composition according to any one of “1” to “6”, further including a nitrogen-containing heterocyclic compound.
“8”
A cured relief pattern obtained by heat-treating a relief pattern formed from the negative photosensitive resin composition was maintained in a high-temperature environment at 150 ° C. for 500 hours and 1000 hours under an atmospheric pressure air atmosphere. When evaluated according to the cross-cut method of the 5600-5-6 standard, the number of lattices adhered to the substrate of the cured relief pattern is 50 or more, according to any one of “1” to “7” It is a negative photosensitive resin composition.
“9”
(1) forming a photosensitive resin layer on the substrate by applying the negative photosensitive resin composition according to any one of “1” to “8” on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the 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.
"10"
The method according to “9”, wherein the substrate is made of copper or a copper alloy.
“11”
It is a cured relief pattern obtained by the method described in “9” or “10”.
“12”
A semiconductor device including the cured relief pattern described in “11”.

  According to the present invention, by adding a compound having two or more alcoholic hydroxyl groups to the photosensitive resin composition, adhesion between copper or a copper alloy and a cured film does not change even when exposed for a long time in a high temperature environment. A photosensitive resin composition is obtained, and a method for producing a cured relief pattern that forms a pattern using the photosensitive resin composition and a semiconductor device can be provided.

  Hereinafter, exemplary modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary. Moreover, the structure represented with the same code | symbol in general formula may mutually be the same, or may differ, when two or more exists in a molecule | numerator.

<Photosensitive resin composition>
Each component which comprises the photosensitive resin composition of this invention is demonstrated concretely below.

(A) Resin (A) Resin used for this invention is demonstrated. The resin (A) of the present invention contains, as a main component, at least one resin selected from the group consisting of polyamide acid, polyamide acid ester, and polyamide acid salt, which is a polyamide or polyimide precursor. Here, the main component means that these resins are contained in an amount of 60% by mass or more of the total resin, and preferably 80% by mass or more. Moreover, other resin may be included as needed.

  The weight average molecular weight of these resins is preferably 1,000 or more, more preferably 5,000 or more, in terms of polystyrene by gel permeation chromatography, from the viewpoint of heat resistance after heat treatment and mechanical properties. The upper limit is preferably 100,000 or less, and more preferably 50,000 or less from the viewpoint of solubility in a developer when a photosensitive resin composition is used.

｛式中、Ｘ₁は、４価の有機基であり、Ｙ₁は、２価の有機基であり、ｎ₁は、２〜１５０の整数であり、そしてＲ₁及びＲ₂は、それぞれ独立に、水素原子、炭素数１〜３０の飽和脂肪族基、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ｍ₁は、２〜１０の整数である。）で表される１価の有機基、又は下記一般式（３）：

（式中、Ｒ₆、Ｒ₇及びＲ₈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ｍ₂は、２〜１０の整数である。）で表される一価のアンモニウムイオン｝
で表される構造を有するポリイミド前駆体である。ポリマーが加熱処理後にイミド環を有する事で、機械物性、耐熱性及び耐薬品性が飛躍的に向上し、強靭な膜が得られる。 Next, details of the resin (A) in the present invention will be described.
[Polyimide precursor]
As the photosensitive resin composition of the present invention, the following general formula (1) which becomes a polymer having an imide ring by heating or treatment with an appropriate catalyst:

{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 And a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, 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 ₁ is an integer of 2 to 10). Monovalent organic group or the following general formula (3):

(Wherein R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10). Monovalent ammonium ion}
It is a polyimide precursor which has a structure represented by these. When the polymer has an imide ring after the heat treatment, mechanical properties, heat resistance and chemical resistance are drastically improved, and a tough film can be obtained.

で表される構造が挙げられるが、これらに限定されるものではない。又、Ｘ₁の構造は１種でも２種以上の組み合わせでも構わない。上記式（６）で表される構造を有するＸ₁基は、耐熱性と感光特性とを両立するという点で特に好ましい。 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 preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring, and more preferably the following formula (6):

Although the structure represented by these is mentioned, it is not limited to these. Further, 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 (6) is particularly preferable in terms of achieving both heat resistance and photosensitive characteristics.

で表される構造、及び下記式（８）：

｛式中、Ｒ₂₃及びＲ₂₄は、それぞれ独立に、メチル基（−ＣＨ₃）、エチル基（−Ｃ₂Ｈ₅）、プロピル基（−Ｃ₃Ｈ₇）又はブチル基（−Ｃ₄Ｈ₉）を表す。｝
で表される構造が挙げられるが、これらに限定されるものではない。又、Ｙ₁の構造は１種でも２種以上の組み合わせでも構わない。上記式（７）及び（８）で表される構造を有するＹ₁基は、耐熱性及び感光特性を両立するという点で特に好ましい。 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 (7):

And a structure represented by the following formula (8):

{In the formula, R ₂₃ and R ₂₄ are each independently 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 ) represents. }
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 (7) and (8) is particularly 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 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 characteristics.

  (A) When using a polyimide precursor as resin, as a system which provides photosensitivity to a photosensitive resin composition, an ester bond type and an ion bond type are mentioned. The former is a method of introducing a photopolymerizable group, that is, a compound having an olefinic double bond, into the side chain of the polyimide precursor by an ester bond, and the latter has a carboxyl group and an amino group of the polyimide precursor ( In this method, a photopolymerizable group is imparted by bonding an amino group of a (meth) acrylic compound via an ionic bond.

The ester bond-type polyimide precursor is first composed of the tetracarboxylic dianhydride containing the above-described tetravalent organic group X ₁ , an alcohol having a photopolymerizable unsaturated double bond, and optionally having 1 carbon atom. After preparing a partially esterified tetracarboxylic acid ester by reacting with -30 saturated aliphatic alcohols, this is polycondensed with the diamine containing the divalent organic group Y ₁ described above. As a result, a polyamic acid ester is obtained.

(Preparation of tetracarboxylic acid ester)
In the present invention, tetracarboxylic dianhydrides containing a tetravalent organic group X ₁ that are suitably used for preparing an ester bond type polyimide precursor include, 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 Anhydride, 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 something. 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 a polyamic acid ester in the present invention include 2-acryloyloxyethyl alcohol and 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, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2- Examples thereof include hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

  Examples of the saturated aliphatic alcohol having 1 to 30 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, and 3-pene. Tanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol Monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, and the like can also be partially mixed and used.

  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 tetracarboxylic acid ester can be obtained.

  The reaction solvent is preferably a solvent that completely dissolves a tetracarboxylic acid ester and a polyamic acid ester that is a polycondensation product of the tetracarboxylic acid ester and a diamine component. For example, N-methyl-2-pyrrolidone, N, N- Examples thereof include dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma butyrolactone.

  Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons include, for example, 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 Etc. These may be used alone or in admixture of two or more as required.

(Preparation of polyimide precursor)
An appropriate dehydration condensing agent such as dicyclocarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline is added to the tetracarboxylic acid ester (typically a solution in the reaction solvent) under ice cooling. 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N′-disuccinimidyl carbonate, etc. are added and mixed to form a tetracarboxylic acid ester as a polyanhydride. In addition, a diamine containing the divalent organic group Y ₁ preferably used in the present invention is separately added by dissolving or dispersing it in a solvent and polycondensed to obtain the desired polyamic acid ester. 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.

  For the purpose of improving the adhesion between the resin layer formed on the substrate and various substrates by applying the photosensitive resin composition of the present invention on the substrate, Diaminosiloxanes such as bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane can also be copolymerized.

  After completion of the 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 obtained. The polymer component is added to the polymer component, and the polymer component is precipitated. Further, the polymer is purified by repeating redissolution and reprecipitation, and the target polyamic acid ester is isolated by vacuum drying. To do. 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.

On the other hand, the polyamic acid salt, which is an ion-bonded polyimide precursor, first obtains polyamic acid, which is a polyimide precursor, by reacting tetracarboxylic dianhydride with diamine. In this case, at least one of R ₁ and R _{2 in} the general formula (1) is a hydroxyl group.

  The tetracarboxylic dianhydride is preferably a tetracarboxylic anhydride containing the structure of the above formula (6), and the diamine is preferably a diamine having the structure of the above formula (7) or (8). By adding a (meth) acrylic compound having an amino group, which will be described later, to the obtained polyamic acid, the amino group of the (meth) acrylic compound having a carboxyl group and an amino group of the polyamic acid forms a salt by ionic bonding. And a polyamic acid salt to which a photopolymerizable group is added.

  Examples of (meth) acrylic compounds having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylamino Dialkylaminoalkyl acrylates or methacrylates such as butyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate, etc. are preferred. Among these, from the viewpoint of photosensitive properties, the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain is C1-C10 dialkylaminoalkyl Acrylate or methacrylate is preferred.

  The compounding amount of the (meth) acrylic compound having an amino group is 1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and 2 to 15 parts by mass is preferable from the viewpoint of photosensitivity characteristics. (B) As a photosensitizer, an (meth) acrylic compound having an amino group is blended in an amount of 1 part by mass or more with respect to 100 parts by mass of the resin (A). Excellent in properties.

  The molecular weight of the ester bond type and the ion bond type polyimide precursor is preferably 8,000 to 150,000, as measured by gel permeation chromatography in terms of polystyrene-reduced weight average molecular weight, and 9,000. More preferably, it is ˜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 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 weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

｛式中、Ｘ₂は、炭素数６〜１５の３価の有機基であり、Ｙ₂は、炭素数６〜３５の２価の有機基であり、Ｒ₉は、炭素数３〜２０のラジカル重合性の不飽和結合基を少なくとも一つ有する有機基であり、そしてｎ₂は、１〜１０００の整数である。但し、複数あるＸ₂とＹ₂はそれぞれ異なる構造を有していてよい。｝
で表される構造を有するポリアミドである。このポリアミドはネガ型感光性樹脂組成物用として好適である。 [polyamide]
One more example of preferable (A) resin in the photosensitive resin composition of this invention is following General formula (4):

{Wherein X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and R ₉ is a carbon group having 3 to 20 carbon atoms. It is an organic group having at least one radical-polymerizable unsaturated bond group, and n ₂ is an integer of 1 to 1000. However, the plurality of X ₂ and Y ₂ may have different structures. }
Is a polyamide having a structure represented by This polyamide is suitable for a negative photosensitive resin composition.

｛式中、Ｒ₂₅は、炭素数２〜１９のラジカル重合性の不飽和結合基を少なくとも一つ有する有機基である。｝
で表される基であることが好ましい。 In the general formula (4), as the group represented by R ₉ , the following general formula (9),

{In the formula, R ₂₅ is an organic group having at least one radical-polymerizable unsaturated bond group having 2 to 19 carbon atoms. }
It is preferable that it is group represented by these.

で表される基の中から選ばれる芳香族基であることが好ましく、そしてアミノ基置換イソフタル酸構造からカルボキシル基及びアミノ基を除いた芳香族基であることがより好ましい。 In the general formula (4), the trivalent organic group represented by X ₂ is preferably a trivalent organic group having 6 to 15 carbon atoms, for example, the following formula (10):

Is preferably an aromatic group selected from the group represented by formula (II), and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from an amino group-substituted isophthalic acid structure.

｛式中、Ｒ₂₆及びＲ₂₇は、それぞれ独立に、水酸基、メチル基（−ＣＨ₃）、エチル基（−Ｃ₂Ｈ₅）、プロピル基（−Ｃ₃Ｈ₇）又はブチル基（−Ｃ₄Ｈ₉）から成る群から選ばれる一つの基であり、そして該プロピル基及びブチル基は、各種異性体を含む｝

｛式中、ｍ₄は、０〜８の整数であり、ｍ₅及びｍ₆は、それぞれ独立に、０〜３の整数であり、ｍ₇及びｍ₈は、それぞれ独立に、０〜１０の整数であり、そしてＲ₂₈及びＲ₂₉は、メチル基（−ＣＨ₃）、エチル基（−Ｃ₂Ｈ₅）、プロピル基（−Ｃ₃Ｈ₇）、ブチル基（−Ｃ₄Ｈ₉）又はこれらの異性体である。｝が挙げられる。 In the general formula (3), the divalent organic group represented by Y ₂ is preferably an organic group having 6 to 35 carbon atoms, and may be an aromatic or aliphatic ring which may be substituted. More preferably, it is a cyclic organic group having 1 to 4 carbon atoms, or an aliphatic group or siloxane group having no cyclic structure. Examples of the divalent organic group represented by Y ₂ include the following general formula (11) and the following general formulas (12) and (13):

{In the formula, R ₂₆ and R ₂₇ are each independently a hydroxyl group, 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 ) is one group selected from the group consisting of, and the propyl group and butyl group include various isomers}

{In the formula, m ₄ is an integer of 0 to 8, m ₅ and m ₆ are each independently an integer of 0 to 3, and m ₇ and m ₈ are each independently 0 to 10 And R ₂₈ and R ₂₉ are a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a propyl group (—C ₃ H ₇ ), a butyl group (—C ₄ H ₉ ) or These isomers. }.

｛式中、ｍ₉は、２〜１２の整数であり、ｍ₁₀は、１〜３の整数であり、ｍ₁₁は、１〜２０の整数であり、そしてＲ₃₀、Ｒ₃₁、Ｒ₃₂及びＲ₃₃は、それぞれ独立に、炭素数１〜３のアルキル基又は置換されていてもよいフェニル基である。｝が好ましいものとして挙げられる。 As an aliphatic group or siloxane group having no cyclic structure, the following general formula (14):

{Wherein m ₉ is an integer from 2 to 12, m ₁₀ is an integer from 1 to 3, m ₁₁ is an integer from 1 to 20, and R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ is each independently an alkyl group having 1 to 3 carbon atoms or an optionally substituted phenyl group. } Is preferable.

The polyamide resin of the present invention can be synthesized, for example, as follows.
(Synthesis of sealed phthalate compound)
First, a compound having a trivalent aromatic group X ₂ is selected from the group consisting of phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group 1 mol of at least one compound (hereinafter referred to as “phthalic acid compound”) is reacted with 1 mol of a compound that reacts with an amino group, and the amino group of the phthalic acid compound is converted into a radical polymerizable compound described later. A compound modified and sealed with a group containing an unsaturated bond (hereinafter referred to as “phthalic acid compound encapsulated body”) is synthesized. These may be used alone or in combination.

  When the phthalic acid compound is sealed with the radical polymerizable unsaturated bond-containing group, negative photosensitivity (photocurability) can be imparted to the polyamide resin.

  The group containing a radically polymerizable unsaturated bond is preferably an organic group having a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and particularly preferably a group containing a methacryloyl group or an acryloyl group.

  The above-mentioned sealed phthalic acid compound is obtained by reacting an amino group of a phthalic acid compound with an acid chloride, isocyanate or epoxy compound having at least one radical polymerizable unsaturated bond group having 3 to 20 carbon atoms. Can be obtained at

  Suitable acid chlorides include (meth) acryloyl chloride, 2-[(meth) acryloyloxy] acetyl chloride, 3-[(meth) acryloyloxy] propionyl chloride, 2-[(meth) acryloyloxy] ethyl chloroformate , 3-[(meth) acryloyloxypropyl] chloroformate and the like. Suitable isocyanates include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, 2- [2- (meth) acryloyloxyethoxy] ethyl isocyanate, and the like. . Suitable epoxy compounds include glycidyl (meth) acrylate. These may be used alone or in combination, but it is particularly preferable to use methacryloyl chloride and / or 2- (methacryloyloxy) ethyl isocyanate.

  Further, as these phthalic acid compound encapsulated bodies, those in which the phthalic acid compound is 5-aminoisophthalic acid can provide a polyamide having excellent photosensitivity and also excellent film characteristics after heat curing. Is preferred.

  The above sealing reaction is allowed to proceed by stirring and dissolving and mixing the phthalic acid compound and the sealing agent in a solvent in the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin dilaurate. Can do.

  As the reaction solvent, those that completely dissolve the product phthalic acid compound encapsulated body are preferable. 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, and hydrocarbons include, for example, 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, and And xylene. These solvents can be used alone or in combination as required.

  Some types of sealants, such as acid chloride, generate hydrogen chloride as a by-product during the sealing reaction. In this case, from the viewpoint of preventing contamination in the subsequent steps, it is preferable to carry out purification as appropriate, such as re-precipitation in water, washing with water and drying, and removal and reduction of ionic components through a column filled with an ion exchange resin.

(Polyamide synthesis)
The phthalic acid compound encapsulated body and a diamine compound having a divalent organic group Y ₂ are mixed in a suitable solvent in the presence of a basic catalyst such as pyridine or triethylamine, and polycondensed, whereby Polyamide can be obtained.

  As a polycondensation method, a phthalic acid compound encapsulated body is made into a symmetrical polyacid anhydride using a dehydrating condensing agent and then mixed with a diamine compound, or a phthalic acid compound encapsulated body is converted to an acid chloride by a known method. Examples thereof include a method of mixing with a diamine compound and a method of reacting a dicarboxylic acid component and an active esterifying agent in the presence of a dehydrating condensing agent to form an active ester and then mixing with the diamine compound.

  Examples of the dehydrating condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1′-carbonyldioxy-di-1,2,3-benzotriazole, N, N Preferred examples include '-disuccinimidyl carbonate.

  Examples of the chlorinating agent include thionyl chloride.

  As an active esterifying agent, N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 2-hydroxyimino-2-cyanoacetic acid ethyl, 2-hydroxyimino- Examples include 2-cyanoacetamide.

The diamine compound having an organic group Y ₂ includes at least one diamine selected from the group consisting of an aromatic diamine compound, an aromatic bisaminophenol compound, an alicyclic diamine compound, a linear aliphatic diamine compound, and a siloxane diamine compound. It is preferable that it is a compound, and it is also possible to use two or more together as desired.

  Examples of aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 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'-diaminodiphenylsulfone, 4,4'- Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane , 3,4'-di Mino diphenylmethane,

  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) pro 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 these benzene rings Is a diamine compound substituted with one or more groups selected from the group consisting of a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, and a halogen atom.

  Examples of diamine compounds in which hydrogen atoms on the benzene ring are substituted include 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4′-diaminobiphenyl and the like can be mentioned.

  Aromatic bisaminophenol compounds include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4′-diaminodiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis- (3-hydroxy-4-aminophenyl) methane, 2,2-bis- (3-hydroxy-4-aminophenyl) Propane, 3,3′-dihydroxy-4,4′-diaminobenzophenone, 3,3′-dihydroxy-4,4′-di Minodiphenyl ether, 4,4′-dihydroxy-3,3′-diaminodiphenyl ether, 2,5-dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis (3-amino-4- Hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) -bis (2-aminophenol) and the like.

  Examples of the alicyclic diamine compound include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, 1,5 -Diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2 , 5-diethylcyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2- (3-aminocyclopentyl) -2-propylamine, mensendiamine, isophoronediamine, norbornane Diamine, 1-cycloheptene-3,7-diamine, , 4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2 4,8,10-tetraoxaspiro- [5,5] -undecane and the like.

  Examples of linear aliphatic diamine compounds include 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane. Hydrocarbon type diamines such as, or alkylene oxide type diamines such as 2- (2-aminoethoxy) ethylamine, 2,2 ′-(ethylenedioxy) diethylamine, bis [2- (2-aminoethoxy) ethyl] ether, etc. Is mentioned.

  Examples of the siloxane diamine compound include dimethyl (poly) siloxane diamine, for example, trade names PAM-E, KF-8010, and X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.

  As the reaction solvent, a solvent that completely dissolves the polymer to be produced is preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone Etc.

  In addition, as a reaction solvent, in some cases, ketones, esters, lactones, ethers, hydrocarbons, and halogenated hydrocarbons may be used as a reaction solvent. Specifically, 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-dichloro Examples include butane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like.

  After completion of the amide polycondensation reaction, the precipitate derived from the dehydration condensing agent that has precipitated in the reaction solution is filtered off as necessary. Next, a poor polyamide solvent such as water or an aliphatic lower alcohol or a mixture thereof is added to the reaction solution to precipitate the polyamide. Further, the precipitated polyamide is redissolved in a solvent and purified by repeating the reprecipitation precipitation, followed by vacuum drying to isolate the target polyamide. In order to further improve the degree of purification, this polyamide solution may be passed through a column packed with an ion exchange resin to remove ionic impurities.

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”) of polyamide is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. If the weight average molecular weight in terms of polystyrene is 7,000 or more, the basic physical properties of the cured relief pattern are secured. Further, when the polystyrene-equivalent weight average molecular weight is 70,000 or less, development solubility when forming a relief pattern is ensured.

  Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. The weight average molecular weight value is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

(B) Photosensitive agent (B) Photosensitive agent used in the present invention will be described. (B) As the photosensitive agent, a photopolymerization initiator and / or a photoacid generator that generates radicals by absorbing and decomposing a specific wavelength are used. (B) The compounding quantity in the photosensitive resin composition of a photosensitive agent is 1-50 mass parts with respect to 100 mass parts of (A) resin. When the amount is 1 part by mass or more, photosensitivity or patterning property is exhibited, and when it is 50 parts by mass or less, the physical properties of the cured photosensitive resin layer are improved.

  In the case of a photopolymerization initiator, the generated radical is (A) by the main transfer skeleton of the resin and a chain transfer reaction, or (A) the (meth) acrylate group introduced into the resin and the radical polymerization reaction, Harden.

  (B) The photopolymerization initiator as the photosensitizer is preferably a photoradical polymerization initiator, such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, fluorenone and the like. Benzophenone derivatives, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, acetophenone derivatives such as 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, etc. Thioxanthone derivatives, benzyl derivatives such as benzyl, benzyldimethyl ketal and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1, -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-ethoxy Oximes such as propanetrione-2- (o-benzoyl) oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, α- ( Photoacid generators such as n-octanesulfonyloxyimino) -4-methoxybenzylcyanide Preferably mentioned are, but not limited thereto. Among the above photopolymerization initiators, oximes are more preferable particularly from the viewpoint of photosensitivity.

  In the case of using a photoacid generator as the photosensitive agent (B) in the negative photosensitive resin composition, it is acidic by irradiation with an actinic ray such as ultraviolet rays, and by its action, a crosslinking which is a component (D) described later It has the effect | action which bridge | crosslinks an agent with resin which is (A) component, or polymerizes crosslinking agents. Examples of this photoacid generator include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, Oxime sulfonic acid esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, naphthoquinone diazide-4-sulfonic acid esters, and the like are used. Such compounds can be used in combination of two or more as required, or in combination with other sensitizers. Among the above photoacid generators, aromatic oxime sulfonates and aromatic N-oxyimide sulfonates are more preferable particularly from the viewpoint of photosensitivity.

(C) Compound containing two or more alcoholic hydroxyl groups (C) A compound containing two or more alcoholic hydroxyl groups used in the present invention will be described. (C) The compound containing two or more alcoholic hydroxyl groups is a compound having two or more alcoholic hydroxyl groups, which are hydroxyl groups bonded to carbon constituting an aliphatic or alicyclic compound, and derived from the skeleton thereof. And a compound containing two or more alcoholic hydroxyl groups.

  (C) By using a compound containing two or more alcoholic hydroxyl groups, the adhesiveness with copper or a copper alloy does not change even when exposed to a high temperature environment for a long time. The chemical mechanism that does not change the adhesiveness is not clear, but the hydroxyl group of the compound containing two or more alcoholic hydroxyl groups interacts with copper or copper alloy by hydrogen bonding, etc., and covers the surface of copper or copper alloy, It is presumed that the oxidation of copper or copper alloy is suppressed even under a high temperature environment, and the adhesiveness between (A) resin and copper or copper alloy copper does not change.

  (C) Examples of the compound containing two or more alcoholic hydroxyl groups include diols having 2 to 30 carbon atoms such as butanediol, nonanediol, and pinacol, 3 to 30 triols such as glycerin, and polyhydric alcohols such as saccharides. .

｛式中、Ｚは、置換基を有しても良い水素原子、炭素原子、酸素原子から構成される炭素数１〜３０の脂肪族又は脂環式構造である。｝の構造を持つ化合物は、１級水酸基の極性が高く、銅と配位し易いために本発明の効果が効果的に得られる。又、水酸基の数が多い程、本発明の効果が得られ易い。さらに、１級水酸基を持つ炭素原子が炭素数１〜３０の脂肪族又は脂環式構造と結合すると、感光性樹脂組成物の塗膜を乾燥中に（Ｃ）アルコール性水酸基を２つ以上含む化合物による架橋反応を抑制することが出来るため好ましい。又、１級水酸基を持つ炭素原子に結合する脂肪族又は脂環式構造は炭素数１〜３０であり、好ましくは炭素数３〜１０であり、さらに好ましくは炭素数４〜８である。１級水酸基を持つ炭素原子に結合する脂肪族又は脂環式構造の炭素数が３以上である場合キュア膜の脱ガスが少なくなり、炭素数が３０以下である場合（Ａ）樹脂との相溶性が向上する。具体例としては、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，７−へプタンジオール、１，８−オクタンジオール、１，９−ノナンジオール、１，１０−デカンジオール、ジプロピレングリコール、ペンタエリトリトール、ジペンタエリトリトール等が挙げられる。 In particular, (C) as a compound containing two or more alcoholic hydroxyl groups, the compound has one or more primary hydroxyl groups, and the primary hydroxyl group is represented by the following general formula (5):

{In formula, Z is a C1-C30 aliphatic or alicyclic structure comprised from the hydrogen atom which may have a substituent, a carbon atom, and an oxygen atom. }, The primary hydroxyl group has a high polarity and is easily coordinated with copper, so that the effects of the present invention can be effectively obtained. In addition, the effect of the present invention is easily obtained as the number of hydroxyl groups increases. Furthermore, when a carbon atom having a primary hydroxyl group is bonded to an aliphatic or alicyclic structure having 1 to 30 carbon atoms, the coating film of the photosensitive resin composition contains (C) two or more alcoholic hydroxyl groups during drying. This is preferable because the crosslinking reaction by the compound can be suppressed. The aliphatic or alicyclic structure bonded to a carbon atom having a primary hydroxyl group has 1 to 30 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. When the carbon number of the aliphatic or alicyclic structure bonded to the carbon atom having a primary hydroxyl group is 3 or more, degassing of the cured film is reduced, and when the carbon number is 30 or less (A) Phase with the resin Solubility is improved. Specific examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. 1,9-nonanediol, 1,10-decanediol, dipropylene glycol, pentaerythritol, dipentaerythritol and the like.

  Further, (C) a compound having two or more alcoholic hydroxyl groups each has one or more primary hydroxyl groups and one or more secondary hydroxyl groups, in addition to the effects of the above-mentioned primary hydroxyl groups, the moderate polarity of the secondary hydroxyl groups Therefore, (A) a resin and (C) a compound containing two or more alcoholic hydroxyl groups interact with each other, and adhesion is more preferable. Specific examples include glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 1,2,6-hexane. And triols.

  Furthermore, (C) when the compound containing two or more alcoholic hydroxyl groups is a polyhydric alcohol compound comprising aldose, ketose, pyranose, furanose, alditol, oxidation of copper or copper alloy is particularly suppressed even in a high temperature environment. Adhesion is maintained. This is considered to have a primary hydroxyl group and a large number of secondary hydroxyl groups, and that these compounds are not denatured even at high temperatures. Specific examples of aldose include erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose and the like. In addition, even if the compound which can become a pyranose structure or a furanose structure by intramolecular hemiacetal reaction among aldoses is used with the structure of a pyranose or a furanose, the effect of this invention is acquired similarly to aldose. Specific examples of pyranose include allopyranose, altropyranose, glucopyranose, mannopyranose, gropyranose, idopyranose, galactopyranose, talopyranose, and the like. Specific examples of furanose include ribofuranose, arabinofuranose, xylofuranose, and lixofuranose. Specific examples of ketose include erythrulose, xylulose, ribulose, psicose, fructose, sorbose, tagatose, cedoheptulose, coliose and the like. Specific examples of alditol include glycerin, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, glucitol, mannitol, iditol, galactitol, and taritol. Among these, alditols have a primary hydroxyl group at both ends, and thus the effects of the present invention are remarkably obtained.

  (C) The compounding quantity of the compound containing two or more alcoholic hydroxyl groups is 0.1-50 mass parts with respect to 100 mass parts of (A) resin, Preferably it is 1-30 mass parts. More preferably, it is 3-20 mass parts. When the said compounding quantity is 0.1 mass part or more, it is excellent in adhesiveness with copper or a copper alloy also in a high temperature environment, and on the other hand, when it is 50 mass parts or less, it is excellent in lithographic property.

  When the (D) nitrogen-containing heterocyclic compound such as azoles and purine derivatives is added to the photosensitive resin composition of the present invention, the effects of the present invention are remarkably exhibited. This forms a strong network structure between an azole or purine derivative and (C) a compound containing two or more alcoholic hydroxyl groups, and copper or a copper alloy. This is probably because the oxidation is strongly suppressed.

  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, 4-methyl-1H-benzotriazole, and 5-methyl-1H-tetrazole. 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-methyladenine, 1-methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) Guanine, N- (3-ethylphenyl) guanine, 2-aza Adenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, it includes 8-aza hypoxanthine or their derivatives.

  In the case where the photosensitive resin composition contains the azole compound or the purine derivative, the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), from the viewpoint of photosensitivity characteristics. 0.5-5 mass parts is more preferable. When the compounding amount of the azole compound with respect to 100 parts by mass of the resin (A) is 0.1 parts by mass or more, even if the photosensitive resin composition of the present invention is formed on copper or a copper alloy and exposed to a high temperature environment, The adhesiveness with copper or a copper alloy is excellent. On the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent.

  The photosensitive resin composition of the present invention may contain (E) a crosslinking agent. When the relief pattern formed by using the photosensitive resin composition of the present invention is heat-cured, the crosslinking agent (A) can crosslink the resin, or the crosslinking agent itself can form a crosslinked network. Can be. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the photosensitive resin composition.

  Examples of the cross-linking agent include ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (above, trade name, Honshu Chemical Industry Co., Ltd.) having one heat crosslinkable group. DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (above, trade name, Asahi Yu) as having two, such as Pa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) Equipment Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol- Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicalak MX-290 (trade name, Sansei Co., Ltd.) (Wa Chemical)

  Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p- TriML-P, TriML-35XL, TriML-TrisCR-HAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc., having three, such as cresol and 2,6-diacetoxymethyl-p-cresol TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, trade names, HML as having 6 products, including Honshu Chemical Industry Co., Ltd.), Nikarac MX-280, Nikalac MX-270 (above, trade name, Sanwa Chemical Co., Ltd.) TPPHBA, HML-TPHAP (or more, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALACK MW-390, NIKALACK MW-100LM (trade names, (Ltd.) manufactured by Sanwa Chemical) and the like can be mentioned.

  Of these, those containing at least two thermally crosslinkable groups are preferred in the present invention, and 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML- are particularly preferred. MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, Product name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicalak MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (trade name, Shikoku Chemicals, Inc.) Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cle , 2,6-diacetoxymethyl-p-cresol, TriML-P, TriML-35XL (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, Asahi Yu Equipment Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicarax MX-280, Nicarac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) and the like, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and the like. More preferably, Nicarax MX-290, Nicarax MX-280, Nicarac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (or above) , Trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), Nikarac MW-390, Nikalac MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), and the like.

  In combination with various performances other than heat resistance and chemical resistance, the blending amount when the photosensitive resin composition contains a crosslinking agent is 0.5 to 20 parts by mass with respect to 100 parts by mass of the resin (A). It is preferable that it is 2-10 parts by mass. 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.

(F) Organic Titanium Compound The photosensitive resin composition of the present invention may contain (F) an organic titanium compound. (F) By containing an organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 200 ° C.

  (F) 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 (F) organic titanium 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, (F) the organotitanium compound is preferably at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. It is preferable from the viewpoint of exhibiting sex. In particular, titanium diisopropoxide bis (ethyl acetoacetate), titanium tetra (n-butoxide), and bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- ( 1H-pyrrol-1-yl) phenyl) titanium is preferred.

  (F) 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) resin, More preferably, it is 0.1-2 mass parts. . 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.

(G) Other components The photosensitive resin composition of this invention may further contain components other than the said (A)-(F) component. The photosensitive resin composition of the present invention is typically used as a photosensitive resin composition in which the above-mentioned components and optional components further used as necessary are dissolved in a solvent to form a varnish. G) A solvent can be mentioned as another component. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the resin (A). 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) resin according to the desired coating film thickness and viscosity of the photosensitive resin composition, Preferably it is the range of 100-1000 mass parts. Can be used.

  Furthermore, the solvent containing alcohol is preferable from a viewpoint of improving the storage stability of the photosensitive resin composition. 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 photosensitive resin composition is improved. When the content is 50% by mass or less, the solubility of the resin (A) is high. Become good.

  Moreover, in order to suppress discoloration on the copper surface, a hindered phenol compound can be arbitrarily 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-t-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-tert-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-tert-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, , 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, , 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, , 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-t-butyl-6-ethyl-3- Droxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-6-ethyl-) 3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl- 5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione,

  1,3,5-tris (4-t-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, etc. However, it is not limited to this. 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) resin, and it is more preferable that it is 0.5-10 mass parts from a viewpoint of a photosensitivity characteristic. preferable. When the compounding quantity with respect to 100 mass parts of (A) resin of a hindered phenol compound is 0.1 mass part or more, for example, when forming the photosensitive resin composition of this invention on copper or a copper alloy, copper or Discoloration / corrosion of the copper alloy is prevented, and on the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent.

  The photosensitive resin composition of this invention may contain components other than the said component. For example, a sensitizer can be arbitrarily blended in order to improve photosensitivity. 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 photosensitive resin composition contains a sensitizer for improving photosensitivity, the blending amount is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the resin (A).
Further, 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 or polyethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Mono- or diacrylate and methacrylate of glycol, mono- or diacrylate and methacrylate of propylene glycol or polypropylene glycol, mono-, di- or triacrylate and methacrylate of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate of 1,4-butanediol and Dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate, neopentyl glycol diacrylate 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 glycerol Mention may be made of compounds such as triacrylates and methacrylates, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

  When the photosensitive resin composition contains the above-mentioned 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) It is preferable that it is 1-50 mass parts with respect to 100 mass parts of resin.

  In addition, an adhesion aid can be arbitrarily blended to improve the adhesion between the film formed using the 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, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane Silane coupling agents such as 3- (trialkoxysilyl) propyl succinic anhydride, and aluminum-based adhesives such as aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethyl acetoacetate aluminum diisopropylate An auxiliary agent etc. are mentioned.

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

  In addition, a thermal polymerization inhibitor can be optionally blended in order to improve the stability of the viscosity and photosensitivity of the 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 the photosensitive resin composition, the range of 0.005-12 mass parts is preferable with respect to 100 mass parts of (A) resin.

<Method for Manufacturing Cured Relief Pattern and Semiconductor Device>
The present invention also includes (1) a step of forming a resin layer on the substrate by applying the above-described photosensitive resin composition of the present invention onto the substrate, and (2) a step of exposing the resin layer. , (3) producing a relief pattern by developing the exposed resin layer, and (4) producing a cured relief pattern by heating the relief pattern to form a cured relief pattern. Provide a method. Hereinafter, typical aspects of each process will be described.

  (1) A step of forming a resin layer on a substrate by applying a photosensitive resin composition onto the substrate.

  In this step, the photosensitive resin composition of the present invention is applied onto a substrate, and then dried as necessary to form a 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 photosensitive resin composition can be dried. As a drying method, methods such as air drying, heat drying using an oven or a hot plate, vacuum drying, and the like are used. Specifically, when performing air drying or heat drying, drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. As described above, the resin layer can be formed on the substrate.

(2) Step of exposing the resin layer In this step, the resin layer formed above is exposed directly or directly through a photomask or reticle having a pattern using an exposure apparatus such as a contact aligner, mirror projection, or stepper. 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 that the temperature is 40 to 120 ° C. and the time is preferably 10 seconds to 240 seconds, but this range is not used unless it inhibits the various characteristics of the photosensitive resin composition of the present invention. Not limited to.

(3) Step of developing the exposed resin layer to form a relief pattern In this step, the exposed or unexposed portion of the exposed photosensitive resin layer is developed and removed. In the composition of the present invention which is a negative photosensitive resin composition, an unexposed portion is developed and removed. As a developing method, an arbitrary method can be selected and used from conventionally known photoresist developing methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment. 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 photosensitive resin composition or a combination of the good solvent and the poor solvent. For example, in the case of a photosensitive resin composition that does not dissolve in an alkaline aqueous solution, good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α -Acetyl-γ-butyrolactone and the like are preferable, and as the poor 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 photosensitive resin composition. Also, two or more of each solvent, for example, several types can 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 development is heated to be converted into a cured relief pattern. 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 180 ° 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 including 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 including a base material that is a semiconductor element and a cured relief pattern of a resin formed on the base material by the above-described cured relief pattern manufacturing method. The present invention can also be applied to a method for manufacturing a semiconductor device using a semiconductor element as a base material and including 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 photosensitive resin composition of the present invention is useful not only for application to semiconductor devices as described above, but also for uses such as interlayer insulation for multilayer circuits, cover coating for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. It is.

  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 the photosensitive resin composition were measured and evaluated according to the following methods.

<Synthesis Example 1> Polyamic acid ester polymer A
Place 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 l 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 liquid was added to 3 l 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 l of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 l of water to precipitate a polymer, and the obtained precipitate was filtered off and dried in vacuo to obtain a polymer A which is a powdered polyamic acid ester. When the molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

<Synthesis Example 2> Polyamic acid ester polymer B
Instead of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example 1, 147.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for the above, the reaction was carried out in the same manner as described in Production Example 1 to obtain a polymer B which is a polyamic acid ester. 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.

<Synthesis Example 3> Polyamic acid polymer C
93.0 g of 4,4′-diaminodiphenyl ether (DADPE) was placed in a 2 l separable flask, 700 ml of N-methylpyrrolidone (NMP) was added and stirred at room temperature to completely dissolve.

  Next, 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was added to this solution with stirring, and the mixture was stirred at room temperature for 2 hours. The polyamic acid reaction solution thus obtained was dropped into 28 L of water to precipitate a polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a polymer C as a powdered polyamic acid. . When the molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 34,000.

<Synthesis Example 4> Polyamide Polymer D
(Synthesis of Phthalic Acid Compound Encapsulated AIPA-MO)
In a separable flask having a volume of 5 l, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. A solution obtained by diluting 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone was added dropwise thereto using a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

  Completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, The reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer D)
Into a separable flask having a volume of 2 liters, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added and mixed, and cooled to 5 ° C. in an ice bath. did. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice-cooling, followed by 4,4′-bis (4-aminophenoxy). ) Biphenyl {Hereinafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

  A mixed liquid of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction liquid, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was dropped into 5 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain polymer D, which is a powdery polyamide. When the molecular weight of the polymer E was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 34,700.

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

(2) Sensitivity The photosensitive resin composition was spin-coated on a 6-inch silicon wafer using a spin coater (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan), and heated on a hot plate at 100 ° C. for 300 seconds. Drying was performed to form a 9 μm thick coating film. A specific wafer position was sequentially irradiated with energy of 100 to 700 mJ / cm ² by an i-line stepper NSR1755i7B (manufactured by Nikon Corporation) using a reticle with a test pattern on the coating film. Subsequently, 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 polyamic acid ester. Got the pattern. The wafer on which the pattern is formed is heat-treated in a nitrogen atmosphere at 200 ° C. for 1 hour and subsequently at 300 ° C. for 2 hours using a temperature-programmed cure furnace (VF-2000 type, manufactured by Koyo Lindberg, Japan). Thus, a polyimide pattern having a thickness of 5 μm was obtained on the silicon wafer. About each obtained pattern, the pattern shape and the width | variety of a pattern part were observed under the optical microscope, and the resolution | decomposability at the time of 350 mJ / cm < ² > exposure was calculated | required.

A pattern having a plurality of openings with different areas is formed by the above-described method by exposing through a reticle with a test pattern, and the area of the obtained pattern openings is ½ or more of the corresponding pattern mask opening area. If it is, it is regarded that it was resolved, and the length of the opening side of the mask corresponding to the resolved opening having the smallest area was defined as the resolution. The resolution was evaluated based on the following criteria.
○: Resolution is less than 30 μm Δ: Resolution is 30 μm or more and less than 50 μm ×: Resolution is 50 μm or more

(3) Copper adhesion test after holding under high temperature environment (number of substrate adhesion grids)
A photosensitive resin composition was spin-coated on a copper substrate, dried to form a 9 μm-thick coating film as a photosensitive resin layer, and then a temperature-programmed curing furnace (VF-2000 type, Koyo Lindberg, Japan) The cured resin coating film having a thickness of 5 μm was obtained by heat treatment (curing) at 200 ° C. for 1 hour and then at 300 ° C. for 2 hours in a nitrogen atmosphere. This cured film was held under an atmospheric pressure air atmosphere at 150 ° C. for 500 hours and 1000 hours using an unsaturated pressure cooker (PC-R8D type, manufactured by HIRAYAMA, Japan), and then JIS K 5600. According to the crosscut method of the -5-6 standard, the adhesive properties between the copper substrate and the cured resin coating film after the cured film was maintained in a high temperature environment were evaluated based on the following criteria.
“Best”: The cured resin coating film adhered to the substrate has a lattice number of 100.
“Good”: The cured resin coating film adhered to the substrate has a lattice number of 80 to 99.
“Slightly good”: The number of grids of the cured resin coating film adhered to the substrate is 50 to 79.
“Slightly bad”: the cured resin coating film adhered to the substrate has a lattice number of 20 to 49.
“Bad”: The number of grids of the cured resin coating film adhered to the substrate is less than 20.

(4) Heat resistance test After a photosensitive resin composition was spin-coated on a copper substrate and dried to form a 9 μm-thick coating film as a photosensitive resin layer, a temperature rising programmed curing furnace (VF-2000 type, A cured resin coating film having a thickness of 5 μm was obtained by heat treatment (curing) at 200 ° C. for 1 hour and then at 300 ° C. for 2 hours in a nitrogen atmosphere using a product of Koyo Lindberg, Japan. The cured film was peeled off from the wafer, and 5 mg of the cured film was measured at 5 ° C. from room temperature to 600 ° C. in a nitrogen atmosphere using a calorimeter measuring device (TGA) (TGA-50, manufactured by Shimadzu Corporation, Japan). The sample was heated at a heating rate of / min, and the 5% weight loss temperature was measured.

<Example 1>
Using the polymer A, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Polymer A 100 g which is a polyamic acid ester (corresponding to the resin (A)) is described as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) -oxime (referred to as “PDO” in Table 1). ) (Corresponding to (B) photosensitive agent) 4 g, 1,9-nonanediol (corresponding to (C) a compound containing two or more alcoholic hydroxyl groups) 10 g, 1,3,5-tris (4-t-butyl- 3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 1.5 g, N-phenyldiethanolamine 10 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] phthalamic acid 1.5 g and 2-nitroso-1-naphthol 0.05 g together with N-methyl-2- Pyrrolidone (hereinafter referred to as NMP) were 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 above mixed solvent to obtain a negative photosensitive resin composition.

<Example 2>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 100 g of the polymer B was used instead of the polymer A which was the resin (A) used in Example 1.

<Example 3>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 50 g of polymer A and 50 g of polymer B were used in place of polymer A which is the resin (A) used in Example 1.

<Example 4>
Polymer C 100 g which is a polyamic acid (corresponding to the resin (A)) was converted into 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) -oxime (described as “PDO” in Table 1). (Corresponding to (B) photosensitizer) 4 g, 1,9-nonanediol (corresponding to a compound containing two or more (C) alcoholic hydroxyl groups) 10 g, 1,3,5-tris (4-t-butyl-3 -Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 1.5 g, diethylaminoethyl methacrylate 72 g, N-phenyldiethanolamine 10 g, tetra 8 g of ethylene glycol dimethacrylate, 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid, and 2-nitroso-1-naphthol With .05g, (in the following referred to NMP) N-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 above mixed solvent to obtain a negative photosensitive resin composition.

<Example 5>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 100 g of the polymer D was used instead of the polymer A which was the resin (A) used in Example 1.

<Example 6>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.1 g of nonanediol was used in place of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1. did.

<Example 7>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 1 g of nonanediol was used instead of 10 g of nonanediol which is a compound containing two or more (C) alcoholic hydroxyl groups used in Example 1.

<Example 8>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 30 g of nonanediol was used instead of 10 g of nonanediol which is a compound containing two or more (C) alcoholic hydroxyl groups used in Example 1.

<Example 9>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 50 g of nonanediol was used instead of 10 g of nonanediol, which was a compound containing two or more (C) alcoholic hydroxyl groups used in Example 1.

<Example 10>
In the same manner as in Example 1, negative photosensitivity was used in the same manner as in Example 1, except that 10 g of pentaerythritol having four primary hydroxyl groups was used instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1. A resin composition was prepared.

<Example 11>
Instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1, 10 g of 1,4-benzenedimethanol in which a carbon atom having a primary hydroxyl group is bonded to a benzene ring. Then, a negative photosensitive resin composition was prepared in the same manner as in Example 1.

<Example 12>
Using 10 g of α, α′-dihydroxy-1,3-diisopropylbenzene having a tertiary hydroxyl group in place of 10 g of nonanediol which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1 A negative photosensitive resin composition was prepared in the same manner as in Example 1.

<Example 13>
A negative photosensitive resin composition as in Example 1 except that 10 g of pinacol having a tertiary hydroxyl group is used instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1. Adjusted.

<Example 14>
In Example 1, 10 g of 1,3,5-pentanetriol having a primary hydroxyl group and a secondary hydroxyl group was used instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1. In the same manner as in Example 1, a negative photosensitive resin composition was prepared.

<Example 15>
A negative photosensitive resin composition in the same manner as in Example 1 except that 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1, is replaced with 10 g of D-xylose which is aldose. Adjusted.

<Example 16>
A negative photosensitive resin composition in the same manner as in Example 1 except that 10 g of nonanediol (C), which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1, is replaced with 10 g of D-glucose which is aldose. Adjusted.

<Example 17>
A negative photosensitive resin composition in the same manner as in Example 1 except that 10 g of D-fructose, which is ketose, is used instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1. Adjusted.

<Example 18>
A negative photosensitive resin in the same manner as in Example 1 except that 10 g of L-fructose, which is an L form, is used instead of 10 g of D-fructose which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 17. The composition was adjusted.

<Example 19>
In the same manner as in Example 1, a negative photosensitive resin composition was prepared using 10 g of erythritol, which is alditol, instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1. did.

<Example 20>
In the same manner as in Example 1, a negative photosensitive resin composition was prepared using 10 g of xylitol, which is alditol, instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1. did.

<Example 21>
In the same manner as in Example 1, a negative photosensitive resin composition was prepared using 10 g of mannitol, which is alditol, instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1. did.

<Example 22>
The negative photosensitive resin composition of Example 1 was further added (D) 3 g of 5-methyl-1H-benzotriazole, which is a nitrogen-containing heterocyclic compound, to the negative photosensitive resin composition of Example 1, and the negative photosensitive resin composition was the same as in Example 1. Adjusted.

<Example 23>
To the negative photosensitive resin composition of Example 1, (D) 3 g of 5-methyl-1H-tetrazole which is a nitrogen-containing heterocyclic compound was further added, and the negative photosensitive resin composition was obtained in the same manner as in Example 1. It was adjusted.

<Example 24>
To the negative photosensitive resin composition of Example 1, 3 g of 8-azaadenine, which is a nitrogen-containing heterocyclic compound (D), was further added to prepare a negative photosensitive resin composition in the same manner as in Example 1.

<Example 25>
Negative photosensitive resin composition as in Example 1, except that (D) 3 g of 5-methyl-1H-benzotriazole, which is a nitrogen-containing heterocyclic compound, was further added to the negative photosensitive resin composition of Example 20. Adjusted.

<Example 26>
To the negative photosensitive resin composition of Example 20, (D) 3 g of 5-methyl-1H-tetrazole, which is a nitrogen-containing heterocyclic compound, was further added, and the negative photosensitive resin composition was obtained in the same manner as in Example 1. It was adjusted.

<Example 27>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 by further adding 3 g of 8-azaadenine, which is a nitrogen-containing heterocyclic compound (D), to the negative photosensitive resin composition of Example 201.

<Example 28>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 by using 70 g of nonanediol instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1. .

<Comparative Example 29>
In the same manner as in Example 1, a negative photosensitive resin composition was prepared using 70 g of xylitol instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1.

<Comparative Example 1>
Polymer A 100 g which is a polyamic acid ester (corresponding to the resin (A)) is described as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) -oxime (referred to as “PDO” in Table 3). ) (Corresponding to (B) photosensitive agent) 4 g, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4 6- (1H, 3H, 5H) -trione 1.5 g, N-phenyldiethanolamine 10 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] phthalamic acid 1.5 g, and 2-nitroso It was dissolved in a mixed solvent composed of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate together with 0.05 g of -1-naphthol. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above mixed solvent to obtain a negative photosensitive resin composition.

<Comparative example 2>
A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 1 except that 100 g of the polymer B was used instead of the polymer A which was the resin (A) used in Comparative Example 1.

<Comparative Example 3>
A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 1 except that 50 g of polymer A and 50 g of polymer B were used instead of polymer A, which was the resin (A) used in Comparative Example 1.

<Comparative example 4>
Polymer C 100 g which is a polyamic acid (corresponding to the resin (A)) was converted to 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) -oxime (described as “PDO” in Table 3). (Corresponding to (B) photosensitizer) 4 g, 1,9-nonanediol (corresponding to a compound containing two or more (C) alcoholic hydroxyl groups) 10 g, 1,3,5-tris (4-t-butyl-3 -Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 1.5 g, diethylaminoethyl methacrylate 72 g, N-phenyldiethanolamine 10 g, tetra 8 g of ethylene glycol dimethacrylate, 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid, and 2-nitroso-1-naphthol With .05g, (in the following referred to NMP) N-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 above mixed solvent to obtain a negative photosensitive resin composition.

<Comparative Example 5>
A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 1 except that 100 g of the polymer D was used instead of the polymer A which was the resin (A) used in Comparative Example 1.

<Comparative Example 6>
A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 1 by further adding 3 g of 8-azaadenine (D) a nitrogen-containing heterocyclic compound to the negative photosensitive resin composition of Comparative Example 1.

<Comparative Example 7>
In the same manner as in Example 1, negative type photosensitivity was used instead of 10 g of nonanediol, which is a compound containing two or more alcoholic hydroxyl groups (C) used in Example 1, and 1-octanol having one hydroxyl group. The resin composition was prepared.

  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 (12)

(A) The following general formula (1):

{Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently And a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, 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 ₁ is an integer of 2 to 10). A monovalent organic group,
Or the following general formula (3):

(Wherein R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10). Monovalent ammonium ion}
A polyamic acid, a polyamic acid ester or a polyamic acid salt, which is a polyimide precursor represented by:
Or the following general formula (4):

{Wherein X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and R ₉ is a carbon group having 3 to 20 carbon atoms. It is an organic group having at least one radical-polymerizable unsaturated bond group, and n ₂ is an integer of 1 to 1000. However, the plurality of X ₂ and Y ₂ may have different structures. }
A resin containing at least a polyamide having a structure represented by:
(B) photosensitive material; and (C) a compound containing two or more alcoholic hydroxyl groups:
A negative photosensitive resin composition comprising:   The negative photosensitive resin composition of Claim 1 whose compound which contains the said (C) 2 or more alcoholic hydroxyl group is 1-50 mass parts with respect to 100 mass parts of resin of the said (A). The compound (C) containing two or more alcoholic hydroxyl groups, of which at least one alcoholic hydroxyl group is represented by the following general formula (5):

{In formula, Z is a C1-C30 aliphatic or alicyclic structure comprised from the hydrogen atom which may have a substituent, a carbon atom, and an oxygen atom. }
The negative photosensitive resin composition of Claim 1 or 2 which is the primary hydroxyl group which has a structure represented by these.   The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the compound (C) having two or more alcoholic hydroxyl groups has three or more alcoholic hydroxyl groups.   The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the compound (C) having two or more alcoholic hydroxyl groups has at least one primary hydroxyl group and one or more secondary hydroxyl groups.   The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the compound (C) containing two or more alcoholic hydroxyl groups is selected from the group consisting of aldose, ketose, pyranose, furanose, and alditol. object.   (D) The negative photosensitive resin composition as described in any one of Claims 1-6 which further contains a nitrogen-containing heterocyclic compound.   A cured relief pattern obtained by heat-treating a relief pattern formed from the negative photosensitive resin composition was maintained in a high-temperature environment at 150 ° C. for 500 hours and 1000 hours under an atmospheric pressure air atmosphere. The negative type according to any one of claims 1 to 7, wherein the number of lattices adhered to the substrate of the cured relief pattern is 50 or more when evaluated according to the cross-cut method of 5600-5-6 standard. Photosensitive resin composition. (1) A step of forming a photosensitive resin layer on the substrate by applying the negative photosensitive resin composition according to any one of claims 1 to 8 on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) The manufacturing method of a hardening relief pattern including the process of forming a hardening relief pattern by heat-processing the said relief pattern.   The method of claim 9, wherein the substrate is formed from copper or a copper alloy.   A cured relief pattern obtained by the method according to claim 9.   A semiconductor device comprising the cured relief pattern according to claim 11.