JP2006184660A - Positive photosensitive resin composition, and semiconductor device and display component using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin for providing a polybenzoxazole resin, a polyimide resin or a copolymer resin thereof excellent in adhesion particularly to metals, and to provide a positive photosensitive resin composition using the polyamide resin and excellent in exposure property. <P>SOLUTION: The positive photosensitive resin composition contains (A) an alkali-soluble resin, (B) a photosensitive diazoquinone compound and (C) a heterocyclic compound containing two or more nitrogen atoms, wherein the component (C) is preferably a heterocyclic compound containing three or more nitrogen atoms. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a positive photosensitive resin composition, and a semiconductor device and a display element using the same.

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protective films and interlayer insulating films of semiconductor elements.
On the other hand, in order to simplify the process, a positive photosensitive resin in which the polybenzoxazole resin or polyimide resin is combined with a photosensitive diazoquinone compound is also used (Patent Document 1).
In recent years, due to miniaturization of semiconductor elements, multi-layer wiring by high integration, transition to chip size package (CSP), wafer level package (WLP), etc., low dielectric constant and copper, aluminum, gold, titanium There is a demand for improving adhesion to wirings or wiring metals such as high performance polybenzoxazole resins and polyimide resins.

Regarding adhesion, it is generally known that by using an organic silicon compound, adhesion with a substrate such as silicon or a nitride film can be improved (Patent Document 2). However, there is a tendency that the adhesion of the resin is insufficient with respect to the material constituting the rewiring represented by copper and the like, and a resin composition having high adhesion to the metal is required.
JP-A-1-46862 JP-A 63-001584

  The present invention relates to a polyamide resin for providing a polybenzoxazole resin or a polyimide resin excellent in adhesion to a metal or a copolymer resin thereof, and a positive photosensitive resin composition excellent in exposure characteristics using them. An object, a semiconductor device, and a display element are provided.

［７］（Ａ）が１００重量部、（Ｂ）が１〜５０重量部、（Ｃ）が０．１〜２０重量部であり、さらにフェノール化合物（Ｄ）が１〜３０重量部含んでいる［５］又は［６］記載のポジ型感光性樹脂組成物。
［８］（Ａ）アルカリ可溶性樹脂が、ポリアミド樹脂である［１］乃至［７］記載のポジ型感光性樹脂組成物。
［９］（Ａ）アルカリ可溶性樹脂が、ポリベンゾオキサゾール前駆体構造、ポリアミド酸構造又はポリアミド酸エステル構造を含むポリアミド樹脂である［８］記載のポジ型感光性樹脂組成物。
［１０］（Ａ）アルカリ可溶性樹脂が、一般式（２）で示される構造を含むポリアミド樹脂である［８］又は［９］記載のポジ型感光性樹脂組成物。

［１１］一般式（２）で示される構造を含むポリアミド樹脂中のＸが、式（３）の群より選ばれてなる［１０］記載のポジ型感光性樹脂組成物。

［１２］一般式（２）で示される構造を含むポリアミド樹脂中のＹが、式（４）の群より選ばれてなる［１０］又は［１１］記載のポジ型感光性樹脂組成物。

［１３］一般式（２）で示される構造を含むポリアミド樹脂が、アルケニル基又はアルキニル基を含む化合物で末端封止された［１０］乃至［１２］のいずれかに記載のポジ型感光性樹脂組成物。
［１４］［１］乃至［１３］のいずれかに記載のポジ型感光性樹脂組成物を用いて作成される半導体装置。
［１５］［１］乃至［１３］のいずれかに記載のポジ型感光性樹脂組成物を用いて作成される表示素子。 Such an object is achieved by the present invention described in the following [1] to [15].
[1] (A) an alkali-soluble resin,
(B) a photosensitive diazoquinone compound, and
(C) a heterocyclic compound containing two or more nitrogen atoms,
A positive photosensitive resin composition comprising:
[2] The positive photosensitive resin composition according to [1], wherein the component (C) is a heterocyclic compound containing three or more nitrogen atoms.
[3] The positive photosensitive resin composition according to [1], wherein the component (C) is a triazole compound.
[4] The positive photosensitive resin composition according to [1], wherein the component (C) is 1,2,4-triazole.
[5]
The positive photosensitive resin composition according to any one of [1] to [4], further comprising (D) a phenol compound.
[6] The positive type according to [1] or [2], wherein the phenol compound (D) is a phenol compound having a structure represented by the general formula (1-1) or a structure represented by the general formula (1-2). Photosensitive resin composition.

[7] 100 parts by weight of (A), 1-50 parts by weight of (B), 0.1-20 parts by weight of (C), and further 1-30 parts by weight of phenolic compound (D). The positive photosensitive resin composition according to [5] or [6].
[8] The positive photosensitive resin composition according to [1] to [7], wherein (A) the alkali-soluble resin is a polyamide resin.
[9] The positive photosensitive resin composition according to [8], wherein (A) the alkali-soluble resin is a polyamide resin containing a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure.
[10] The positive photosensitive resin composition according to [8] or [9], wherein (A) the alkali-soluble resin is a polyamide resin containing a structure represented by the general formula (2).

[11] The positive photosensitive resin composition according to [10], wherein X in the polyamide resin having a structure represented by the general formula (2) is selected from the group of the formula (3).

[12] The positive photosensitive resin composition according to [10] or [11], wherein Y in the polyamide resin having a structure represented by the general formula (2) is selected from the group of the formula (4).

[13] The positive photosensitive resin according to any one of [10] to [12], wherein the polyamide resin having the structure represented by the general formula (2) is end-capped with a compound containing an alkenyl group or an alkynyl group. Composition.
[14] A semiconductor device produced using the positive photosensitive resin composition according to any one of [1] to [13].
[15] A display element produced using the positive photosensitive resin composition according to any one of [1] to [13].

  According to the present invention, a polybenzoxazole resin, a polyimide resin excellent in adhesion to a metal, a polyamide resin intended to provide a resin that is a copolymer thereof, and a positive photosensitive resin excellent in exposure characteristics using them. Resin composition and a semiconductor device using the same can be obtained.

  The present invention relates to a positive photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photosensitive diazoquinone compound, and (C) a heterocyclic compound containing two or more nitrogen atoms. Is. The following is an example, and the present invention is not limited to the following. Hereinafter, each component of the positive photosensitive resin composition of the present invention will be described in detail.

The alkali-soluble resin (A) used in the present invention is a resin having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or side chain, and is a cresol type novolak resin, polyhydroxystyrene, or polyamide resin. Of these, polyamide resins are preferred. The polyamide resin is a resin having a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure and having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or side chain. Among these, a polyamide resin having a structure represented by the general formula (2) is preferable from the viewpoint of heat resistance after the final heating. Further, some of these resins may be ring-closed to have a polybenzoxazole structure or a polyimide structure.
X in the polyamide resin having the structure represented by the general formula (2) represents a divalent to tetravalent organic group, R ₈ is a hydroxyl group or O—R ₁₀ , and m is an integer of 0 to 2. is there. Each R ₈ may be the same or different. Y in the general formula (2) represents a divalent to hexavalent organic group, R ₉ is a hydroxyl group, a carboxyl group, O—R ₁₀ or COO—R ₁₀ , and n is an integer of 0 to 4. Each R ₉ may be the same or different. Here, R ₁₀ is an organic group having 1 to 15 carbon atoms. However, when R ₈ has no hydroxyl group, at least one R ₉ must be a carboxyl group. When R ₉ does not have a carboxyl group, at least one R ₈ must be a hydroxyl group.

The polyamide resin containing the structure represented by the general formula (2) is, for example, a compound selected from a diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, and the structure of Z blended as necessary. Reacts with a compound selected from tetracarboxylic anhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, etc. Is obtained. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.
In the polyamide resin containing the structure represented by the general formula _{(2), O-R 10} , COO-R 10 as a substituent of O-R _10, Y as a substituent of X is a hydroxyl group, an alkaline aqueous solution of the carboxyl group Is a group protected by R ₁₀ which is an organic group having 1 to 15 carbon atoms, and a hydroxyl group or a carboxyl group may be protected if necessary. Examples of R ₁₀ include formyl, methyl, ethyl, propyl, isopropyl, tertiary butyl, tertiary butoxycarbonyl, phenyl, benzyl, tetrahydrofuranyl, tetrahydropyranyl and the like. It is done.

When this polyamide resin is heated at about 300 to 400 ° C., it is dehydrated and closed, and a heat resistant resin is obtained in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both.

等であるが、これらに限定されるものではない。 X in general formula (2)
For example,

However, it is not limited to these.

より選ばれるものであり、又２種類以上用いても良い。 Among these, particularly preferred are:

Two or more types may be used.

等であるが、これらに限定されるものではない。 Y that can be used in the polyamide resin having the structure represented by the general formula (3) is, for example,

However, it is not limited to these.

より選ばれるものであり、又２種類以上用いても良い。 Among these, particularly preferred are:

Two or more types may be used.

等が挙げられるが、これらに限定されるものではない。
これらの中で特に好ましいものとしては、

より選ばれるものであり、又２種類以上用いても良い。 In the present invention, it is desirable to seal the end from the viewpoint of storage stability. For sealing, a derivative having an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group can be introduced as an acid derivative or an amine derivative at the end of the polyamide represented by the general formula (2). Specifically, for example, a diamine having a structure of X or a compound selected from bis (aminophenol), 2,4-diaminophenol and the like, a silicone diamine having a structure of Z blended as necessary, and a structure of Y are included. General formula (2) obtained by reacting a compound selected from tetracarboxylic acid anhydride, trimellitic acid anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, etc. After synthesizing a polyamide resin having the structure shown, an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group as the terminal amino group contained in the polyamide resin Is preferably used to cap as an amide. Examples of the group derived from an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include:

However, it is not limited to these.
Among these, particularly preferred are:

Two or more types may be used.

等が挙げられるが、これらに限定されるものではなく、又２種類以上用いても良い。 Furthermore, Z of the polyamide resin including the structure represented by the general formula (2) used as necessary is, for example,

However, it is not limited to these, and two or more types may be used.

  Z of the polyamide resin having the structure represented by the general formula (2) is used when particularly excellent adhesion is required to a substrate such as a silicon wafer, for example. Up to%. When it exceeds 40 mol%, the solubility of the resin in the exposed area is extremely lowered, developing residue (scum) is generated, and pattern processing becomes impossible.

これらの内で、特に好ましいのは、フェノール化合物と１，２−ナフトキノン−２−ジアジド−５−スルホン酸又は１，２−ナフトキノン−２−ジアジド−４−スルホン酸とのエステルである。それらについては例えば、下記のものが挙げられるが、これらに限定されるものではない。これらは２種以上用いても良い。

The photosensitive diazoquinone compound (B) used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is known from US Pat. Nos. 2,729,975, 2,797,213 and 3,669,658. It is a substance. For example, the following are mentioned.

Among these, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid is particularly preferable. Examples of these include, but are not limited to, the following. Two or more of these may be used.

  The amount of the (B) photosensitive diazoquinone compound used in the present invention is 1 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin. If the amount is less than 1 part by weight, a good pattern cannot be obtained, and if it exceeds 50 parts by weight, the sensitivity is greatly reduced.

  Among the heterocyclic compounds containing two or more nitrogen atoms (C) of the present invention, a heterocyclic compound is a ring formed from atoms of two or more elements (in addition to carbon, nitrogen, oxygen, sulfur, etc.). Refers to a cyclic compound comprising In the present invention, a heterocyclic compound containing two or more nitrogen atoms means a cyclic compound containing at least a carbon atom and two or more nitrogen atoms.

  (C) The heterocyclic compound containing two or more nitrogen atoms is imidazole, benzimidazole, 2-aminobenzimidazole, dimethylbenzimidazole, 2-mercapto-1,3. 4-thiadiazol, 2,5-dimethyl-1,3,4-thiadiazol, 4-phenyl-1,2,3-thiadiazol, 2-amino-1,3,4-thiadiazol, Examples include 2-amino-5-ethyl-1,3,4-oxadiazol, but are not limited thereto.

  The heterocyclic compound (C) of the present invention containing 3 or more nitrogen atoms is 1,2,4-triazole, 1,3,4-triazole, 1,2,3-triazole, 1,2,5-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-amino-5 Benzyl-4H-1,2,4-triazole, 3-amino-5-cyclobutyl-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4- Triazol, 4-amino-3,5-dipropyl-4H-1,2,4-triazole, 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole, 3- Amino-5-isopropyl-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H 1,2,4-triazole, 4-amino-3-mercapto-4H-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 4- Amino-3-mercapto-5- (trifluoromethyl) -4H-1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,4-triazole, 3-amino- 5-methyl-4H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-3,5-dimethyl-1,2,4-thiazol, 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole, 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol, 4- Amino-5-phenyl-4H-1,2,4-triazol-3-thiol, 3-bromo-5-nitro-1 , 2,4-triazol, 3,5-diamino-1H-1,2,4-triazole, 3-hexylthio-1H-1,2,4-triazole, 3-nitro-1,2 , 4-triazole, 3-propylthio-4H-1,2,4-triazole, 1- (2,4,6-triisopropylbenzenesulfonyl) -1,2,4-triazole, 1- Trimethylsilyl-1,2,4-triazole, benzotriazole, benzotriazole-4-sulfonic acid, 1-hydroxybenzotriazole, 1,3,5-triazine, 2-amino-4- [3 , 5-Bis (trifluoromethyl) phenyl] amino-1,3,5-triazine, 2-amino-4-cyclopropyl-6-hydroxy-1,3,5-triazine, 2-amino-4,6- Dichloro-s-triazine, 3 Amino-5,6-dimethyl-1,2,4-triazine, 3-amino-5,6-diphenyl-1,2,4-triazine, 2-amino-4-methoxy-6- (methylthio) -1, 3,5-triazine, 2-amino-1,3,5-triazine, 3-amino-5,6-dimethyl-1,2,4-triazine, 2-amino-4- (2-fluorophenylamino)- 1,3,5-triazine, 2-amino-4-hydroxy-6-methyl-1,3,5-triazine, 2-amino-1,3,5-triazine-4,6-dithiol, 2, 4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, 2,4 -Diamino-6-undecyl-s-triazine, 2-chloro -4,6-bis (ethylamino) -1,3,5-triazine, 2-chloro-4,6-dimethoxy-1,3,5-triazine, 2,4,6-trichloro-1,3,5 Triazine, 2,4-bis (trichloromethyl) -6-methyl-1,3,5-triazine, 2- [2- (2-furan-2-yl) vinyl] -4,6-bis (trichloromethyl) ) -1,3,5-triazine, 2-chloro-4,6-bis (ethylamino) -1,3,5-triazine, hexahydro-1,3,5-triethyl-s-triazine, 2- [2 -(5-Methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (N-carboxymethyl-N-phenyl) amino-4,6- Dimercapto-1,3,5-triazine, 5,6-diph Nyl-3- (2-pyridyl) -1,2,4-triazine, 5,6-diphenyl-1,2,4-tri, 1,3,5-tribenzylhexahydro-s-triazine, 2,4 , 6-Tripyridyl-s-triazine, 1,2,3-benzotriazine, 3-hydroxy-1,2,3-benzotriazine and the like, but are not limited thereto.

  The (C) triazole compound of the present invention refers to a compound containing a hetero five-membered ring composed of 3 atoms of nitrogen and 2 atoms of carbon. Of these compounds, 1,2,4-triazole is particularly preferred.

  The (C) heterocyclic compound containing two or more nitrogen atoms of the present invention improves the adhesion between the photosensitive resin and the substrate (single metal film or alloy film such as copper, aluminum or titanium, particularly copper). It is used to make it.

  The addition amount of the heterocyclic compound containing two or more nitrogen atoms (C) of the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyamide. If the amount is less than 0.1 parts by weight, it is not preferable because the effect of improving the adhesiveness cannot be obtained. If the amount exceeds 20 parts by weight, the mechanical strength of the polybenzoxazole film formed on the semiconductor element is lowered and the stress relaxation effect is reduced. Therefore, it is not preferable.

The (D) phenol compound of the present invention is a phenol compound different from (A) an alkali-soluble resin, (B) a photosensitive diazoquinone compound, and (C) a heterocyclic compound containing two or more nitrogen atoms, Any compound containing a phenolic hydroxyl group in the molecule may be used. (D) As a phenol compound, the phenol compound containing the structure shown by the structure shown by General formula (1-1) or General formula (1-2) is preferable.

  As a technique for adding a phenol compound to a positive resist composition, for example, JP-A-3-200251, JP-A-3-200262, JP-A-3-200263, JP-A-3-200244, These are disclosed in, for example, Kaihei 4-1650, JP-A-4-11260, JP-A-4-12356, and JP-A-4-12357. However, when the phenolic compounds as shown in these are used in a positive photosensitive resin composition based on the polyamide resin in the present invention, the effect of improving the sensitivity is small. However, when a phenol compound having a structure represented by the general formula (1-1) and / or a phenol compound having a structure represented by the general formula (1-2) is used in the present invention, these are not used and the aromatic ring is used. Compared with the case of using a phenol compound other than these, such as a phenol compound having no substituent, the dissolution rate of the exposed portion in the developer is increased, the sensitivity is improved, and the occurrence of scum is further suppressed. In addition, the film loss at the unexposed area as seen when the sensitivity is improved by reducing the molecular weight is very small.

Examples of the phenol compound containing the structure represented by the general formula (1-1) include, but are not limited to, the following compounds. Two or more types may be used.

Examples of the phenol compound having the structure represented by the general formula (1-2) include, but are not limited to, the following compounds. Two or more types may be used.

In the present invention, in addition to the phenol compound having the structure represented by the general formula (1-1) or the phenol compound having the structure represented by (1-2), the following phenol compounds may be added as necessary. However, it is not limited to these.

  The preferred addition amount of the phenol compound containing the structure represented by the general formula (1-1) or the phenol compound (D) having the structure represented by (1-2) is 1 to 30 with respect to 100 parts by weight of the alkali-soluble resin. Parts by weight. If it is less than 1 part by weight, the sensitivity at the time of development is lowered, and if it exceeds 30 parts by weight, the film of the unexposed part is significantly reduced at the time of development.

  If necessary, additives such as a leveling agent, a silane coupling agent, a titanate coupling agent, and their respective reactants can be added to the positive photosensitive resin composition in the present invention.

  The polyamide resin of the present invention is dissolved in a solvent and used in the form of a varnish. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropio And the like, and may be used alone or in combination.

  In the method of using the positive photosensitive resin composition of the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. In the case of a semiconductor device, the coating amount is applied so that the final film thickness after curing is 0.1 to 50 μm. If the film thickness is less than the lower limit value, it will be difficult to fully function as a protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. Takes a long time to reduce throughput. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, after prebaking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the desired pattern shape. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

  Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a salt, and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

  Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment is performed to form an oxazole ring and / or an imide ring, thereby obtaining a final pattern rich in heat resistance.

  The positive photosensitive resin composition according to the present invention is not only used for semiconductors, but also as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, interlayer insulation films for elements in display elements, etc. Is also useful. As other semiconductor device manufacturing methods, known methods can be used.

[Synthesis of polyamide resin]
A thermometer containing 17.1 g (0.055 mol) of 4,4′-oxydiphthalic anhydride, 12.4 g (0.167 mol) of 2-methyl-2-propanol and 10.9 g (0.138 mol) of pyridine Into a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 150 g of N-methyl-2-pyrrolidone was added and dissolved. 14.9 g (0.110 mol) of 1-hydroxy-1,2,3-benzotriazole was added dropwise to this reaction solution together with 30 g of N-methyl-2-pyrrolidone, and then 22.7 g (0.110 mol) of dicyclohexylcarbodiimide. Was added dropwise together with 50 g of N-methyl-2-pyrrolidone and allowed to react overnight at room temperature. Thereafter, 27.1 g of a dicarboxylic acid derivative (active ester) obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole with this reaction solution. (0.055 mol) and 44.8 g (0.122 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane with 70 g of N-methyl-2-pyrrolidone are added at room temperature. Stir for 2 hours. Thereafter, the reaction was terminated by stirring for 12 hours at 75 ° C. using an oil bath. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the general formula (1) And X is the following formula X-1, Y is the following formulas Y-1 and Y-2, and a polyamide resin (A-1) having a = 100 and b = 0 was synthesized.

[Preparation of resin composition]
10 g of synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone (B-1) having the following structure, 0.2 g of heterocyclic compound (C-1) containing two or more nitrogen atoms, and 70 g of γ-butyrolactone After dissolution, the mixture was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition.

[Developability evaluation]
This positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 10 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: remaining pattern and blank pattern with a width of 0.88 to 50 μm are drawn), Nikon Corporation i-line stepper NSR-4425i The exposure amount was increased by 200 mJ / cm ² to 10 mJ / cm ² steps. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 80 seconds, and then rinsed with pure water for 30 seconds. When the pattern was observed, it was confirmed that the pattern was well opened up to a pattern of 5 μm with an exposure amount of 530 mJ / cm ² .

[Adhesion evaluation]
This positive photosensitive resin composition was applied onto a 6-inch silicon wafer that had been plated with copper to a thickness of 5 μm after curing using a spin coater, and then dried at 120 ° C. for 4 minutes on a hot plate, Using a clean oven, heat curing was performed at an oxygen concentration of 1000 ppm or less at 150 ° C./30 minutes + 280 ° C./60 minutes. The coating film of the unexposed part which did not perform pattern opening of the obtained coating film was cut into 100 square grids at 1 mm square. Cellotape (registered trademark) was affixed and peeled off, but the number of peeled coatings (referred to as “the number of peeling after curing”) was 0, and the adhesion of the cured film to the metal was also It was confirmed that it was excellent.
[Adhesion evaluation 2]
The substrate in the physical property evaluation 1 was replaced with a 6-inch bare silicon wafer, and the same adhesion was evaluated. As a result, it was confirmed that the number of peeling of the coating film was zero.

[Synthesis of polyamide resin]
After dissolving 44.0 g (0.12 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in 200 g of N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone 50.6 g (0.24 mol) of trimellitic anhydride chloride dissolved in 160 g was added while cooling to 5 ° C. or lower. Further, 22.8 g (0.29 mol) of pyridine was added and stirred at 20 ° C. or lower for 3 hours. Next, after adding 44.0 '(diaminodiphenyl ether) 24.0g (0.12mol), it was made to react at room temperature for 5 hours. Next, the internal temperature was raised to 85 ° C. and stirred for 3 hours. After completion of the reaction, the filtered reaction mixture was poured into water / methanol = 5/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the general formula (1) A target polyamide resin (A-2) having a = 100 and b = 0 was synthesized in which X is a mixture of the following formulas X-1 and X-2 and Y is the following formula Y-3. .

[Production of resin composition, developability and evaluation of physical properties]
10 g of synthesized polyamide resin (A-2), 2 g of photosensitive diazoquinone (B-1) having the following structure, 0.05 g of heterocyclic compound (C-2) containing two or more nitrogen atoms, and 70 g of γ-butyrolactone After dissolution, the mixture was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that a pattern with an exposure amount of 550 mJ / cm ² and 4 μm was satisfactorily opened with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Example 1, and the number of peeled coatings was 0 for both the copper-plated product and the silicon wafer (hereinafter referred to as both substrates), and it was confirmed that the adhesion was excellent. It was done.

Using 10 g of the polyamide resin (A-1) of Example 1, 2 g of photosensitive diazoquinone (B-2) having the following structure, 0.2 g of a heterocyclic compound (C-3) containing two or more nitrogen atoms, After being dissolved in 70 g of γ-butyrolactone, it was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that a pattern with an exposure amount of 520 mJ / cm ² and 4 μm was satisfactorily opened in a development time of 80 seconds. The physical property evaluation was made in the same manner as in Example 1. The number of peeled coating films was 0 on both substrates, and it was confirmed that the adhesion was excellent.

Using 10 g of the polyamide resin (A-1) of Example 1, 2 g of photosensitive diazoquinone (B-2) having the following structure, 0.2 g of a heterocyclic compound (C-3) containing two or more nitrogen atoms, After dissolving in 1.5 g of the compound (D-1) having a phenolic hydroxyl group and 70 g of γ-butyrolactone, the solution was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. When the evaluation was performed in the same manner as in Example 1, it was confirmed that a pattern with an exposure amount of 380 mJ / cm ² and a size of 3 μm was satisfactorily opened in a development time of 80 seconds. The physical property evaluation was made in the same manner as in Example 1. The number of peeled coating films was 0 on both substrates, and it was confirmed that the adhesion was excellent.

Using 10 g of the polyamide resin (A-2) of Example 2, 2 g of photosensitive diazoquinone (B-2) having the following structure, 0.5 g of a heterocyclic compound (C-3) containing two or more nitrogen atoms, After dissolving in 1.5 g of the compound (D-2) having a phenolic hydroxyl group and 70 g of γ-butyrolactone, it was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that a pattern with an exposure amount of 340 mJ / cm ² and a size of ² μm was satisfactorily opened with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Example 1. The number of peeled coating films was 0 on both substrates, and it was confirmed that the adhesion was excellent.

[Preparation of display element and characteristics evaluation]
After forming an ITO film on the glass substrate by vapor deposition, the ITO film was divided into stripes by an ordinary photolithography method using a photoresist. On top of this, the positive photosensitive resin composition obtained in Example 1 was applied to form a resin layer having a thickness of about 2 μm. Next, using a parallel exposure machine (light source: high-pressure mercury lamp), exposure was performed through a glass mask for 10 seconds at an exposure intensity of 25 mW / cm 2. Thereafter, the resin layer was immersed and developed in a 2.38% tetramethylammonium hydroxide aqueous solution for 25 seconds to expose portions other than the ITO edge on each stripe, and the ITO edge portion and the ITO removed portion were exposed. Processing was performed so that the resin layer was formed only on the top. Thereafter, the entire resin layer was subjected to post-exposure for 40 seconds at an exposure intensity of 25 mW / cm ² using the parallel exposure machine used at the time of exposure, and then heated at 250 ° C. in air using a hot air circulation dryer. Time-hardening was performed.
After depositing copper phthalocyanine as a hole injection layer and bis-N-ethylcarbazole as a hole transport layer on this substrate under a reduced pressure of 1 × 10 ⁻⁴ Pa or less, N, N′-diphenyl was used as a light emitting layer. -N, N'-m-toluyl-4,4'-diamino-1,1'-biphenyl and tris (8-quinolinolate) aluminum were deposited in this order as an electron injection layer. Further, after an aluminum layer is deposited on the second electrode as a second electrode, the aluminum layer is formed into a stripe shape in a direction perpendicular to the stripe of the ITO film by a normal photolithography method using a photoresist. Divided. After the obtained substrate was dried under reduced pressure, the sealing glass plate was bonded using an epoxy adhesive to produce a display element. This display element was treated at 80 ° C. for 200 hours and then applied to both electrodes to drive sequentially. However, the element emitted light without any problem.

(Comparative Example 1)
10 g of the polyamide resin (A-1) of Example 1 was dissolved in 2 g of photosensitive diazoquinone (B-1) having the following structure and 70 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter. Thus, a positive photosensitive resin composition was obtained. When the evaluation was performed in the same manner as in Example 1, it was confirmed that the pattern had an exposure amount of 540 mJ / cm ² and an opening of 5 μm with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Example 1. The number of peeled coating films was 100 for the copper-plated product and 80 for the silicon wafer, and it was confirmed that the adhesion was inferior.

(Comparative Example 2)
10 g of the polyamide resin (A-1) of Example 1 was dissolved in 2 g of photosensitive diazoquinone (B-2) having the following structure and 70 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter. Thus, a positive photosensitive resin composition was obtained. Evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that the pattern had an exposure amount of 530 mJ / cm ² and an opening of 6 μm with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Example 1. The number of peeled coating films was 100 for the copper-plated product and 90 for the silicon wafer, and it was confirmed that the adhesion was inferior.

(Comparative Example 3)
0.2 g of a heterocyclic compound (C-4) containing only one nitrogen atom was added to the varnish of Comparative Example 2 to obtain a positive photosensitive resin composition. Evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that the pattern had an exposure amount of 560 mJ / cm ² and a pattern of 4 μm with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Example 1. The number of peeled coating films was 60 for the copper-plated product and 80 for the silicon wafer, and it was confirmed that the adhesion was inferior.

(Comparative Example 4)
To the varnish of Comparative Example 2, 0.2 g of the compound (C-5) containing two or more nitrogen atoms but not a heterocyclic compound was added to obtain a positive photosensitive resin composition. When the evaluation was performed in the same manner as in Example 1, it was confirmed that the pattern had an exposure amount of 570 mJ / cm ² and a pattern of 6 μm with a development time of 80 seconds. The physical property evaluation was made in the same manner as in Example 1, and the number of peeled coating films was 90 for the copper-plated product and 80 for the silicon wafer, confirming poor adhesion.

  The present invention relates to a polyamide resin for providing a polybenzoxazole resin or a polyimide resin excellent in adhesion to a metal or a copolymer resin thereof, and a positive photosensitive resin composition excellent in exposure characteristics using them. An object and a semiconductor device are provided.

Claims (15)

(A) an alkali-soluble resin,
(B) a photosensitive diazoquinone compound, and
(C) a heterocyclic compound containing two or more nitrogen atoms,
A positive photosensitive resin composition comprising:   The positive photosensitive resin composition according to claim 1, wherein the component (C) is a heterocyclic compound containing three or more nitrogen atoms.   The positive photosensitive resin composition according to claim 1, wherein component (C) is a triazole compound.   The positive photosensitive resin composition according to claim 1, wherein component (C) is 1,2,4-triazole.   The positive photosensitive resin composition according to claim 1, further comprising (D) a phenol compound. The positive photosensitive resin composition according to claim 1 or 2, wherein the phenol compound (D) is a phenol compound containing a structure represented by the general formula (1-1) or a structure represented by the general formula (1-2). .

6. (A) is 100 parts by weight, (B) is from 1 to 50 parts by weight, (C) is from 0.1 to 20 parts by weight, and the phenol compound (D) is contained from 1 to 30 parts by weight. Or the positive photosensitive resin composition of 6.   (A) The positive-type photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is a polyamide resin.   The positive photosensitive resin composition according to claim 8, wherein (A) the alkali-soluble resin is a polyamide resin containing a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure. The positive photosensitive resin composition according to claim 8 or 9, wherein (A) the alkali-soluble resin is a polyamide resin having a structure represented by the general formula (2).

The positive photosensitive resin composition according to claim 10, wherein X in the polyamide resin having a structure represented by the general formula (2) is selected from the group of the formula (3).

The positive photosensitive resin composition according to claim 10 or 11, wherein Y in the polyamide resin having a structure represented by the general formula (2) is selected from the group of the formula (4).

  The positive photosensitive resin composition according to any one of claims 10 to 12, wherein the polyamide resin containing the structure represented by the general formula (2) is end-capped with a compound containing an alkenyl group or an alkynyl group.   A semiconductor device produced using the positive photosensitive resin composition according to claim 1.   The display element produced using the positive photosensitive resin composition in any one of Claims 1 thru | or 13.