JP5205772B2 - Positive photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device and display device using the same - Google Patents

Description

  The present invention relates to a polyamide resin, a positive photosensitive resin composition, a cured film, a protective film, an insulating film, a semiconductor device using the same, and a display device.

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.
Here, in order to simplify the process when a polybenzoxazole resin or a polyimide resin is used, a positive photosensitive resin composition in which a diazoquinone compound of a photosensitive material is combined with these resins is also used (for example, patents). Reference 1). In recent years, since the semiconductor element has been reduced in size, increased in multi-layer wiring by higher integration, and shifted to a chip size package (CSP) or wafer level package (WLP), the damage to the chip is reduced. Benzoxazole resins and polyimide resins are required. When these positive photosensitive resins are used in an actual process, the problem is exposure characteristics, and the exposure time is particularly important among them. That is, in order to improve throughput, a positive photosensitive resin that is highly sensitive and can be exposed in a short time is desired. In addition, since a fine pattern needs to be formed with the miniaturization of a semiconductor, a positive photosensitive resin having high resolution is desired.
However, it has been difficult to satisfy high sensitivity and high resolution at the same time with conventional positive photosensitive resin compositions using polybenzoxazole resin or polyimide resin.

JP-A-1-46862

  The present invention has been made in view of the above circumstances, and its object is to provide a polyamide resin and a positive photosensitive resin that simultaneously satisfy high sensitivity and high resolution when applied to a positive photosensitive resin composition. It is to provide a composition. Another object is to provide a cured film, a protective film, an insulating film, a semiconductor device, and a display device.

（式中Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_０、Ｒ_１は有機基であり、同一でも異なっていてもよい。Ｐ、ｑは０〜３の整数である。）

（Ｒ_２は、有機基であり、ポリアミド樹脂のアミン末端に反応する官能基である。ｒは０〜７の整数であり、Ｒ_３は、水素原子、炭化水素基、または炭化水素基以外の極性基の中から選ばれたものであり、同一でも異なっていても良い。ｓおよびｔは、０〜３の整数である。）
［２］さらに、前記式（１）とは異なるジアミンと、カルボン酸誘導体とを、反応して得られる繰り返し単位を含む、［１］に記載のポリアミド樹脂。
［３］一般式（３）で示されるポリアミド樹脂であって、
前記ポリアミド樹脂のアミン末端の一部に、一般式（２）で示される化合物を反応させることにより、末端を封止してなることを特徴とするポリアミド樹脂。

（＊はＮＨ基に結合することを示す。式中、Ｙ_１は有機基であり、Ｒ_４は、水酸基、カルボキシル基、Ｏ−Ｒ_５、ＣＯＯ−Ｒ_５のいずれかであり、同一でも異なっていてもよい。ｎは０〜８の整数である。Ｒ_５は、炭素数１〜１５の有機基である。式中Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_０、Ｒ_１は有機基であり、同一でも異なっていてもよい。ｐ、ｑは０〜３の整数である。）

（Ｒ_２は、有機基であり、ポリアミド樹脂のアミン末端に反応する官能基である。ｒは０〜７の整数であり、Ｒ_３は、水素原子、炭化水素基、または炭化水素基以外の極性基の中から選ばれたものであり、同一でも異なっていても良い。ｓおよびｔは、０〜３の整数である。）
［４］一般式（４）で示されるポリアミド樹脂であって、
前記ポリアミド樹脂のアミン末端の一部に、一般式（２）で示される化合物を反応させる
ことにより、末端を封止してなることを特徴とするポリアミド樹脂。

（式中Ｙ_２は有機基であり、Ｚは、Ｘと異なる有機基である。ａ、ｂはモルパーセントを示し、ａ＋ｂ＝１００で、ａが６０以上１００以下、ｂが０以上４０以下である。Ｒ_６は、水酸基、Ｏ−Ｒ_８のいずれかであり、同一でも異なっていてもよい。Ｒ_８は、炭素数１〜１５の有機基である。Ｒ_４及びＲ_７は、水酸基、カルボキシル基、Ｏ−Ｒ_５、ＣＯＯ−Ｒ_５のいずれかであり、同一でも異なっていてもよい。ｌ、ｍ、ｎは０〜８の整数である。式中Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_０、Ｒ_１は有機基であり、同一でも異なっていてもよい。ｐ、ｑは０〜３の整数である。）

（Ｒ_２は、有機基であり、ポリアミド樹脂のアミン末端に反応する官能基である。ｒは０〜７の整数であり、Ｒ_３は、水素原子、炭化水素基、または炭化水素基以外の極性基の中から選ばれたものであり、同一でも異なっていても良い。ｓおよびｔは、０〜３の整数である。）
［５］一般式（２）で示される化合物による前記ポリアミド樹脂のアミン末端封止率が、５０〜１００％である［１］ないし［４］のいずれかに記載のポリアミド樹脂。
［６］一般式（２）で示される化合物において、ｓ＝０、ｔ＝０である［１］ないし［５］に記載のポリアミド樹脂。
［７］一般式（２）のＲ_２が、水酸基、ハロゲン、またはベンゾトリアゾル基からなる群から選択されるものである［１］ないし［６］に記載のポリアミド樹脂。
［８］［１］ないし［７］のいずれかに記載のポリアミド樹脂（Ａ）と、感光性ジアゾキノン化合物（Ｂ）とを含むことを特徴とするポジ型感光性樹脂組成物。
［９］さらに、フェノール性水酸基を有する化合物（Ｃ）を含んでなるものである、［８］に記載のポジ型感光性樹脂組成物。
［１０］前記フェノール性水酸基を有する化合物（Ｃ）が、下記式（５）の群より選ばれてなる［９］に記載のポジ型感光性樹脂組成物。

［１１］［８］ないし［１０］のいずれかに記載のポジ型感光性樹脂組成物の硬化物で構成されていることを特徴とする硬化膜。
［１２］［１１］に記載の硬化膜で構成されていることを特徴とする保護膜。
［１３］［１１］に記載の硬化膜で構成されていることを特徴とする絶縁膜
［１４］［１１］に記載の硬化膜を有することを特徴とする半導体装置。
［１５］［１１］に記載の硬化膜を有することを特徴とする表示体装置。 [1] A polyamide resin having a repeating unit obtained by reacting at least one bisaminophenol represented by the following general formula (1) with a carboxylic acid derivative,
A polyamide resin characterized in that the polyamide resin is end-capped by reacting a part of the amine terminal of the polyamide resin with a compound represented by the following formula (2).

(In the formula, A is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —C (CF ₃ ) ₂ —, or a single bond. R ₀ and R ₁ are organic groups; (It may be the same or different. P and q are integers of 0 to 3.)

(R ₂ is an organic group and is a functional group that reacts with the amine terminal of the polyamide resin. R is an integer of 0 to 7, and R ₃ is other than a hydrogen atom, a hydrocarbon group, or a hydrocarbon group. (It is selected from polar groups and may be the same or different. S and t are integers of 0 to 3.)
[2] The polyamide resin according to [1], further comprising a repeating unit obtained by reacting a diamine different from the formula (1) with a carboxylic acid derivative.
[3] A polyamide resin represented by the general formula (3),
A polyamide resin obtained by sealing a terminal by reacting a compound represented by the general formula (2) with a part of the amine terminal of the polyamide resin.

(* Indicates bonding to an NH group. In the formula, Y ₁ is an organic group, R ₄ is any one of a hydroxyl group, a carboxyl group, O—R ₅ , and COO—R ₅ , which are the same or different. N is an integer of 0 to 8. R ₅ is an organic group having 1 to 15 carbon atoms, wherein A represents —CH ₂ —, —C (CH ₃ ) ₂ —, —. O—, —C (CF ₃ ) ₂ —, or a single bond, R ₀ and R ₁ are organic groups, which may be the same or different, and p and q are integers of 0 to _3. )

(R ₂ is an organic group and is a functional group that reacts with the amine terminal of the polyamide resin. R is an integer of 0 to 7, and R ₃ is other than a hydrogen atom, a hydrocarbon group, or a hydrocarbon group. (It is selected from polar groups and may be the same or different. S and t are integers of 0 to 3.)
[4] A polyamide resin represented by the general formula (4),
A polyamide resin obtained by sealing a terminal by reacting a compound represented by the general formula (2) with a part of the amine terminal of the polyamide resin.

(In the formula, Y ₂ is an organic group, and Z is an organic group different from X. a and b represent mole percent, a + b = 100, a is 60 or more and 100 or less, and b is 0 or more and 40 or less. R ₆ is either a hydroxyl group or O—R ₈ , which may be the same or different, R ₈ is an organic group having 1 to 15 carbon atoms, R ₄ and R ₇ are a hydroxyl group, A carboxyl group, O—R ₅ , or COO—R ₅ , which may be the same or different, and l, m, and n are integers of 0 to 8. In the formula, A is —CH ₂ —, And —C (CH ₃ ) ₂ —, —O—, —C (CF ₃ ) ₂ —, or a single bond, R ₀ and R ₁ are organic groups, which may be the same or different, p, q Is an integer from 0 to 3.)

(R ₂ is an organic group and is a functional group that reacts with the amine terminal of the polyamide resin. R is an integer of 0 to 7, and R ₃ is other than a hydrogen atom, a hydrocarbon group, or a hydrocarbon group. (It is selected from polar groups and may be the same or different. S and t are integers of 0 to 3.)
[5] The polyamide resin according to any one of [1] to [4], wherein the amine terminal blocking ratio of the polyamide resin by the compound represented by the general formula (2) is 50 to 100%.
[6] The polyamide resin according to [1] to [5], in which s = 0 and t = 0 in the compound represented by the general formula (2).
[7] The polyamide resin according to [1] to [6], wherein R _{2 in the} general formula (2) is selected from the group consisting of a hydroxyl group, a halogen, or a benzotriazole group.
[8] A positive photosensitive resin composition comprising the polyamide resin (A) according to any one of [1] to [7] and a photosensitive diazoquinone compound (B).
[9] The positive photosensitive resin composition according to [8], further comprising a compound (C) having a phenolic hydroxyl group.
[10] The positive photosensitive resin composition according to [9], wherein the compound (C) having a phenolic hydroxyl group is selected from the group of the following formula (5).

[11] A cured film comprising a cured product of the positive photosensitive resin composition according to any one of [8] to [10].
[12] A protective film comprising the cured film according to [11].
[13] A semiconductor device comprising the cured film according to [11], comprising the cured film according to [11].
[15] A display device having the cured film according to [11].

  ADVANTAGE OF THE INVENTION According to this invention, when applied to a positive photosensitive resin composition, the polyamide resin and positive photosensitive resin composition which satisfy | fill simultaneously high sensitivity and high resolution are provided. Further, a cured film, a protective film, an insulating film, a semiconductor device, and a display device are provided.

（式中Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_０、Ｒ_１は有機基であり、同一でも異なっていてもよい。ｐ、ｑは０〜３の整数である。）

（Ｒ_２は、有機基であり、ポリアミド樹脂のアミン末端に反応する官能基である。ｒは０
〜７の整数であり、Ｒ_３は、水素原子、炭化水素基、または炭化水素基以外の極性基の中から選ばれたものであり、同一でも異なっていても良い。ｓおよびｔは、０〜３の整数である。） The polyamide resin of the present invention is a polyamide resin having a repeating unit obtained by reacting at least one bisaminophenol represented by the following formula (1) with a carboxylic acid derivative, the amine of the polyamide resin The terminal is blocked by reacting a compound represented by the following formula (2) with a part of the terminal.

(In the formula, A is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —C (CF ₃ ) ₂ —, or a single bond. R ₀ and R ₁ are organic groups; (It may be the same or different. P and q are integers of 0 to 3.)

(R ₂ is an organic group and a functional group that reacts with the amine terminal of the polyamide resin. R is 0.
Is an integer of ˜7, and R ₃ is selected from a hydrogen atom, a hydrocarbon group, or a polar group other than a hydrocarbon group, and may be the same or different. s and t are integers of 0-3. )

  The positive photosensitive resin composition of the present invention comprises a polyamide resin (A), a photosensitive diazoquinone compound (B), and a compound (C) having a phenolic hydroxyl group. The protective film and insulating film of the present invention are characterized by being composed of a cured film of the positive photosensitive resin composition. Furthermore, the semiconductor device and display device of the present invention are characterized by having a cured film.

  Hereinafter, the polyamide resin, photosensitive resin composition, insulating film, protective film, semiconductor device, and display device of the present invention will be described.

（式中Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_０、Ｒ_１は有機基であり、同一でも異なっていてもよい。ｐ、ｑは０〜３の整数である。）

（Ｒ_２は、有機基であり、ポリアミド樹脂のアミン末端に反応する官能基である。ｒは０〜７の整数であり、Ｒ_３は、水素原子、炭化水素基、または炭化水素基以外の極性基の中から選ばれたものであり、同一でも異なっていても良い。ｓおよびｔは、０〜３の整数である。） The polyamide resin of the present invention contains a specific bisaminophenol represented by the following general formula (1), and by sealing the amine terminal of the polyamide resin with a specific compound represented by the general formula (2), When a polyamide resin is applied to a positive photosensitive resin composition, both high resolution and high sensitivity can be achieved.

(In the formula, A is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —C (CF ₃ ) ₂ —, or a single bond. R ₀ and R ₁ are organic groups; (It may be the same or different. P and q are integers of 0 to 3.)

(R ₂ is an organic group and is a functional group that reacts with the amine terminal of the polyamide resin. R is an integer of 0 to 7, and R ₃ is other than a hydrogen atom, a hydrocarbon group, or a hydrocarbon group. (It is selected from polar groups and may be the same or different. S and t are integers of 0 to 3.)

  The polyamide resin of the present invention has a repeating unit obtained by reacting at least one bisaminophenol represented by the general formula (1) and a carboxylic acid derivative, and has one amine terminal of the polyamide resin. The part is not particularly limited as long as it is end-capped by reacting the compound represented by the general formula (2).

The polyamide resin of the present invention is obtained by reacting at least one bisaminophenol represented by the general formula (1) with a carboxylic acid derivative such as dicarboxylic acid or dicarboxylic acid chloride. At this time, when dicarboxylic acid is used, an active ester type carboxylic 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. .

  When the polyamide resin of the present invention is heated at about 200 to 400 ° C., it undergoes dehydration and ring closure, and a heat-resistant resin in the form of polyimide resin, polybenzoxazole resin, or copolymerization of polybenzoxazole resin and polyimide resin is obtained.

（＊はＮＨ基に結合することを示す。式中、Ｙ_１は有機基であり、Ｒ_４は、水酸基、カルボキシル基、Ｏ−Ｒ_５、ＣＯＯ−Ｒ_５のいずれかであり、同一でも異なっていてもよい。ｎは０〜８の整数である。Ｒ_５は、炭素数１〜１５の有機基である。式中Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_０、Ｒ_１は有機基であり、同一でも異なっていてもよい。ｐ、ｑは０〜３の整数である。） As one embodiment of the polyamide resin, the polyamide resin is represented by the general formula (3).

(* Indicates bonding to an NH group. In the formula, Y ₁ is an organic group, R ₄ is any one of a hydroxyl group, a carboxyl group, O—R ₅ , and COO—R ₅ , which are the same or different. N is an integer of 0 to 8. R ₅ is an organic group having 1 to 15 carbon atoms, wherein A represents —CH ₂ —, —C (CH ₃ ) ₂ —, —. O—, —C (CF ₃ ) ₂ —, or a single bond, R ₀ and R ₁ are organic groups, which may be the same or different, and p and q are integers of 0 to _3. )

In the polyamide resin represented by the general formula (3), Y ₁ substituents, O—R ₅ and COO—R ₅ have a hydroxyl group and a carboxyl group of 1 to 15 carbon atoms for the purpose of adjusting solubility in an alkaline aqueous solution. It is a group protected by R ₅ which is an organic group. Examples of R ₅ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.

The substituents R ₀ and R ₁ of X in the polyamide resin represented by the general formula (3) of the present invention are not particularly limited, and examples thereof include a hydrocarbon group or a polar group other than a hydrocarbon group. Among these, a hydrocarbon group is preferable from the viewpoint of improving film characteristics.

A in X of the polyamide resin represented by the general formula (3) of the present invention is —CH ₂ from the viewpoints of solubility in a developer, sensitivity, resolution, cyclability at low temperature curing, and water absorption after curing. -, - O -, - C (CF 3) 2 - are preferred, sensitivity, -C terms of resolution _{(CF 3) 2} are particularly preferred.

（ここで＊はＣ＝Ｏ基に結合することを示す。Ｒ_１１〜Ｒ_１４は有機基である。） Y ₁ of the polyamide resin represented by the general formula (3) of the present invention is an organic group and is not particularly limited. For example, aromatic compounds such as benzene ring and naphthalene ring, bisphenols, pyrroles, pyridine And heterocyclic compounds such as furans, and more specifically, those represented by the following formula (6) can be preferably mentioned. These may be used alone or in combination of two or more.

(Here, * indicates bonding to a C═O group. R _{11 to} R ₁₄ are organic groups.)

As shown in the general formula (3), 0 to 8 R ₄ are bonded to Y ₁ . (In formula (6), R ₄ is omitted)

Among these, those represented by the following formulas (7) and (8) are particularly preferred from the viewpoints of solubility in a developer, dielectric properties after curing, heat resistance, electrical properties, mechanical properties, and the like. Regarding the structure derived from tetracarboxylic dianhydride in the following formula (7), the position where both C═O groups are bonded to the meta position, and both the para positions are listed. A structure including each of the para positions may be used.

（式中、＊はＣ＝Ｏ基に結合することを示す。Ｒ_１５は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。Ｒ_１６は、水素原子又は炭素数１〜１５の有機基から選ばれた１つを示し、一部が置換されていてもよい。ｖ＝０〜２の整数である。）

(In the formula, * indicates bonding to a C═O group. R ₁₅ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, R ₁₆ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted, and is an integer of v = 0 to 2. is there.)

（式中、＊はＣ＝Ｏ基に結合することを示す。）

(In the formula, * indicates binding to a C═O group.)

  The polyamide resin of the present invention includes, in addition to the repeating unit obtained by reacting at least one bisaminophenol selected from the group represented by the formula (1) with a carboxylic acid derivative, the formula (1) and May have a repeating unit obtained by reacting a different diamine with a carboxylic acid derivative.

（式中Ｙ_２は有機基であり、Ｚは、Ｘと異なる有機基である。ａ、ｂはモルパーセントを示し、ａ＋ｂ＝１００で、ａが６０以上１００以下、ｂが０以上４０以下である。Ｒ_６は、水酸基、Ｏ−Ｒ_８のいずれかであり、同一でも異なっていてもよい。Ｒ_８は、炭素数１〜１５の有機基である。Ｒ_４及びＲ_７は、水酸基、カルボキシル基、Ｏ−Ｒ_５、ＣＯＯ−Ｒ_５のいずれかであり、同一でも異なっていてもよい。ｌ、ｍ、ｎは０〜８の整数である。式中Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_０、Ｒ_１は有機基であり、同一でも異なっていてもよい。ｐ、ｑは０〜３の整数である。） In addition to the repeating unit obtained by reacting at least one bisaminophenol selected from the group represented by the formula (1) with a carboxylic acid derivative, a diamine different from the general formula (1), As one embodiment of a polyamide resin having a repeating unit obtained by reacting an acid derivative, the polyamide resin is represented by the following general formula (4).

(In the formula, Y ₂ is an organic group, and Z is an organic group different from X. a and b represent mole percent, a + b = 100, a is 60 or more and 100 or less, and b is 0 or more and 40 or less. R ₆ is either a hydroxyl group or O—R ₈ , which may be the same or different, R ₈ is an organic group having 1 to 15 carbon atoms, R ₄ and R ₇ are a hydroxyl group, A carboxyl group, O—R ₅ , or COO—R ₅ , which may be the same or different, and l, m, and n are integers of 0 to 8. In the formula, A is —CH ₂ —, And —C (CH ₃ ) ₂ —, —O—, —C (CF ₃ ) ₂ —, or a single bond, R ₀ and R ₁ are organic groups, which may be the same or different, p, q Is an integer from 0 to 3.)

In the polyamide resin represented by the general formula (4), Y ₂ substituents O—R ₅ and COO—R ₅ are organic groups having 1 to 15 carbon atoms for the purpose of adjusting solubility in an alkaline aqueous solution. And R ₅ protected group. Examples of R ₅ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.

  In the polyamide resin represented by the general formula (4) of the present invention, a and b represent mole percent, a + b = 100, a is 60 or more and 100 or less, and b is 0 or more and 40 or less. From the viewpoint of the sensitivity and resolution of the conductive resin composition, a is particularly preferably from 70 to 100 and b is from 0 to 30.

（ここで＊はＮＨ基に結合することを示す。式中Ｄは、−Ｓ−、−ＣＯ−、−ＮＨＣＯ−である。Ｒ_１７はアルキル基、アルキルエステル基、ハロゲン原子のうちから選ばれた少なくとも１つを表し、それぞれ同じでも異なっていても良い。また、Ｒ_１８は水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを表す。ｔは０〜２の整数である。）
（ここで＊はＮＨ基に結合することを示す。Ｒ_１９〜Ｒ_２２は有機基である。） Z in the polyamide resin represented by the formula (4) is an organic group, and examples thereof include aromatic compounds such as benzene ring and naphthalene ring, heterocyclic compounds such as bisphenols, pyrroles and furans, and siloxane compounds. More specifically, preferred are those represented by the following formula (9). These may be used singly or in combination of two or more if necessary so as not to affect the high cyclization property when cured at low temperature.

(Here, * indicates bonding to an NH group. In the formula, D is -S-, -CO-, or -NHCO-. R ₁₇ is selected from an alkyl group, an alkyl ester group, and a halogen atom.) R ₁₈ may be the same or different, and R ₁₈ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, and t is an integer of 0 to 2. is there.)
(Here, * indicates bonding to an NH group. R _{19 to} R ₂₂ are organic groups.)

Among these, those represented by the following formula (10) are preferable from the viewpoints of solubility in a developing solution, adhesion to an adherend, dielectric properties after curing, heat resistance, electrical properties, mechanical properties, and the like.

（ここで＊はＣ＝Ｏ基に結合することを示す。Ｒ_２５〜Ｒ_２８は有機基である。） Y ₂ of the polyamide resin represented by the general formula (4) of the present invention is an organic group and is not particularly limited. For example, aromatic compounds such as benzene ring and naphthalene ring, bisphenols, pyrroles, pyridine And heterocyclic compounds such as furans, and more specifically, those represented by the following formula (11) can be preferably mentioned. These may be used alone or in combination of two or more.

(Here, * indicates bonding to a C═O group. R _{25 to} R ₂₈ are organic groups.)

As shown in the general formula (4), 0 to 8 R ₇ are bonded to Y ₂ . (In formula (11), R ₇ is omitted)

Among these, those represented by the following formulas (12) and (13) are particularly preferable from the viewpoints of solubility in a developer, dielectric properties after curing, heat resistance, electrical properties, mechanical properties, and the like. Regarding the structure derived from tetracarboxylic dianhydride in the following formula (12), the position where both C═O groups are bonded to the meta position, and both the positions in the para position are listed. A structure including each of the para positions may be used.

（式中、＊はＣ＝Ｏ基に結合することを示す。Ｒ_２９は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。Ｒ_３０は、水素原子又は炭素数１〜１５の有機基から選ばれた１つを示し、一部が置換されていてもよい。ｙ＝０〜２の整数である。）

(In the formula, * represents bonding to a C═O group. R ₂₉ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, R ₃₀ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted, and an integer of y = 0 to 2. is there.)

（式中、＊はＣ＝Ｏ基に結合することを示す。）

(In the formula, * indicates binding to a C═O group.)

（Ｒ_２は、有機基であり、ポリアミド樹脂のアミン末端に反応する官能基である。ｒは０〜７の整数であり、Ｒ_３は、水素原子、炭化水素基、または炭化水素基以外の極性基の中から選ばれたものであり、同一でも異なっていても良い。ｓおよびｔは、０〜３の整数である。） The compound represented by the general formula (2) used for sealing the amine terminal of the polyamide resin used in the present invention may be used alone or in combination of two or more. The compound represented by the general formula (2) used for sealing the amine terminal of the polyamide resin imparts a thermopolymerizable functional group to the terminal of the polyamide resin, and the positive photosensitive resin composition described later. It is used for crosslinking with polyamide resins or other components in the curing step, and has an advantage that mechanical properties such as heat resistance of the cured film are improved. Moreover, since the water-soluble functional group is not generated when the amine terminal of the polyamide resin is sealed with the compound represented by the general formula (2) as in the present invention, the development process of the positive photosensitive resin composition described later However, the difference in solubility in the developing solution between the exposed portion and the unexposed portion becomes large, so that it has an advantage of high resolution.

(R ₂ is an organic group and is a functional group that reacts with the amine terminal of the polyamide resin. R is an integer of 0 to 7, and R ₃ is other than a hydrogen atom, a hydrocarbon group, or a hydrocarbon group. (It is selected from polar groups and may be the same or different. S and t are integers of 0 to 3.)

  The amine terminal blocking ratio of the polyamide resin of the compound represented by the general formula (2) used for sealing the amine terminal of the polyamide resin used in the present invention is preferably 50 to 100%, and 70 to 100%. Is particularly preferred. By setting the amine terminal blocking rate of the polyamide resin within the above range, water-soluble functional groups are reduced at the end of the polyamide resin, and the dissolution rate of the polyamide resin in the developer can be lowered. As well as improved mechanical properties after curing.

  S and t of the compound represented by the general formula (2) used for sealing the amine terminal of the polyamide resin used in the present invention are selected from integers of 0 to 3, among which s = 0 and t = 0 are preferable from the viewpoint of dissolution rate.

R ₁ of the compound represented by the general formula (2) used for sealing the amine terminal of the polyamide resin used in the present invention is particularly limited as long as it reacts with the amine terminal of the polyamide resin terminal. Although it is not a thing, from a reactive viewpoint with the amine terminal of a polyamide resin, it is preferable that they are a hydroxyl group, a halogen, and a benzotriazole group, and the benzotriazole group which is excellent in the reactivity with an amine terminal is especially preferable.

R ₃ of the compound represented by the general formula (2) used for sealing the amine terminal of the polyamide resin used in the present invention is selected from polar groups other than hydrogen atoms, hydrocarbon groups, and hydrocarbon groups However, from the viewpoint of mechanical properties and resolution, a hydrogen atom or a hydrocarbon group having a low polarity and good terminal crosslinkability is preferable, and a hydrogen atom is particularly preferable.

  Further, the end of the polyamide resin may be sealed with an acid anhydride or an acid derivative further containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. Thereby, the mechanical properties of the cured film can be further improved. 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, for example, formula (14), The group etc. which have an alkynyl group shown by (15) can be mentioned. These may be used alone or in combination of two or more.

Of these, a group represented by the following formula (16) is particularly preferable. Thereby, especially storability can be improved.

The positive photosensitive resin composition of the present invention contains a photosensitive agent. Thereby, a chemical reaction is caused by irradiation with actinic radiation, and the actinic radiation irradiated portion (hereinafter referred to as an exposed portion) is easily dissolved in an alkaline aqueous solution, and is referred to as an actinic radiation unexposed portion (hereinafter referred to as an unexposed portion). ) And a difference in solubility.
Examples of the photosensitive agent include esters of a phenol compound and 1,2-naphthoquinone-2-diazido-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Specific examples include ester compounds represented by formula (17) to formula (22). Two or more of these may be used. In the formulas (17) to (22), Q represents a hydrogen atom, a 1,2-naphthoquinone-2-diazide-5-sulfonyl group, or a 1,2-naphthoquinone-2-diazide-4-sulfonyl group.

式中Ｑは、水素原子、式（２１）、式（２２）のいずれかから選ばれるものである。ここで各化合物のＱのうち、少なくとも１つは式（２１）、式（２２）である。

In the formula, Q is selected from a hydrogen atom, formula (21), and formula (22). Here, at least one of Q of each compound is represented by formula (21) or formula (22).

  The addition amount of the photosensitive diazoquinone compound (B) used in the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin (A). More preferably, it is 10 to 40 parts by weight. When the addition amount is within the above range, the sensitivity is particularly excellent.

  Furthermore, in this invention, the compound which has a phenolic hydroxyl group can be used together so that it can pattern without high scum and high sensitivity.

  Specific examples of the structure include those represented by the following formula (5). These may be used alone or in combination of two or more.

  Although content of the compound which has the said phenolic hydroxyl group is not specifically limited, 1-30 weight part is preferable with respect to 100 weight part of said polyamide resins, More preferably, it is 1-20 weight part. When the addition amount is in the above range, the occurrence of scum is further suppressed during development, and the sensitivity is improved by promoting the solubility of the exposed area.

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

  The positive photosensitive resin composition of the present invention is preferably dissolved in a solvent and used in the form of a varnish. Examples of the solvent 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-methoxypro Pionate etc. are mentioned, You may use individually or in mixture.

Next, a method for producing a cured film will be described.
The cured film of this invention can be obtained through the following processes, for example.
The positive photosensitive composition described above is applied to a support (for example, a silicon wafer, a ceramic substrate, an aluminum substrate, etc.) (application step). When applied on the semiconductor element, the applied amount is applied so that the thickness of the cured film is, for example, 0.1 to 30 μm. If the thickness of the film is less than the lower limit, it may be difficult to fully function as a protective (surface) film of a semiconductor element. If the upper limit is exceeded, a fine processing pattern may be obtained. It can be difficult. 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, for example, after pre-baking at 60 to 130 ° C. to dry the coating film, actinic radiation is irradiated to a desired pattern shape (exposure process). As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used, but those having a wavelength of, for example, 200 to 500 nm are preferable.

Next, a relief pattern is prepared (development process) by dissolving and removing the exposed portion with a developer. The development mechanism of the positive photosensitive resin composition is as follows.
In the unexposed area, the diazoquinone compound acts with the polyamide resin, exhibits a dissolution inhibiting effect, and becomes hardly soluble in the alkaline aqueous solution. On the other hand, in the exposed area, the diazoquinone compound undergoes a chemical change and becomes soluble in an alkaline aqueous solution. By utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, it is possible to produce a coating film pattern of only the unexposed portion.
Examples of the developer used in the development step include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and first amines such as ethylamine and n-propylamine. Secondary amines such as amines, diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide; tetraethylammonium An aqueous solution of an alkali such as a quaternary ammonium salt such as hydroxide and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to this can be preferably used. As a developing method, for example, a spray, paddle, immersion, ultrasonic method, or the like is possible.

  Next, the relief pattern formed by development is rinsed (cleaned) (rinsing step). As the rinsing liquid, for example, distilled water can be used.

Next, heat treatment is performed to form a closed ring structure (for example, an oxazole ring, an imide ring, etc.) to obtain a patterned cured film rich in heat resistance (heating step).
Although heat processing temperature is not specifically limited, 150-380 degreeC is preferable and 280-380 degreeC is especially preferable.

  Next, the use of the cured film of the positive photosensitive resin composition according to the present invention will be described. The cured film, which is a cured product of the positive photosensitive resin composition, is used not only for semiconductor devices such as semiconductor elements, but also for display devices such as TFT liquid crystal and organic EL, interlayer insulating films for multilayer circuits, and flexible copper-clad It is also useful as a plate cover coat, solder resist film or liquid crystal alignment film.

  Examples of semiconductor device applications include a passivation film formed by forming a cured film of the above-described positive photosensitive resin composition on a semiconductor element, and a cured film of the above-described positive photosensitive resin composition formed on the passivation film. A protective film such as a buffer coating film, an insulating film such as an interlayer insulating film formed by forming a cured film of the above-mentioned positive photosensitive resin composition on a circuit formed on a semiconductor element, Examples include an α-ray blocking film, a planarizing film, a protrusion (resin post), and a partition wall.

  Examples of display device applications include a protective film formed by forming a cured film of the above-described positive photosensitive resin composition on a display element, an insulating film or a planarizing film for TFT elements and color filters, MVA, and the like. Protrusions for a liquid crystal display device, partition walls for an organic EL element cathode, and the like. The use method is based on forming a cured film of the positive photosensitive resin composition patterned on the substrate on which the display element and the color filter are formed according to the semiconductor device application by the above method. . High transparency is required for display device applications, especially for insulating films and flattening films. Transparency can be achieved by introducing a post-exposure step before curing the positive photosensitive resin composition layer. It is also possible to obtain a resin layer that is excellent in practical use, which is more preferable in practical use.

Hereinafter, the present invention will be described specifically by way of examples.
Example 1
[Synthesis of polyamide resin]
Dicarboxylic acid obtained by reacting 4.13 g (0.016 mol) of diphenyl ether-4,4′-dicarboxylic acid with 4.32 g (0.032 mol) of 1-hydroxy-1,2,3-benzotriazole Mixture of derivatives (0.016 mol) and 7.33 g (0.020 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were thermometer, stirrer, raw material inlet, and drying. Into a four-necked separable flask equipped with a nitrogen gas inlet tube, 57.0 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 2.04 g (0.008 mol) of a carboxylic acid derivative obtained by reacting 5-norbornene-2carboxylic acid with 1-hydroxy-1,2,3-benzotriazole was added, and the mixture was further stirred for 12 hours. The reaction was terminated. 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, dried under vacuum, and the desired polyamide resin ( A-1) was obtained.

[Synthesis of photosensitizer]
51 parts by weight (0.12 mol) of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and 1,2-naphthoquinonediazide-4- 72.5 parts by weight (0.27 mol) of sulfonic acid chloride is dissolved in 450 ml of tetrahydrofuran, and 28.3 parts by weight (0.28 mol) of triethylamine is added dropwise. After reacting at room temperature for 20 hours, the precipitated hydrochloride of triethylamine was removed by filtration and poured into 10 L of ion-exchanged water to obtain a precipitate. The precipitate was agglomerated and vacuum dried at room temperature for 48 hours. This is designated as photosensitive agent (B-1).

[Preparation of positive photosensitive resin resin composition]
10 g of the synthesized polyamide resin (A-1) and 2 g of the synthesized photosensitizer (B-1) are dissolved in 70 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Got.

<< Example 2 >>
In the synthesis of the polyamide resin of Example 1, the amount of carboxylic acid derivative obtained by reacting 5-norbornene-2carboxylic acid with 1-hydroxy-1,2,3-benzotriazole was 1.53 g (0. (006 mol) to synthesize a polyamide resin (A-2). A positive photosensitive resin composition was prepared in the same manner as in Example 1 except for the synthesis of the polyamide resin.

Example 3
In the synthesis of the polyamide resin of Example 1, the amount of carboxylic acid derivative obtained by reacting 5-norbornene-2carboxylic acid with 1-hydroxy-1,2,3-benzotriazole was 1.22 g (0. The polyamide resin was synthesized (A-3). A positive photosensitive resin composition was prepared in the same manner as in Example 1 except for the synthesis of the polyamide resin.

Example 4
In the synthesis of the polyamide resin of Example 1, 4.13 g (0.016 mol) of diphenyl ether-4,4′-dicarboxylic acid was changed to 2.66 g (0.016 mol) of isophthalic acid to synthesize a polyamide resin (A -4). A positive photosensitive resin composition was prepared in the same manner as in Example 1 except for the synthesis of the polyamide resin.

Example 5
In the synthesis of the polyamide resin of Example 1, 7.33 g (0.020 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was converted to 2,2-bis (3-amino-4). Polyamide resin was synthesized by changing to 5.17 g (0.020 mol) of -hydroxyphenyl) propane (A-5). A positive photosensitive resin composition was prepared in the same manner as in Example 1 except for the synthesis of the polyamide resin.

Example 6
In the synthesis of the polyamide resin of Example 1, 7.33 g (0.020 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was converted to 4,4-methylenebis (2-amino-3). , 6-dimethylphenol) was changed to 5.73 g (0.020 mol) to synthesize a polyamide resin (A-6). A positive photosensitive resin composition was prepared in the same manner as in Example 1 except for the synthesis of the polyamide resin.

≪Comparative example 1≫
In the synthesis of the polyamide resin of Example 1, a polyamide resin was synthesized without adding a carboxylic acid derivative obtained by reacting 5-norbornene-2carboxylic acid with 1-hydroxy-1,2,3-benzotriazole. (A-7). A positive photosensitive resin composition was prepared in the same manner as in Example 1 except for the synthesis of the polyamide resin.

The following evaluation was performed about the positive photosensitive resin composition and cured film which were obtained by each Example and the comparative example. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.
1. Developability The positive photosensitive resin composition obtained in each Example and Comparative Example was coated on a silicon wafer using a spin coater, and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a film thickness of about 10 μm. Coating film was obtained. 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 Use the exposure dose from 100mJ / cm2 to 1
The exposure was increased by 0 mJ / cm 2 step. Next, the exposed area was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 100 seconds, rinsed with pure water for 30 seconds, then the pattern was observed, and a line at an exposure amount of 300 mJ / cm 2 was obtained. Among these continuous patterns, the minimum width of a line that was well opened was confirmed.
As a result, in Comparative Example 1, the minimum width of a well-opened line in a continuous pattern of lines at an exposure amount of 300 mJ / cm 2 is 8 μm, whereas in Examples 1 to 6, the minimum line width is 5 μm. The following good results were obtained.

2. Film characteristics (water absorption)
The positive photosensitive resin compositions obtained in each Example and Comparative Example were applied on a 6-inch silicon wafer using a spin coater so as to have a thickness of 5 μm after curing, and then heated at 120 ° C. for 4 minutes on a hot plate. Dried, then using a clean oven, oxygen concentration 1000ppm or less,
Curing was performed at 150 ° C./30 minutes + 320 ° C./30 minutes. Next, the obtained cured film was immersed in 3% hydrogen fluoride water, and the film was peeled off from the silicon wafer. The obtained film was sufficiently washed with pure water and then dried in an oven over 60 ° C./5 hours. After the obtained film was dried at 50 ° C. for 24 hours, the water absorption was measured by a method of immersing the dried film in pure water maintained at 23 ° C. (conforming to JIS-K7209).

Claims (12)

A polyamide resin (A) and a photosensitive diazoquinone compound (B), wherein the polyamide resin reacts with at least one bisaminophenol represented by the following general formula (1) and a carboxylic acid derivative. The end unit is blocked by reacting a carboxylic acid derivative obtained by reacting 5-norbornene-2carboxylic acid with 1-hydroxy1,2,3-benzotriazole at the amine end. And a positive-type photosensitive resin composition having a terminal sealing ratio of 50% to 100%.

(In the formula, A is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —C (CF ₃ ) ₂ —, or a single bond. R ₀ and R ₁ are organic groups; (It may be the same or different. P and q are integers of 0 to 3.)   The positive photosensitive resin composition according to claim 1, wherein the terminal blocking rate is 60% or more and 100% or less.   The positive photosensitive resin composition of Claim 1 or 2 in which the said polyamide resin contains the repeating unit obtained by reacting the diamine different from Formula (1), and a carboxylic acid derivative. The polyamide resin is a polyamide resin represented by the general formula (3), and a carboxylic acid obtained by reacting an amine terminal with 5-norbornene-2carboxylic acid and 1-hydroxy1,2,3-benzotriazole. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein a terminal is sealed by reacting a derivative .

(* Indicates bonding to an NH group. In the formula, Y ₁ is an organic group, R ₄ is any one of a hydroxyl group, a carboxyl group, O—R ₅ , and COO—R ₅ , which are the same or different. N is an integer of 0 to 8. R5 is an organic group having 1 to 15 carbon atoms, wherein A is —CH ₂ —, —C (CH ₃ ) ₂ —, —O. _{-, - C (CF 3)} 2 -, or _.R 0, _{R 1} is a single bond is an organic group, which may be the same or different .p, q is an integer of 0 to 3). The polyamide resin is a polyamide resin represented by the general formula (4),
The end of the polyamide resin is sealed by reacting a carboxylic acid derivative obtained by reacting 5-norbornene-2carboxylic acid with 1-hydroxy1,2,3-benzotriazole at the amine end of the polyamide resin. The positive photosensitive resin composition according to any one of claims 1 to 4.

(In the formula, Y ₂ is an organic group, and Z is an organic group different from X. a and b represent mole percent, a + b = 100, a is 60 or more and 100 or less, and b is 0 or more and 40 or less. R ₆ is either a hydroxyl group or O—R ₈ , which may be the same or different, R ₈ is an organic group having 1 to 15 carbon atoms, R ₄ and R ₇ are a hydroxyl group, A carboxyl group, O—R ₅ , or COO—R ₅ , which may be the same or different, and l, m, and n are integers of 0 to 8. In the formula, A is —CH ₂ —, And —C (CH ₃ ) ₂ —, —O—, —C (CF ₃ ) ₂ —, or a single bond, R ₀ and R ₁ are organic groups, which may be the same or different, p, q Is an integer from 0 to 3.) Furthermore, the positive photosensitive resin composition of any one of Claim 1 thru | or 5 which comprises the compound (C) which has a phenolic hydroxyl group. The positive photosensitive resin composition according to claim 6 , wherein the compound (C) having a phenolic hydroxyl group is selected from the group of the following formula (5).

It claims 1 to cured film, which is composed of a cured product of the positive photosensitive resin composition according to any one of 7. A protective film comprising the cured film according to claim 8 . An insulating film comprising the cured film according to claim 8. A semiconductor device comprising the cured film according to claim 8 . A display device comprising the cured film according to claim 8 .