JP2008156614A - Positive photo sensitive resin composition, cured membrane, protective membrane, insulating membrane and semiconductor device and display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photo sensitive resin composition that uses a polyamide resin showing high cyclization ratio, even when cured at a low temperature. <P>SOLUTION: The polyamide resin comprises a bis(aminophenol) having a phenolic hydroxyl group on the adjacent position of the amino group and a structure originating from the carboxyl group, and the distance is less than 2.930 Å between the oxygen atom of the hydroxyl group originating from the bis(aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group. The polyamide resin is used as the positive photo sensitive resin composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to 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, polyimide resins having excellent heat resistance and excellent electrical and mechanical properties have been used for the protective film and insulating film of semiconductor elements, but recently there is no carbonyl group derived from a highly polar imide ring. Therefore, polybenzoxazole resin, which is considered to have good moisture resistance reliability, is beginning to be used in the most advanced semiconductor elements. Further, photosensitive resin compositions have been developed that impart photosensitivity to the polybenzoxazole resin or the polyimide resin itself so that a part of the relief pattern forming process can be simplified, and are effective in shortening the process and improving the yield.
More recently, positive photosensitive resin compositions that can be developed with an aqueous alkaline solution have been developed from the viewpoint of safety. For example, Patent Document 1 discloses a positive photosensitive resin composition composed of a polybenzoxazole precursor resin as a base resin and a diazoquinone compound as a photosensitive agent. This has high heat resistance, excellent electrical properties, and fine processability, and has the potential as an insulating resin composition as well as a protective film for semiconductor elements. The development mechanism of this positive photosensitive resin composition is as follows. The unexposed portion of the diazoquinone compound is insoluble in the aqueous alkali solution and has resistance against this by interacting with the base resin. On the other hand, upon exposure, the diazoquinone compound undergoes a chemical change, becomes soluble in an aqueous alkaline solution, and promotes dissolution of the base resin. By utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, a relief pattern of only the unexposed portion can be created.

The polybenzoxazole precursor resin in the positive photosensitive resin composition in which the relief pattern is formed is finally dehydrated and closed by curing at a high temperature close to 300 ° C., and becomes a polybenzoxazole resin having high heat resistance. On the other hand, in recent years, due to the remarkable miniaturization and high integration of semiconductor elements, the heat resistance of memory elements in particular has been lower than that of conventional ones, and a polybenzoxazole precursor resin that can be cured at a lower temperature is required to improve the yield. Has been. What is important when curing at a low temperature is the cyclization rate of the resin after curing. When the cyclization rate is low, the water absorption is increased due to the influence of the remaining alkali-soluble groups, so that not only the moisture resistance reliability and chemical resistance are lowered, but also the dielectric constant is increased.
However, in the case of a general polybenzoxazole precursor resin, it is more difficult to ring-close than a polyimide precursor resin, and the cyclization rate was not particularly high when cured at a low temperature.
Therefore, development of a photosensitive resin composition that has a high cyclization rate even when cured at a low temperature has been strongly desired recently.

Japanese Examined Patent Publication No. 1-46862

  The present invention has been made in view of the above circumstances, and its object is to provide a positive photosensitive resin composition, a cured film, a protective film, an insulating film, and a high cyclization rate even when cured at a low temperature. A semiconductor device and a display device using the same are provided.

（式（４）中、Ｘ、Ｙは有機基である。ａ、ｂ、ｃ、ｄはモルパーセントを示し、ａ＋ｂ＝１００、ｃ＋ｄ＝１００で、ａ、ｃがそれぞれ３０以上１００以下、ｂ、ｄがそれぞれ０以上〜７０以下である。Ｒ_５、Ｒ_１０は水酸基又は−Ｏ−Ｒ_１１であり、同一でも異なっても良い。Ｒ_６は水酸基、カルボキシル基、−Ｏ−Ｒ_１１、−ＣＯＯ−Ｒ_１１のいずれかであり、同一でも異なっても良い。ｍは０〜２の整数、ｎは０〜４の整数、ｐは２である。Ｒ_１１は炭素数１〜１５の有機基である。式（４−１）で、Ｒ_５として水酸基がない場合、Ｒ_６は少なくとも１つはカルボキシル基でなければならない。また、Ｒ_６としてカルボキシル基がない場合、Ｒ_５は少なくとも１つは水酸基でなければならない。）
［６］［１］乃至［５］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。
［７］更にフェノール化合物（Ｃ）を含むものである［６］に記載のポジ型感光性樹脂組成物。
［８］［６］または［７］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。
［９］［８］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。
［１０］［８］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。
［１１］［８］に記載の硬化膜を有していることを特徴とする半導体装置。
［１２］［８］に記載の硬化膜を有していることを特徴とする表示体装置。 Such an object is achieved by the present invention described in the following [1] to [12].
[1] A polyamide resin having a structure derived from bis (aminophenol) having a phenolic hydroxyl group at a site adjacent to an amino group and a carboxylic acid, the oxygen atom of the hydroxyl group derived from bis (aminophenol), and the hydroxyl group A polyamide resin, wherein the distance between the carbon atom of the carbonyl group in the amide bond adjacent to is 2.930 mm or less.
[2] The polyamide resin according to [1], wherein the bis (aminophenol) has a substituent at a site adjacent to both amino groups.
[3] The polyamide resin according to [1] or [2], wherein the bis (aminophenol) has a substituent at a site adjacent to both hydroxyl groups.
[4] The polyamide resin according to any one of [1] to [3], wherein the polyamide resin includes a polybenzoxazole precursor structure.
[5] The polyamide resin according to [4], wherein the polybenzoxazole precursor resin includes a structure represented by formula (4-1) or formula (4-2).

(In the formula (4), X and Y are organic groups. A, b, c and d represent mole percent, and a + b = 100 and c + d = 100, and a and c are 30 or more and 100 or less, b, d is from 0 to 70. R ₅ and R ₁₀ are a hydroxyl group or —O—R ₁₁ and may be the same or different, and R ₆ is a hydroxyl group, a carboxyl group, —O—R ₁₁ , —COO. -R ₁₁ , which may be the same or different, m is an integer of 0 to 2, n is an integer of 0 to 4, and p is 2. R ₁₁ is an organic group having 1 to 15 carbon atoms. In formula (4-1), when R ₅ does not have a hydroxyl group, at least one R ₆ must be a carboxyl group, and when R ₆ does not have a carboxyl group, R ₅ must have at least one Must be a hydroxyl group.)
[6] A positive photosensitive resin composition comprising the polyamide resin (A) according to [1] to [5] and a photosensitive diazoquinone compound (B).
[7] The positive photosensitive resin composition according to [6], further containing a phenol compound (C).
[8] A cured film comprising a cured product of the positive photosensitive resin composition according to [6] or [7].
[9] A protective film comprising the cured film according to [8].
[10] An insulating film comprising the cured film according to [8].
[11] A semiconductor device comprising the cured film according to [8].
[12] A display device having the cured film according to [8].

  According to the present invention, there are provided a positive photosensitive resin composition, a cured film, a protective film, an insulating film, a semiconductor device using the same, and a display device that have a high cyclization rate even when cured at a low temperature. It is.

The polyamide resin (A) used in the present invention is composed of bis (aminophenol) having a phenolic hydroxyl group at a site adjacent to an amino group and a structure derived from carboxylic acid. The distance between the oxygen atom and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group is 2.930 、 ２ or less.
The bis (aminophenol) has a substituent at a site adjacent to both amino groups. Furthermore, the said bis (aminophenol) has a substituent in the site | part which both hydroxyl groups adjoin.
The positive photosensitive resin composition includes the polyamide resin (A) and the photosensitive diazoquinone compound (B). The protective film and the insulating film are formed of a cured film that is a cured product of the positive photosensitive resin composition. Furthermore, the semiconductor device and the display device are characterized by being formed of the protective film and the insulating film.
Hereinafter, each component of the polyamide resin and the positive photosensitive resin composition of the present invention will be described in detail. The following is an example, and the present invention is not limited to the following.

  Conventionally, there has been no polyamide resin containing a polybenzoxazole precursor structure that satisfies a high cyclization rate even when cured at a low temperature. On the other hand, in the present invention, a bis (aminophenol) having a phenolic hydroxyl group at a site adjacent to an amino group and a polyamide resin having a structure derived from a carboxylic acid, the oxygen atom of the hydroxyl group derived from bis (aminophenol) By using a polyamide resin whose distance from the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group is 2.930 mm or less, a polybenzo having a high cyclization rate even when cured at low temperature A polyamide resin containing an oxazole precursor structure is obtained.

In the case of a polyimide precursor resin, the cyclization mechanism is thought to be that the nitrogen atom of the amide bond in the polyimide precursor resin nucleophilically attacks the carbonyl carbon in the carboxyl group and forms an imide ring by dehydration cyclization reaction. In contrast,
In the case of a polybenzoxazole precursor resin, the ring-closing mechanism is such that the oxygen atom of the hydroxyl group derived from bis (aminophenol) first forms an intermediate by nucleophilic attack on the carbon atom of the carbonyl group in the amide bond, A reaction process in which the intermediate forms an oxazole ring by a dehydration cyclization reaction is considered. However, since the reaction requires more heat energy, the polybenzoxazole precursor resin is more than the polyimide precursor resin. It was difficult to close the ring and could not be cured at a low temperature.
Thus, in the ring closure of the polybenzoxazole precursor resin, since the oxygen atom of the hydroxyl group derived from bis (aminophenol) must first nucleophilicly attack the carbon atom of the carbonyl group in the amide bond, The distance between is expected to be important.

In the conventional polybenzoxazole precursor resin, the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group is longer than about 2.940 mm. . In this case, it is difficult for the ring closure reaction to proceed when cured at a low temperature.
In view of the above results, as a result of intensive studies, a polyoxygen compound in which the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group is 2.930 mm or less. It has been found that the benzoxazole precursor resin exhibits a high cyclization rate even when cured at a low temperature. This is because the distance is shorter than the conventional polybenzoxazole precursor resin, the oxygen atom of the hydroxyl group derived from bis (aminophenol) is likely to nucleophilic attack to the carbon atom of the carbonyl group in the amide bond, This is thought to be due to the fact that the ring-closing reaction was sufficiently advanced even with lower heat energy. Preferably, when the distance is 2.920 mm or less, a high cyclization rate is more easily obtained when cured at a low temperature.

  When changing the distance between certain atoms in two types of atomic groups selected from functional groups, substituents, linking groups, etc. bonded on the aromatic ring, the method is to substitute at the site adjacent to the atomic group. The method of changing the said distance by introduce | transducing group by the steric hindrance with the atomic group is mentioned.

  Specifically, the bis (aminophenol) has a substituent at a site adjacent to both amino groups, the oxygen atom of the hydroxyl group derived from bis (aminophenol) in the polybenzoxazole precursor resin, and its This is important in order to make the distance between the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group less than 2.930 mm.

（式中、Ｒ_１はアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、単結合、又は式（２）の群から選ばれる有機基である。Ｒ_２はアルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。Ｒ_３は水素原子、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。）

（式中、＊は式（１）のアミノフェノール構造に結合することを示す。） More specifically, examples of the bis (aminophenol) include a compound represented by the formula (1). As a result, the amide bond in the polyamide resin is pushed out to the hydroxyl group side by steric hindrance with the substituent (R ₂ ) at the ortho position of the amino group of formula (1), and the carbonyl carbon of the amide bond and the oxygen atom of the hydroxyl group The distance is considered to be shorter than 2.930 mm, and the oxygen atom of the hydroxyl group derived from bis (aminophenol) is likely to nucleophilic attack the carbon atom of the carbonyl group in the amide bond, and even when cured at low temperature, The effect which becomes a conversion rate can be given.

(In the formula, R ₁ is alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, a single bond, or an organic group selected from the group of formula (2). R ₂ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, and may be the same or different, and R ₃ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group. And may be the same or different.)

(In the formula, * indicates binding to the aminophenol structure of formula (1).)

（式中、Ｒ_４はアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、単結合から選ばれる有機基である。Ｒ_２はアルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。Ｒ_３は水素原子、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。） The bis (aminophenol) is more preferably bis (aminophenol) represented by the following formula (3).

(In the formula, R ₄ represents an organic group selected from alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and a single bond. R ₂ represents an alkyl group and an alkoxy group. R ₃ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. good.)

When it is desired to obtain an effect of increasing the cyclization rate when cured at a low temperature, the use of bis (aminophenol) having a substituent also at the ortho position (R ₃ ) of the phenolic hydroxyl group is the same as above. It is considered that the hydroxyl group is pushed closer to the amide bond side due to steric hindrance with the substituent, and is more preferable because the distance between the carbonyl carbon of the amide bond and the hydroxyl group is 2.930 mm or less.

Particularly preferably, when bis (aminophenol) in which R ₂ in formula (1) is an alkyl group or an alkoxy group, and R ₃ is an alkyl group or an alkoxy group is used at a low temperature, It is preferable that a polyamide resin having sufficient solubility in an alkaline aqueous solution and having a better balance can be obtained while maintaining a higher cyclization rate.
Examples of the alkyl _{groups, -CH 3, -CH 2 CH 3} , -CH 2 CH 2 CH 3, -CH (CH 3) 2, -CH 2 CH 2 CH 2 CH 3, -CH 2 CH _{(CH 3) 2, -CH (} CH 3) (CH 2 CH 3), - C (CH 3) 3, -CH 2 CH 2 CH 2 CH 2 CH 3, -CH 2 CH 2 CH (CH 3) 2 _{, -CH 2 CH (CH 3)} (CH 2 CH 3), - CH (CH 2 CH 3) (CH 2 CH 3), - CH (CH 3) (CH 2 CH 2 CH 3), - CH (CH _{3) (CH (CH 3)} 2), - CH 2 CH 2 CH 2 CH 2 CH 2 CH 3, -CH (CH 3) (CH 2 CH 2 CH 2 CH 3), - CH (CH 3) (CH _{2 CH (CH 3) 2)} , - CH 2 CH 2 CH 2 CH ₂ CH ₂ CH ₂ CH _3, etc. _{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 3 and the like. Specific examples of the alkoxy _{group, -OCH 3, -OCH 2 CH 3} , -OCH 2 CH 2 CH 3, -OCH (CH 3) 2, -OCH 2 CH 2 CH 2 CH 3, -OCH 2 CH _{(CH 3) 2, -OCH (} CH 3) (CH 2 CH 3), - OC (CH 3) 3 and the like.

Specific examples of R _{1 in} formula ( ₁ ), R _{4 in} formula (3), and substituted alkylene include —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, _{-CH (CH 2 CH 3) -} , - C (CH 3) (CH 2 CH 3) -, - C (CH 2 CH 3) (CH 2 CH 3) -, - CH (CH 2 CH 2 CH 3) _{-, - C (CH 3)} (CH 2 CH 2 CH 3) -, - CH (CH (CH 3) 2) -, - C (CH 3) (CH (CH 3) 2) -, - CH (CH _{2 CH 2 CH 2 CH 3)} -, - C (CH 3) (CH 2 CH 2 CH 2 CH 3) -, - CH (CH 2 CH (CH 3) 2) -, - C (CH 3) (CH _{2 CH (CH 3) 2)} -, - CH (CH 2 CH 2 CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 _{CH 2 CH 2 CH 2 CH 3} ) -, - CH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) - Among them, —CH ₂ —, —CH (CH ₃ ) —, and —C (CH ₃ ) ₂ — maintain a higher cyclization rate even when cured at a lower temperature. However, it is preferable because a polyamide resin having sufficient solubility in not only an alkaline aqueous solution but also a solvent and having a better balance can be obtained.

The distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) in the present invention and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group can be determined by computational chemistry. For the calculation, for example, a personal computer in which a central processing unit (CPU) is equipped with an Intel Pentium (registered trademark) 4 processor and a 512 Mbyte memory can be used. A specific method for obtaining the distance will be described below.
With Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft, a structure in which two benzoic acids are bonded to the two amino groups of bis (aminophenol) with an amide bond is drawn. After structural optimization was performed by the molecular mechanics method (MM2 method) attached to Chem3D (trademark) Ultra (version 8.0) manufactured by Chem3D, the structure after the structural optimization was further converted to WinMOPAC (manufactured by Fujitsu Limited). In the molecular orbital method (PM5 method) attached to version 3.9.0), the MMOK keyword, which is the molecular dynamics correction of the amide bond, was input to optimize the structure. The distance between the oxygen atom of the hydroxyl group derived from two bis (aminophenols) in the structure after this structure optimization and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was measured and averaged. The value was used.

  The polyamide resin (A) used in the present invention has a polybenzoxazole precursor structure, but is not limited thereto and may have another structure. Examples of other structures include a structure having at least one of a polybenzoxazole structure and a polyimide structure, and having a hydroxyl group, a carboxyl group, an ether group or an ester group in the main chain or side chain, a polyimide precursor structure, a polyamide It is an acid ester structure. For example, a polyamide resin having a structure represented by the formula (4-1) is preferable from the viewpoint of heat resistance and reliability after final heating. More preferred is a polybenzoxazole precursor resin represented by the formula (4-2).

（式（４）中、Ｘ、Ｙは有機基である。ａ、ｂ、ｃ、ｄはモルパーセントを示し、ａ＋ｂ＝１００、ｃ＋ｄ＝１００で、ａ、ｃがそれぞれ３０以上１００以下、ｂ、ｄがそれぞれ０以上〜７０以下である。Ｒ_５、Ｒ_１０は水酸基又は−Ｏ−Ｒ_１１であり、同一でも異なっても良い。Ｒ_６は水酸基、カルボキシル基、−Ｏ−Ｒ_１１、−ＣＯＯ−Ｒ_１１のいずれかであり、同一でも異なっても良い。ｍは０〜２の整数、ｎは０〜４の整数、ｐは２である。Ｒ_１１は炭素数１〜１５の有機基である。式（４−１）で、Ｒ_５として水酸基がない場合、Ｒ_６は少なくとも１つはカルボキシル基でなければならない。また、Ｒ_６としてカルボキシル基がない場合、Ｒ_５は少なくとも１つは水酸基でなければならない。）

(In the formula (4), X and Y are organic groups. A, b, c and d represent mole percent, and a + b = 100 and c + d = 100, and a and c are 30 or more and 100 or less, b, d is from 0 to 70. R ₅ and R ₁₀ are a hydroxyl group or —O—R ₁₁ and may be the same or different, and R ₆ is a hydroxyl group, a carboxyl group, —O—R ₁₁ , —COO. -R ₁₁ , which may be the same or different, m is an integer of 0 to 2, n is an integer of 0 to 4, and p is 2. R ₁₁ is an organic group having 1 to 15 carbon atoms. In formula (4-1), when R ₅ does not have a hydroxyl group, at least one R ₆ must be a carboxyl group, and when R ₆ does not have a carboxyl group, R ₅ must have at least one Must be a hydroxyl group.)

（式中、＊は式（４）のアミノフェノール構造に結合することを示す。） (In the formula (4), R ₁ and R ₇ are alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, a single bond, or a group of the formula (2). R ₂ and R ₈ are any of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different, and R ₃ and R ₉ are a hydrogen atom, an alkyl group, Any one of an alkoxy group, an acyloxy group, and a cycloalkyl group, which may be the same or different.)

(In the formula, * indicates binding to the aminophenol structure of formula (4).)

When a and c are 30 mole percent or more, a polyamide resin having a high cyclization rate is obtained even when cured at a low temperature.

The polyamide resin containing the structure represented by the formula (4-1) is, for example, a bis (aminophenol) having a phenolic hydroxyl group at the site adjacent to the amino group represented by the formula (1), and a diamine containing X if necessary. Alternatively, a compound selected from bis (aminophenol), 2,4-diaminophenol, and the like, tetracarboxylic dianhydride containing Y, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid And obtained by reacting a compound selected from hydroxydicarboxylic acid derivatives and the like.
The polybenzoxazole precursor resin represented by the formula (4-2) includes, for example, bis (aminophenol) having a phenolic hydroxyl group at a site adjacent to the amino group represented by the formula (1), and X if necessary. It is obtained by reacting a compound selected from bis (aminophenol), 2,4-diaminophenol and the like with a compound selected from dicarboxylic acid containing Y, dicarboxylic acid dichloride, dicarboxylic acid derivative and the like. 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.

（式中、Ｒ_１はアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、単結合、又は式（２）の群から選ばれる有機基である。Ｒ_２はアルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。Ｒ_３は水素原子、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。）

（式中、＊は式（１）のアミノフェノール構造に結合することを示す。）

(In the formula, R ₁ is alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, a single bond, or an organic group selected from the group of formula (2). R ₂ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, and may be the same or different, and R ₃ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group. And may be the same or different.)

(In the formula, * indicates binding to the aminophenol structure of formula (1).)

In the polyamide resin represented by the formula (4), —O—R ₁₁ as a substituent of X, —O—R ₁₁ and —COO—R ₁₁ as a substituent of Y are a hydroxyl group and a carboxyl group with respect to an alkaline aqueous solution. For the purpose of adjusting the solubility, it is a group protected with R ₁₁ 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 ₁₁ 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.

  When this polyamide resin is heated at a high temperature, it is 280 ° C. to 380 ° C., and when it is heated at a low temperature, it is subjected to dehydration ring closure when treated at 150 ° C. to 280 ° C., and a polybenzoxazole resin or A heat-resistant resin is obtained in the form of copolymerization. Heat treatment at a low temperature is effective in improving yield even in a semiconductor element having low heat resistance.

  X in 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. Preferred examples include those represented by the following formula (5). 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.

As shown in Formula (4), in Formula (4-1), 0 to 2 R ₅ are bonded to X, and in Formula (4-2), 2 R ₁₀ are bonded to X ( In formula (5), R ₅ and R ₁₀ are omitted).

Y in the formula (4) is an organic group, and examples thereof are the same as those described above, for example, aromatic compounds such as benzene ring and naphthalene ring, bisphenols, pyrroles, pyridines, furans, and siloxane compounds. 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.

In the case of formula (4-1), 0 to 4 R ₆ are bonded to Y (in formula (6), R ₆ is omitted).

  In the formula (4), b which is the mole percent of the repeating unit containing X may be zero.

Further, the polyamide resin represented by the above formula (4) includes an acid anhydride containing an amino group at the terminal of the polyamide resin, an aliphatic group having at least one alkenyl group or alkynyl group, or a cyclic compound group. Preferably capped as an amide. Thereby, preservability can be improved. Examples of such a group derived from an acid anhydride containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include formula (7) and formula (8). ) And the like. These may be used alone or in combination of two or more.

  Of these, a group selected from the formula (9) is particularly preferable. Thereby, especially storability can be improved.

  The method is not limited to this method, and the terminal carboxylic acid contained in the polyamide resin is converted into an amide by using an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. It can also be capped.

  The photosensitive diazoquinone compound (B) used in the present invention is, for example, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Can be mentioned. Specific examples include ester compounds represented by the formulas (10) to (13). These may be used alone or in combination of two or more.

式中Ｑは、水素原子、式（１４）、式（１５）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（１４）、式（１５）である。

In the formula, Q is selected from a hydrogen atom, formula (14), and formula (15). Here, at least one of Q of each compound is represented by formula (14) or formula (15).

  Furthermore, in the present invention, the phenolic compound (C) can be used in combination so that the patterning can be performed with high sensitivity and without resin residue (scum) after development. Specific examples of the structure include those represented by formula (16), but are not limited thereto. These may be used alone or in combination of two or more.

The resin composition and the positive photosensitive resin composition in the present invention may contain additives such as a leveling agent and a silane coupling agent as necessary.

In the present invention, these components are 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. When applied on a semiconductor element, the applied amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is below the lower limit value, it will be difficult to fully function as a protective film and insulating film for semiconductor elements, and if the film thickness exceeds the upper limit value, it will be difficult to obtain a fine relief pattern. , Processing takes time and throughput decreases. 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, or an oxazole ring and an imide ring, and a cured product having high heat resistance is obtained.
The heat treatment can be performed at a high temperature or a low temperature, and the heat treatment temperature at a high temperature is preferably 280 ° C to 380 ° C, more preferably 290 ° C to 350 ° C. The heat treatment temperature at low temperature is preferably 150 ° C. to 280 ° C., more preferably 180 ° C. to 260 ° C.

  Next, 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 usage method is based on forming the positive photosensitive resin composition layer 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>
Calculation of the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group. For the calculation, the central processing unit (CPU) is connected to Intel Pentium. A notebook personal computer VersaPro NX VY22S manufactured by NEC Corporation equipped with a (registered trademark) 4 processor and a 512 Mbyte memory was used. Two ChemoDraw (registered trademark) Pro (version 8.0) manufactured by Cambridge Software Co., benzoic acid is bonded to two amino groups of 4,4'-methylenebis (2-amino-3,6-dimethylphenol) by amide bonds. The following bonded structure was drawn from the benzoic acid side on the left.

The drawn structure is referred to as Chem3D (registered trademark) Ultra (version 8).
. After structural optimization by the molecular mechanics method (MM2 method) attached to 0), the structure after the structure optimization is attached to WinMOPAC (version 3.9.0) manufactured by Fujitsu Limited. In the molecular orbital method (PM5 method), the structure optimization was performed in a state where the MMOK keyword, which is molecular mechanics correction of an amide bond, was input. The distance between the oxygen atom of the hydroxyl group derived from two bis (aminophenols) in the structure after this structure optimization and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was measured and averaged. However, a value of 2.908cm was obtained.

Synthesis of polyamide resin Dicarboxylic acid obtained by reacting 0.360 mol of isophthalic acid, 0.540 mol of diphenyl ether-4,4′-dicarboxylic acid and 1.800 mol of 1-hydroxy-1,2,3-benzotriazole 409.94 g (0.900 mol) of acid derivative (active ester) and 286.37 g (1.000 mol) of 4,4′-methylenebis (2-amino-3,6-dimethylphenol) were thermometer and stirrer. Into a four-necked separable flask equipped with a raw material inlet and a dry nitrogen gas inlet tube, 2950 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath. Next, 34.43 g (0.200 mol) of 4-ethynylphthalic anhydride dissolved in 100 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 3 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed well with water, dried under vacuum, and the formula (4-2) ), A = 100, b = 0, the number average molecular weight was 12000, and the target polyamide resin (A-1) comprising the compound shown in Table 1 was obtained.

Synthesis of naphthoquinonediazide sulfonic acid ester compound 15.82 g (0.025 mol) of phenol formula (B-1) and 8.40 g (0.083 mol) of triethylamine were thermometer, stirrer, raw material inlet, dry nitrogen gas. Into a four-necked separable flask equipped with an introduction tube, 135 g of tetrahydrofuran was added and dissolved. After cooling the reaction solution to 10 ° C. or lower, 22.30 g (0.083 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride was gradually added dropwise with 100 g of tetrahydrofuran so as not to exceed 10 ° C. . Thereafter, the mixture was stirred at 10 ° C. or lower for 5 minutes and then stirred at room temperature for 5 hours to complete the reaction. 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 formula (Q-1 The naphthoquinone diazide sulfonic acid ester compound represented by the structure

Preparation of Positive Photosensitive Resin Composition After dissolving 100 g of synthesized polyamide resin (A-1) and 15 g of naphthoquinone diazide sulfonic acid ester compound having the structure of formula (Q-1) in 200 g of N-methyl-2-pyrrolidone And filtered through a 0.2 μm Teflon (registered trademark) filter to obtain a positive photosensitive resin composition.

Evaluation of Sensitivity This positive photosensitive resin composition was applied on a silicon wafer using a spin coater and then pre-baked at 120 ° C. for 3 minutes on a hot plate to obtain a coating film having a thickness of about 8.1 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern having a width of 0.88 to 50 μm are drawn), and an i-line stepper (manufactured by Nikon Corporation, 4425i). ) And changed the exposure amount. Next, the exposed area was dissolved and removed by paddle development twice in 150 seconds in a 2.38% tetramethylammonium hydroxide aqueous solution, and then rinsed with pure water for 10 seconds. As a result, the exposure amount 260 mJ / cm ²
It was confirmed that the pattern was formed from the portion irradiated with. (Sensitivity is 260 mJ / cm ² ). The film thickness after development showed a very high value of 8.0 μm.

Evaluation of cyclization rate The above positive photosensitive resin composition was applied onto two silicon wafers using a spin coater, and then pre-baked at 120 ° C. for 4 minutes on a hot plate to form a coating film having a thickness of about 1 μm. Obtained. Next, one film-coated silicon wafer was immersed in 2% hydrofluoric acid to obtain a film. The film was measured using a Fourier transform infrared spectrophotometer PARAGON1000 (Perkin Elmer) was calculated ratio of the peak (A) associated with the wholly aromatic amide group and 1490cm ^-1 of 1650 cm ^-1. Next, after another silicon wafer with a coating film was heated at 250 ° C./90 minutes using an oven, a cured film was obtained in the same manner, and measured by Fourier transform infrared spectrophotometer at 1650 cm ^−1. The ratio (B) of the peak associated with the amide group of 1490 cm ^{−1 and} the total aromatic of 1490 cm ⁻¹ was calculated. The cyclization rate was a value obtained by multiplying (1- (B / A)) by 100. The cyclization rate thus determined was 95%.

Evaluation of water absorption rate The above positive photosensitive resin composition was applied onto a 6-inch silicon wafer using a spin coater and then pre-baked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 10 μm. . Next, the silicon wafer with a coating film was heated at 250 ° C./90 minutes using an oven. The cured coating film was cut with a cutter so as to form a 5 cm square mesh, and then immersed in 2% hydrofluoric acid to obtain a 5 cm square film. The water absorption of this film was measured according to the test standard JIS-K7209, and a value of 0.65% was obtained.

<Example 2>
Calculation of distance between oxygen atom of hydroxyl group derived from bis (aminophenol) and carbon atom of carbonyl group in amide bond adjacent to the hydroxyl group Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft The following structure in which two benzoic acids are bonded to two amino groups of 3,3′-diamino-4,4′-dihydroxydiphenylmethane by amide bonds was drawn from the benzoic acid side on the left. Otherwise, the calculation was performed in the same manner as in Example 1, and the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was 2. A value of 949 cm was obtained.

Synthesis of polyamide resin In the synthesis of polyamide resin in Example 1, the molar ratio of isophthalic acid and diphenyl ether-4,4'-dicarboxylic acid was changed to 0.340 mol and 0.510 mol, respectively, and 4,4'- Methylenebis (2-amino-3,6-dimethylphenol) was reduced to 200.46 g (0.700 mol), instead of 69.08 g (0.300 mol) of 3,3′-diamino-4,4′-dihydroxydiphenylmethane. )
The amount of 4-ethynylphthalic anhydride added was also changed to 51.64 g (0.300 mol) and reacted in the same manner, represented by formula (4-2), a = 70, b = 30, number average A polyamide resin (A-4) having a molecular weight of 9100 and comprising the compounds shown in Table 1 was synthesized.
In addition, the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) of the polyamide resin (A-4) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group depends on each bis (aminophenol). ) And recalculated according to the molar ratio of 2.908 × 0.7 + 2.949 × 0.3 = 2.920Å. Otherwise, a positive photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

<Example 3>
Calculation of distance between oxygen atom of hydroxyl group derived from bis (aminophenol) and carbon atom of carbonyl group in amide bond adjacent to the hydroxyl group Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft The following structure, in which two benzoic acids are bonded to the two amino groups of 2,2-bis (3-amino-4-hydroxyphenyl) propane by amide bonds, was drawn from the left benzoic acid side. Otherwise, the calculation was performed in the same manner as in Example 1, and the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was 2. A value of 956 kg was obtained.

Synthesis of Polyamide Resin In the synthesis of polyamide resin in Example 2, 2,2-bis (3-amino-4-hydroxyphenyl) propane 77. instead of 3,3′-diamino-4,4′-dihydroxydiphenylmethane. The reaction was carried out in the same manner using 50 g (0.300 mol), a polyamide represented by the formula (4-2), a = 70, b = 30, a number average molecular weight of 9400, and comprising the compounds shown in Table 1. Resin (A-5) was synthesized.
In addition, the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) of the polyamide resin (A-5) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group is determined by each bis (aminophenol). ) To obtain a value of 2.908 × 0.7 + 2.956 × 0.3 = 2.922Å. Otherwise, a positive photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

<Example 4>
Calculation of the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group
With Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft, benzoic acid is bonded to the two amino groups of 4,4′-ethylidenebis (2-amino-3,6-dimethylphenol) by an amide bond. The following bonded structure was drawn from the benzoic acid side on the left. Otherwise, the calculation was performed in the same manner as in Example 1, and the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was 2. A value of 906cm was obtained.

Synthesis of polyamide resin In the synthesis of the polyamide resin in Example 1, the molar ratio of isophthalic acid and diphenyl ether-4,4′-dicarboxylic acid was changed to 0.344 mol and 0.516 mol, respectively, and 4,4′- In place of methylenebis (2-amino-3,6-dimethylphenol), 300.40 g (1.000 mol) of 4,4′-ethylidenebis (2-amino-3,6-dimethylphenol) was used. The amount of ethynyl phthalic anhydride added was changed to 48.20 g (0.280 mol) and reacted in the same manner, represented by formula (4-2), where a = 100, b = 0, and the number average molecular weight At 10200, a polyamide resin (A-6) composed of the compounds shown in Table 1 was synthesized. Otherwise, a positive photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

<Example 5>
Synthesis of Polyamide Resin In the synthesis of polyamide resin in Example 4, the molar ratio of isophthalic acid and diphenyl ether-4,4′-dicarboxylic acid was changed to 0.252 mol and 0.588 mol, respectively, and 4,4′- Ethylidenebis (2-amino-3,6-dimethylphenol) is reduced to 210.28 g (0.700 mol), instead of 69.08 g (0.300 g) of 3,3′-diamino-4,4′-dihydroxydiphenylmethane. Mole)
The amount of 4-ethynylphthalic anhydride added was also changed to 55.08 g (0.320 mol) and reacted in the same manner, represented by formula (4-2), a = 70, b = 30, number average A polyamide resin (A-7) having a molecular weight of 9500 and comprising the compounds shown in Table 1 was synthesized.
In addition, the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) of the polyamide resin (A-7) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group depends on each bis (aminophenol). ) And recalculated according to the molar ratio of 2.906 × 0.7 + 2.949 × 0.3 = 2.919Å. Otherwise, a positive photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

<Example 6>
Synthesis of polyamide resin In the synthesis of polyamide resin in Example 5, 2,2-bis (3-amino-4-hydroxyphenyl) propane 77. instead of 3,3′-diamino-4,4′-dihydroxydiphenylmethane. The reaction was carried out in the same manner using 50 g (0.300 mol), a polyamide represented by the formula (4-2), a = 70, b = 30, number average molecular weight 9600, and comprising the compounds shown in Table 1. Resin (A-8) was synthesized.
In addition, the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) of the polyamide resin (A-8) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group is determined by each bis (aminophenol). ) Was recalculated according to the molar ratio of 2.906 × 0.7 + 2.956 × 0.3 = 2.921Å. Otherwise, a positive photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

<Example 7>
Calculation of the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group
Benzoic acid is bonded to two amino groups of 4,4′-ethylidenebis (2-amino-3-methyl-6-cyclohexylphenol) with Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft The following structure in which two are bound together is drawn from the left benzoic acid side. Otherwise, the calculation was performed in the same manner as in Example 1, and the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was 2. A value of 884 cm was obtained.

Synthesis of polyamide resin In the synthesis of the polyamide resin in Example 4, instead of 4,4′-ethylidenebis (2-amino-3,6-dimethylphenol),
The reaction was similarly carried out using 436.64 g (1.000 mol) of 4,4′-ethylidenebis (2-amino-3-methyl-6-cyclohexylphenol), which was represented by the formula (4-2), = 100, b = 0, the number average molecular weight was 9200, and a polyamide resin (A-9) comprising the compounds shown in Table 1 was synthesized.

<Comparative Example 1>
Calculation of distance between oxygen atom of hydroxyl group derived from bis (aminophenol) and carbon atom of carbonyl group in amide bond adjacent to the hydroxyl group Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft The following structure, in which two benzoic acids are bonded to the two amino groups of 2,2-bis (3-amino-4-hydroxyphenyl) propane by amide bonds, was drawn from the left benzoic acid side. Otherwise, the calculation was performed in the same manner as in Example 1, and the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was 2. A value of 956 kg was obtained.

Synthesis of polyamide resin Dicarboxylic acid derivative (active ester) 433 obtained by reacting 0.880 mol of diphenyl ether-4,4′-dicarboxylic acid with 1.760 mol of 1-hydroxy-1,2,3-benzotriazole .36 g (0.880 mol) and 2,2-bis (3-amino-4-hydroxyphenyl) propane 258.32 g (1.000 mol) were thermometer, stirrer, raw material inlet, dry nitrogen gas inlet tube In a four-necked separable flask, and 2760 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, 34.43 g (0.200 mol) of 4-ethynylphthalic anhydride dissolved in 100 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed well with water, dried under vacuum, and the formula (4-2) ), A = 0, b = 100, a number average molecular weight of 10,000, and the target polyamide resin (A-2) comprising the compounds shown in Table 1 was obtained. Otherwise, a positive photosensitive resin composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

<Comparative example 2>
Calculation of distance between oxygen atom of hydroxyl group derived from bis (aminophenol) and carbon atom of carbonyl group in amide bond adjacent to the hydroxyl group Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft The following structure in which two benzoic acids are bonded to the two amino groups of 3,3′-diamino-4,4′-dihydroxydiphenyl ether by an amide bond, the central 3,3′-diamino-4, It was drawn from the 4'-dihydroxydiphenyl ether side. Otherwise, the calculation was performed in the same manner as in Example 1, and the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was 2. A value of 954 kg was obtained.

In the synthesis of the polyamide resin in Example 1, the molar ratio of isophthalic acid to diphenyl ether-4,4′-dicarboxylic acid was changed to 0.200 mol and 0.700 mol, respectively, and 4,4′-methylenebis (2- Instead of amino-3,6-dimethylphenol, 232.25 g of 1,3'-diamino-4,4'-dihydroxydiphenyl ether (1
. 000 moles), a polyamide resin (A-) represented by the formula (4-2), having a = 0, b = 100, a number average molecular weight of 11000 and comprising the compounds shown in Table 1. 3) was synthesized. Otherwise, a positive photosensitive resin composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

  The structures of B-1 and Q-1 of Examples and Comparative Examples, and Table 1 are shown below.

  As shown in Table 1, the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group is 2.930、２ or less. Examples 1, 4, and 7 using phenol), Examples 2, 3, and 5 using these bis (aminophenol) and other bis (aminophenol) so that the distance does not exceed 2.930 mm. No. 6 shows a high cyclization rate even when cured at a low temperature of 250 ° C.

The positive photosensitive resin composition obtained in Example 1 and each comparative example was coated on a semiconductor element to form a pattern in the same manner as in Example 1, and cured using an oven to form a protective film. Thus, a semiconductor device can be obtained.
The semiconductor device thus obtained is expected to operate normally. However, when the positive photosensitive resin composition of Example 1 is used, the water absorption is lower than that of the comparative example, and thus more reliable. It is expected to work excellently.

The calculation example of other bis (aminophenol) is described below.
Calculation of distance between oxygen atom of hydroxyl group derived from bis (aminophenol) and carbon atom of carbonyl group in amide bond adjacent to the hydroxyl group Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft The following structure, in which two benzoic acids are bonded to the two amino groups of 2,2-bis (3-amino-4-hydroxy-2-methylphenyl) propane with an amide bond, I drew from. Otherwise, the calculation was performed in the same manner as in Example 1, and the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was 2. A value of 915 Å was obtained.

Calculation of distance between oxygen atom of hydroxyl group derived from bis (aminophenol) and carbon atom of carbonyl group in amide bond adjacent to the hydroxyl group Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft Then, the following structure in which two benzoic acids are bonded to two amino groups of 4,4′-methylenebis (2-amino-3-methylphenol) by an amide bond was drawn from the benzoic acid side on the left. Otherwise, the calculation was performed in the same manner as in Example 1, and the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was 2. A value of 921 Å was obtained.

Calculation of distance between oxygen atom of hydroxyl group derived from bis (aminophenol) and carbon atom of carbonyl group in amide bond adjacent to the hydroxyl group Chem Draw (registered trademark) Pro (version 8.0) manufactured by Cambridge Soft The following structure, in which two benzoic acids are bonded to the two amino groups of 4,4′-thiobis (2-amino-3,6-dimethylphenol) by an amide bond, is depicted from the left benzoic acid side. It was. Otherwise, the calculation was performed in the same manner as in Example 1, and the distance between the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the carbon atom of the carbonyl group in the amide bond adjacent to the hydroxyl group was 2. A value of 906cm was obtained.

  As can be seen from these calculation results, the bis (aminophenol) having a substituent at the adjacent site of both amino groups is the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the amide bond adjacent to the hydroxyl group. Since the distance between the carbon atom of the carbonyl group and the carbon atom is less than 2.930 mm, when the polyamide resin using these bis (aminophenol) is cured at a low temperature of 250 ° C., a high cyclization rate is obtained. It is expected to be.

The positive photosensitive resin composition of the present invention has a high cyclization rate characteristic even when cured at a low temperature, and is suitably used for a protective film, an insulating film and the like of a semiconductor device and a display device.

Claims (12)

A polyamide resin having a structure derived from bis (aminophenol) having a phenolic hydroxyl group at a site adjacent to an amino group and a carboxylic acid, and adjacent to the oxygen atom of the hydroxyl group derived from bis (aminophenol) and the hydroxyl group A polyamide resin characterized in that the distance from the carbon atom of the carbonyl group in the amide bond is 2.930 mm or less. The polyamide resin according to claim 1, wherein the bis (aminophenol) has a substituent at a site adjacent to both amino groups. The polyamide resin according to claim 1 or 2, wherein the bis (aminophenol) has a substituent at a site adjacent to both hydroxyl groups. The polyamide resin according to claim 1, wherein the polyamide resin contains a polybenzoxazole precursor structure. The polyamide resin according to claim 4, wherein the polybenzoxazole precursor resin includes a structure represented by the formula (4-1) or the formula (4-2).

(In the formula (4), X and Y are organic groups. A, b, c and d represent mole percent, and a + b = 100 and c + d = 100, and a and c are 30 or more and 100 or less, b, d is from 0 to 70. R ₅ and R ₁₀ are a hydroxyl group or —O—R ₁₁ and may be the same or different, and R ₆ is a hydroxyl group, a carboxyl group, —O—R ₁₁ , —COO. -R ₁₁ , which may be the same or different, m is an integer of 0 to 2, n is an integer of 0 to 4, and p is 2. R ₁₁ is an organic group having 1 to 15 carbon atoms. In formula (4-1), when R ₅ does not have a hydroxyl group, at least one R ₆ must be a carboxyl group, and when R ₆ does not have a carboxyl group, R ₅ must have at least one Must be a hydroxyl group.) A positive photosensitive resin composition comprising the polyamide resin (A) according to claim 1 and a photosensitive diazoquinone compound (B). The positive photosensitive resin composition according to claim 6, further comprising a phenol compound (C). A cured film comprising a cured product of the positive photosensitive resin composition according to claim 6 or 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.