JP5035094B2 - Photosensitive resin composition, insulating film, protective film and electronic device - Google Patents

Description

  The present invention relates to a photosensitive resin composition, an insulating film, a protective film, and an electronic device.

  In recent years, metal wiring (generally copper and copper alloys, etc.) has been reduced due to downsizing of semiconductor elements, multilayer wiring by high integration, transition to chip size package (CSP), wafer level package (WLP), etc. In addition, the surface protective film and the interlayer insulating film are often formed directly. For this reason, the adhesion to wiring such as copper and copper alloy has greatly affected the reliability of semiconductor elements, and higher adhesion to wiring such as copper and copper alloy is desired. Yes.

  In addition, from the viewpoint of package characteristics and productivity, it is desirable that the insulating film and the protective film can be cured at a low temperature of 200 to 300 ° C. while having excellent mechanical properties such as elongation of the cured film. It is coming. If it can be cured at a low temperature, it can prevent damage to the highly integrated semiconductor element or the like from heat, and productivity can be improved.

In order to meet such demands, there is a method of adding an additive component to the resin composition in order to improve adhesion with copper and a copper alloy (for example, see Patent Documents 1 and 2). Adhesion could not be obtained.
In addition, when a conventional insulating film or the like is cured at a low temperature, abnormalities in appearance such as wrinkles and cracks may occur on the surface during processing with a flux or the like used when placing solder balls or the like.

JP-A-2005-336125 JP-A-2005-173528

  An object of the present invention is to provide a photosensitive resin composition excellent in permeability to i-line (365 nm), curability at low temperature, and adhesion to copper and copper alloy metal wiring, and an insulating film and a protective film using the same. To provide electronic equipment.

（式中、Ａはアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−
ＮＨＣＯ−、単結合、−Ｃ（ＣＦ₃）₂−から選ばれる有機基であり、Ｂは有機基である。Ｒ¹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。Ｒ²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。ｎは、２〜５００である。）
（２）前記窒素含有環状化合物は、テトラゾール基を含むものである、（１）に記載の感光性樹脂組成物。
（３）前記テトラゾール基を有する窒素含有環状化合物は、式（２−１）および式（２−２）で示される化合物の少なくとも一方を含むものである、（２）に記載の感光性樹脂組成物。

（４）前記窒素含有化合物の含有量は、前記ポリアミド樹脂（Ａ）全体の１．０〜１０．０重量％である、（１）ないし（３）のいずれかに記載の感光性樹脂組成物。
（５）前記ポリアミド樹脂（Ａ）の末端のいずれか一方が、三重結合を有する有機基である（１）ないし（４）のいずれかに記載の感光性樹脂組成物。
（６）前記ポリアミド樹脂（Ａ）のＲ¹が、アルキル基、又はアルコキシ基であり、かつ
、Ｒ²がアルキル基、又はアルコキシ基である、（１）ないし（５）のいずれかに記載の
感光性樹脂組成物。
（７）（１）ないし（６）のいずれかに記載の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絶縁膜。
（８）（１）ないし（６）のいずれかに記載の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保護膜。
（９）半導体素子または液晶表示素子の保護膜として用いられるものである（８）に記載
の保護膜。
（１０）（８）または（９）に記載の保護膜を有することを特徴とする電子機器。
（１１）（７）に記載の絶縁膜を有することを特徴とする電子機器。 Such an object is achieved by the present invention described in the following (1) to (11).
(1) A photosensitive resin composition comprising a polyamide resin (A) and a photosensitive agent (B),
The polyamide resin (A) has a polybenzoxazole precursor structure represented by the following general formula (1), and has at least one nitrogen-containing cyclic compound at the side chain and terminal of the polyamide resin (A). A photosensitive resin composition characterized by the above.

(In the formula, A represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —
NHCO-, a single bond, -C (CF _{3) 2} - is an organic group selected from, B is an organic group. R ¹ is any ^one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. R ² 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. n is 2 to 500. )
(2) The photosensitive resin composition according to (1), wherein the nitrogen-containing cyclic compound includes a tetrazole group.
(3) The photosensitive resin composition according to (2), wherein the nitrogen-containing cyclic compound having a tetrazole group includes at least one of the compounds represented by formula (2-1) and formula (2-2).

(4) The photosensitive resin composition according to any one of (1) to (3), wherein the content of the nitrogen-containing compound is 1.0 to 10.0% by weight of the entire polyamide resin (A). .
(5) The photosensitive resin composition according to any one of (1) to (4), wherein any one of the ends of the polyamide resin (A) is an organic group having a triple bond.
(6) The polyamide resin (A) according to any one of (1) to (5), wherein R ¹ is an alkyl group or an alkoxy group, and R ² is an alkyl group or an alkoxy group. Photosensitive resin composition.
(7) An insulating film comprising a cured product of the photosensitive resin composition according to any one of (1) to (6).
(8) A protective film comprising a cured product of the photosensitive resin composition according to any one of (1) to (6).
(9) The protective film according to (8), which is used as a protective film for a semiconductor element or a liquid crystal display element.
(10) An electronic apparatus comprising the protective film according to (8) or (9).
(11) An electronic apparatus comprising the insulating film according to (7).

  According to the present invention, a photosensitive resin composition excellent in permeability to i-line, curability at low temperature, and adhesiveness with copper and copper alloy metal wiring, and an insulating film, a protective film, and an electronic device using the same Obtainable.

Hereinafter, the photosensitive resin composition, the insulating film, the protective film, and the electronic device of the present invention will be described.
The photosensitive resin composition of the present invention is a photosensitive resin composition containing a polyamide resin (A) and a photosensitive agent (B), and the polyamide resin (A) is represented by the general formula (1). It has a polybenzoxazole precursor structure and has at least one nitrogen-containing cyclic compound at the side chain and terminal of the polyamide resin (A).
In addition, the insulating film of the present invention is characterized by being composed of a cured product of the photosensitive resin composition described above.
Moreover, the protective film of this invention is comprised with the hardened | cured material of the photosensitive resin composition as described above, It is characterized by the above-mentioned.
An electronic device according to the present invention includes the protective film described above.
In addition, an electronic device according to the present invention includes the insulating film described above.

（式中、Ａはアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−
ＮＨＣＯ−、単結合、−Ｃ（ＣＦ₃）₂−から選ばれる有機基であり、Ｂは有機基である。Ｒ¹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。Ｒ²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。ｎは、２〜５００である。）

(In the formula, A represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —
NHCO-, a single bond, -C (CF _{3) 2} - is an organic group selected from, B is an organic group. R ¹ is any ^one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. R ² 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. n is 2 to 500. )

First, the photosensitive resin composition, the insulating film, and the protective film will be described.
As shown in FIG. 1, the semiconductor device 10 includes a silicon wafer 1, an aluminum pad 2 provided on a part of the silicon wafer 1 (upper side in FIG. 1), and an upper portion of the silicon wafer 1 excluding the aluminum pad 2. A protective film 3 provided so as to cover the conductor, a conductor part 4 formed on the upper side of the protective film 3, and an insulation provided so as to cover the conductor part 4 leaving the barrier metal 5 joined to the conductor part 4 A film 6 and solder bumps 7 provided on the barrier metal 5 for electrical connection with external electrodes are provided.
The protective film 3 is composed of a passivation film 31 and a buffer coat film 32, and the passivation film 31 is bonded to the silicon wafer 1. The passivation film 31 and the buffer coat film 32 have a recess 33 so that the aluminum pad 2 is exposed.
The conductor portion 4 includes a metal film 41 provided on the upper surface of the buffer coat film 32 and the inner surface of the recess 33, and a pad portion 42 that fills the recess 33 and is electrically connected to the solder bump 7.
The lower side of the barrier metal 5 is joined to the pad portion 42.

  The photosensitive resin composition of the present invention is suitably used for the buffer coat film 32, the insulating film 6 and the like of the semiconductor device 10 as described above, but is particularly used for the insulating film 6 in direct contact with the copper wiring. It is preferable. Thereby, a semiconductor device with excellent reliability can be provided.

（式中、Ａはアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−
ＮＨＣＯ−、単結合、−Ｃ（ＣＦ₃）₂−から選ばれる有機基であり、Ｂは有機基である。Ｒ¹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。Ｒ²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。ｎは、２〜５００である。） Such a photosensitive resin composition is composed of a resin composition containing a polyamide resin (A) and a photosensitizer (B), and the polyamide resin (A) is a polybenzoxazole represented by the general formula (1). By having a precursor structure and having at least one or more nitrogen-containing cyclic compounds at the side chain and terminal of the polyamide resin (A), the i-line transmission at the time of exposure is excellent. Furthermore, even when the photosensitive resin composition is cured at a low temperature, the cyclization reaction of the polyamide resin (A) is likely to proceed, so that a cured film having excellent heat resistance can be obtained. Furthermore, the adhesiveness with the metal wiring of copper and a copper alloy can be improved in the state which maintained mechanical characteristics, such as the tensile elongation rate of a cured film.

(In the formula, A represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —
NHCO-, a single bond, -C (CF _{3) 2} - is an organic group selected from, B is an organic group. R ¹ is any ^one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. R ² 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. n is 2 to 500. )

（式中、Ａはアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−
ＮＨＣＯ−、単結合、−Ｃ（ＣＦ₃）₂−から選ばれる有機基であり、Ｂは有機基である。Ｒ¹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。Ｒ²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。ｎは、２〜５００である。） (Polyamide resin)
Next, the base polyamide resin (A) will be described.
None of the conventional polyamide resins having a polybenzoxazole derivative structure improve both i-line permeability and cyclization rate when cured at low temperatures. In contrast, in the present invention, since the polyamide resin has a polybenzoxazole precursor structure represented by the general formula (1), both i-line permeability and cyclization rate when cured at low temperature are improved. It became possible.
The reason why the permeability to i-line is improved is that the aromatic ring is bent through R ¹ due to steric hindrance between the substituents because the amino group on the aromatic ring has a substituent at an adjacent site (ortho position). This is probably because the planar structure is difficult to take and charge transfer is difficult to occur. The reason for the improvement in the cyclization rate when cured at low temperature is that the substituent at the ortho position of the amino group (R ¹
) Sterically pushes the amide bond in the polyamide resin and brings the distance between the carbonyl carbon of the amide bond and the phenolic hydroxyl group closer.

(In the formula, A represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —
NHCO-, a single bond, -C (CF _{3) 2} - is an organic group selected from, B is an organic group. R ¹ is any ^one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. R ² 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. n is 2 to 500. )

（式中、Ｒ⁶はアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、単結合、−Ｃ（ＣＦ₃）₂−又は式（５）の群から選ばれる有機基である。Ｒ⁷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。Ｒ⁸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、＊は一般式（４）のアミノフェノール構造に結合することを示す。） The polybenzoxazole precursor represented by the general formula (1) includes a bis (aminophenol) compound represented by the general formula (4) and a carboxylic acid or a carboxylic acid derivative such as an acid anhydride or an acid dianhydride. It can obtain by reaction of. When dicarboxylic acid is used as the carboxylic acid, an active ester type dicarboxylic acid derivative previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like is used to increase the reaction yield or the like. Also good.

(Wherein R ⁶ is alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, a single bond, —C (CF ₃ ) ₂ — or formula (5) An organic group selected from the group: R ⁷ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group;
It may be the same or different. R ⁸ 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 the general formula (4).)

  Specific examples of the bis (aminophenol) compound represented by the general formula (4) of the present invention include those represented by the following formulas (6) to (11), but are not limited thereto. Absent. These may be used alone or in combination of two or more.

  Among these bis (aminophenol) compounds, bis (aminophenol) represented by Formulas 6-1 and 7-4 is particularly preferable because of its excellent cyclization rate and low-temperature curability.

In order to further increase the cyclization rate when cured at a low temperature, the ortho-position (R ⁸ ) of the phenolic hydroxyl group of bis (aminophenol) represented by the general formula (4) is not a hydrogen atom but a substituent. It is considered that the use of bis (aminophenol) having a amide bond is considered to make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and is more preferable.

It is particularly preferable to use bis (aminophenol) in which R ⁷ of the bis (aminophenol) represented by the general formula (4) is an alkyl group or an alkoxy group, and R ⁸ is an alkyl group or an alkoxy group. preferable. As a result, it is possible to obtain a more balanced polyamide resin with sufficient solubility in an aqueous alkali solution while achieving both i-line permeability and improved cyclization when cured at low temperatures. It becomes.

  Among the bis (aminophenol) compounds, bis (aminophenol) represented by formulas 6-2 and 7-3 is particularly preferable because it is further excellent in cyclization rate and low-temperature curability.

Specific examples of R ⁶ alkylene and substituted alkylene of bis (aminophenol) represented by the general formula (4) 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 (C
_{H (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 ) — and the like. Among these, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — are compatible with both i-line permeability and cyclization rate when cured at low temperature. It is possible to obtain a polyamide resin having sufficient solubility in an aqueous solution and having a better balance.

As said polyamide resin (A), you may have the structure of both the polybenzoxazole precursor shown by General formula (1), and another polyamide type compound, for example. Specifically, as the polyamide-based compound, a polyamide-based compound having at least one of a polybenzoxazole compound and a polyimide compound and having a hydroxyl group, a carboxyl group, an ether bond or an ester bond in the main chain or side chain, a general formula ( 1) Polybenzoxazole precursors different from the polybenzoxazole precursor structure represented by the formula, polyimide precursors, polyamide compounds having a polyamic acid ester structure, and the like. An example of such a polyamide compound is a polyamide compound represented by the following general formula (3).

D in the general formula (3) is a cyclic compound group, and examples thereof include aromatic compounds such as a benzene ring and a naphthalene ring, heterocyclic compounds such as bisphenols, pyridines and furans, and siloxane compounds. Specifically, those represented by the following formula (12) can be preferably exemplified. These may be used singly or in combination of two or more as required so as not to affect the high transparency to i-line and the cyclization rate when cured at low temperature.

Particularly preferable examples of the formula (12) include those represented by the following formula (13).

E in the general formula (3) is a cyclic compound group and is not particularly limited, and examples thereof include dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, acid anhydride, acid dianhydride, and siloxane compound. Specifically, carboxylic acids of the following formulas (14) and (15) are exemplified.

  Specific examples include those represented by the following formulas (16) to (17), but are not limited thereto. These may be used alone or in combination of two or more.

  In addition, as the carboxylic acid, a compound having 3 or more carboxyl groups, a compound having one acid anhydride group and one or more carboxyl groups, and a compound having two acid anhydride groups are used. After the introduction, it may react with a bis (aminophenol) compound represented by the general formula (4) and a compound group represented by the formula (12). Thereby, it becomes possible to improve adhesiveness with a metal wiring (especially copper wiring) etc. Examples of the nitrogen-containing cyclic compound include pyrrole, 3-pyrroline, pyrrolidine, pyrazole, 2-pyrazolin, pyrazolidine, imidazole, oxazole, thiazole, 1,2,3-oxadiazole, triazole, tetrazole, 1,3, 4-thiadiazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, pyrazine, piperazine, 1,3,5-triazine, indole, benzimidazole, benzothiazole, purine, quinoline, isoquinoline, cinnoline, quinoxaline, carbazole, acridine, phenothiazine, etc. And a group having a tetrasol structure is preferable. Specifically, (1H-tetrazol-5-yl) amino group, 1- (1H-tetrazol-5-yl) methylamino group, 3- (1H-tetrazol-5-yl) benzamino group and the like can be mentioned. In this case, the side chain of the polyamide resin (A) represented by the general formula (1) has a nitrogen-containing cyclic compound.

The polyamide resin (A) has at least one nitrogen-containing cyclic compound at a side chain and a terminal. Thereby, it is excellent in adhesiveness with a metal wiring (especially copper wiring) etc.
Examples of the nitrogen-containing cyclic compound include pyrrole, 3-pyrroline, pyrrolidine, pyrazole, 2-pyrazolin, pyrazolidine, imidazole, oxazole, thiazole, 1,2,3-oxadiazole, triazole, tetrazole, 1,3,4 -Thiadiazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, pyrazine, piperazine, 1,3,5-triazine, indole, benzimidazole, benzothiazole, purine, quinoline, isoquinoline, cinnoline, quinoxaline, carbazole, acridine, phenothiazine, etc. Examples thereof include groups having a structure, and among them, a group having a pyrazole, triazole, or tetrasol structure is preferable. Specifically, 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazoyl) amino group, 4- (1H-pyrazoyl) amino group, 5- (1H-pyrazoyl) amino group, 1- ( 3-1H-pyrazolyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazolyl) methylamino group, (1H-tetrazol-5-yl) amino group, 1- (1H-tetrazol-5-yl) methylamino group, 3- (1H-tetrazol-5-yl) benzamino group and the like can be mentioned. Among these, the compounds represented by formula (2-1) and formula (2-2) are preferable. Thereby, especially adhesiveness with the metal wiring of copper and a copper alloy can be improved more.

Thus, the polyamide resin (A) of the present invention has at least one nitrogen-containing cyclic compound at the side chain and terminal. Thereby, it is excellent in adhesiveness with the metal wiring of a cured film.
The reason for this is that the polyamide resin (A) has at least one nitrogen-containing cyclic compound at the side chain and the terminal thereof, so that the nitrogen-containing cyclic compound reacts with the metal wiring of copper and copper alloy.
In contrast, in the method of simply adding a nitrogen-containing compound to the photosensitive resin composition, it is difficult to obtain sufficient adhesion because the polyamide resin (A) itself does not react with copper and copper alloy metal wiring. Become. In other words, when a nitrogen-containing compound is added, in order to obtain sufficient adhesion with copper and copper alloy metal wiring, the reaction between the nitrogen-containing compound copper and copper alloy metal wiring, and the nitrogen-containing compound and polyamide resin (A) Both reactions with (A) must be sufficiently carried out. Usually, in the method of simply adding a nitrogen-containing compound, the nitrogen-containing compound and the polyamide resin (
The reaction with A) becomes insufficient.
Since the polyamide resin (A) of the present invention has at least one nitrogen-containing cyclic compound at the side chain and terminal (that is, the resin skeleton has a nitrogen-containing compound), the nitrogen-containing cyclic compound and copper and copper alloy metal wiring React to obtain excellent adhesion.

  In addition, the polyamide resin (A) of the present invention may have an unsaturated group introduced at one end of the polyamide resin (A) for the purpose of improving mechanical properties such as tensile elongation of the cured film of the photosensitive resin composition. Good. Examples of such unsaturated groups include acid anhydrides containing an alkenyl group, an aliphatic group having at least one alkynyl group, and a cyclic compound group. Thereby, the mechanical characteristics of the cured film can be improved. Examples of the 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 alkenyl represented by the formula (18) A group having a group, a group having an alkynyl group represented by formula (19), and the like.

Among these, particularly preferred are those selected from the formula (20), and two or more of these may be used. Thereby, especially the mechanical characteristics of a cured film can be improved.

(Photosensitive agent)
Next, the photosensitive agent (B) will be described. The photosensitive resin composition contains a photosensitive agent (B). Accordingly, a chemical reaction is caused by irradiation with ultraviolet rays or the like, so that it can be easily dissolved in an alkaline aqueous solution, and a difference in solubility can be provided.
Examples of the photosensitive agent (B) include esters of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Specific examples include ester compounds represented by formula (21) to formula (24). Two or more of these may be used. Q in formulas (21) to (24) represents a hydrogen atom, a 1,2-naphthoquinone-2-diazide-5-sulfonyl group, or a 1,2-naphthoquinone-2-diazide-4-sulfonyl group.

In the formula, Q is selected from a hydrogen atom, formula (25), and formula (26). Here, at least one of Q of each compound is represented by formula (25) or formula (26).
The content of the photosensitive agent (B) is preferably 1 to 50% by weight, and particularly preferably 5 to 30% by weight, based on the entire photosensitive resin composition. When the content is within the above range, the sensitivity is particularly excellent.

Although the said photosensitive resin composition is not specifically limited, It is preferable to use together the compound which has a phenolic hydroxyl group further. Thereby, higher sensitivity can be achieved. Furthermore, patterning can be performed with high resolution without developing residue (scum) during development.
Examples of such a compound having a phenolic hydroxyl group include those represented by the formulas (27) to (33).

Among these compounds having a phenolic hydroxyl group, those selected from the formula (34) are preferable. Two or more of these may be used. Thereby, especially sensitivity can be improved.

  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 polyamide resins (A), and 1-20 weight part is especially preferable. When the content is within the above range, the sensitivity is particularly excellent.

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

  The photosensitive resin composition of the present invention is preferably used by dissolving in a solvent and forming 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-methoxy A propionate etc. are mentioned, You may use individually or in mixture.

Next, an insulating film, a protective film, and an electronic device will be described.
The insulating film and protective film of the present invention can be obtained, for example, through the following steps.
The above-described photosensitive resin composition 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. and drying the coating film, actinic radiation is irradiated to a desired pattern shape (irradiation step). 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 portion irradiated with actinic radiation with a developer (development process). Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, diethylamine, di- Secondary amines such as n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary compounds such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as an ammonium salt and an aqueous solution in which an appropriate amount of a water-soluble organic solvent or a surfactant such as methanol or ethanol is added thereto can be suitably 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 rinse liquid, for example, distilled water is used.

Next, heat treatment is performed to form a closed ring structure (for example, an oxazole ring, an imide ring, etc.) to obtain a final pattern with high heat resistance (heating step). By this heating process, it can be set as the hardened | cured material of the above-mentioned resin composition.
Although heat processing temperature is not specifically limited, 150-400 degreeC is preferable and 200-300 degreeC is especially preferable.

  The cured product of the above-described photosensitive resin composition thus obtained is a protective film of a semiconductor element, an interlayer insulating film of a multilayer circuit, a cover coat film of a flexible copper-clad plate, by a support that forms the cured product. It can be used as a solder resist film, a liquid crystal alignment film, an interlayer insulating film of an element in a display device, and the like.

  Although the thickness of the said protective film is not specifically limited, 0.1-50 micrometers is preferable and 1-30 micrometers is especially preferable. When the thickness is within the above range, the balance between the workability and the film physical properties of the protective film is particularly excellent.

  Specifically, as a semiconductor device application, a passivation film obtained by forming a film composed of a cured product of the above-described photosensitive resin composition on a semiconductor element, and the above-described passivation film formed on a semiconductor element. A buffer coat film obtained by forming a film composed of a cured product of the photosensitive resin composition, a film composed of a cured product of the above-mentioned photosensitive resin composition on a circuit formed on a semiconductor element An interlayer insulating film obtained by the formation can be given.

  Specific examples of the display device application include a TFT interlayer insulating film, a TFT element flattening film, a color filter flattening film, a projection for an MVA type liquid crystal display, a cathode partition for an organic EL element, and the like. The method of use is by forming a film composed of a cured product of the photosensitive resin composition patterned on the substrate on which the display element and the color filter are formed in accordance with the semiconductor application by the above method. . High transparency is required for display device applications, especially interlayer insulating films and planarization films, but by introducing a post-exposure process before curing the photosensitive resin composition layer, transparency is improved. An excellent film can be obtained, which is more preferable in practical use.

  The electronic device of the present invention has the above-described protective film and / or insulating film, and specifically includes a semiconductor device, a liquid crystal display device, an organic EL device, an interlayer insulating film of a multilayer circuit, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.
Example 1
1. Synthesis of polyamide resin (A-1) 17.8 g (77.8 mmol) of diphenyl ether-4,4′-dicarboxylic acid and 23.3 g (155.6 mmol) of 1-hydroxy-1,2,3-benzotriazole 38.3 g (77.8 mmol) of a mixture of dicarboxylic acid derivatives obtained by reacting with bis (3-amino-4-hydroxy-2,5-dimethylphenyl) methane 18.0 g (62.9 mmol) ) And 3.2 g (37.5 mmol) of 5-amino-1H-tetrazole are placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. 2-Pyrrolidone (hereinafter referred to as NMP) 315.0 g was added and dissolved, and stirred at room temperature for 2 hours. Then, it was made to react at 75 degreeC for 12 hours using the oil bath. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and polyamide resin (A- 1) was obtained (content of nitrogen-containing cyclic compound 5.4% by weight).

2. Synthesis of photosensitizer 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene 51 g (120 mmol) and 1,2-naphthoquinonediazide-4- 72.5 g (270 mmol) of sulfonic acid chloride is dissolved in 450 ml of tetrahydrofuran, and 28.3 g (280 mmol) 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).

3. Production of photosensitive resin composition 100 g of synthesized polyamide resin (A-1) and 17 g of photosensitive diazoquinone (B-1) were dissolved in 300 g of γ-butyrolactone and then filtered through a 0.2 μm fluororesin filter. As a result, a positive photosensitive resin composition was obtained.

(Example 2)
Example 1 was repeated except that the following polyamide resin was used.
Synthesis of polyamide resin (A-2) In Example 1, instead of 3.2 g (37.5 mmol) of 5-amino-1H-tetrazole, 6.0 g of 3- (1H-tetrazol-5-yl) aniline (37 The polyamide resin (A-2) was obtained in the same manner as in Example 1 except that the amount was 0.5 mmol) (content of nitrogen-containing cyclic compound was 9.6% by weight).

(Example 3)
Example 1 was repeated except that the following polyamide resin was used.
Synthesis of polyamide resin (A-3) In the same manner as in Example 1, except that 5-amino-1H-tetrazole was changed to 1.6 g (18.7 mmol), the mixture was reacted at 75 ° C. for 12 hours. 3.2 g (18.7 mmol) of 5-ethynyl-isobenzofuran-1,3-dione dissolved in 11.5 g of NMP was added and stirred for 2 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 polyamide resin (A- 3) was obtained (content of nitrogen-containing cyclic compound 2.6% by weight).

Example 4
Example 1 was repeated except that the following polyamide resin was used.
Synthesis of polyamide resin (A-4) In the synthesis of the polyamide resin of Example 3, 0.6 g (7.5 mmol) of 5-amino-1H-tetrazole and 5-ethynyl-isobenzofuran-1,3-dione were added. 5.2g (
A polyamide resin (A-4) was obtained in the same manner as in Example 1 except that the amount was 30.0 mmol) (content of nitrogen-containing cyclic compound was 1.0% by weight).

(Example 5)
Example 1 was repeated except that the following polyamide resin was used.
Synthesis of polyamide resin (A-5) In the synthesis of the polyamide resin of Example 3, 4.0 g (30.0 mmol) of 5-amino-1H-tetrazole and 5-ethynyl-isobenzofuran-1,3-dione were added. A polyamide resin (A-5) was obtained in the same manner as in Example 1 except that the amount was 0.5 g (7.5 mmol) (content of nitrogen-containing cyclic compound was 6.6% by weight).

(Example 6)
Example 1 was repeated except that the following polyamide resin was used.
Synthesis of Polyamide Resin (A-6) In the synthesis of the polyamide of Example 1, 11.8 g (62.9 mmol) of bis (3-amino-4-hydroxy-2,5-dimethylphenyl) methane was 11.8 g ( 41.3 mmol) and a polyamide resin (A-6) was obtained in the same manner as in Example 1 except that 5.0 g (21.5 mmol) of bis (3-amino-4-hydroxyphenyl) ether was used. (Content of nitrogen-containing cyclic compound is 1.5% by weight).

(Example 7)
Example 1 was repeated except that the following polyamide resin was used.
Synthesis of polyamide resin (A-7) In the synthesis of the polyamide of Example 6, 5.0 g (21.5 mmol) of bis (3-amino-4-hydroxyphenyl) ether was converted to bis (3-amino-4-hydroxyphenyl). ) A polyamide resin (A-7) was obtained in the same manner as in Example 1 except that 5.0 g (21.5 mmol) of methane was used (content of nitrogen-containing cyclic compound: 3.1% by weight).

(Comparative Example 1)
Example 1 was repeated except that the following polyamide resin was used.
Synthesis of polyamide resin (a-1) In Example 1, 18.0 g (62.9 mmol) of bis (3-amino-4-hydroxy-2,5-dimethylphenyl) methane was converted to hexafluoro-2,2-bis. The same procedure as in Example 1 was conducted except that 16.2 g (62.9 mmol) of (3-amino-4-hydroxyphenyl) propane and 1.2 g (37.5 mmol) of 5-amino-1H-tetrazole were used. Thus, a polyamide resin (a-1) was obtained (content of nitrogen-containing cyclic compound: 2.2% by weight).

(Comparative Example 2)
Example 1 was repeated except that the following polyamide resin was used.
Synthesis of polyamide resin (a-2) 14.7 g (64.4 mmol) of diphenyl ether-4,4′-dicarboxylic acid and 19.2 g (128.8 mmol) of 1-hydroxy-1,2,3-benzotriazole 31.7 g (64.4 mmol) of a mixture of dicarboxylic acid derivatives obtained by reacting with bis (3-amino-4-hydroxy-2,5-dimethylphenyl) methane 22.4 g (78.2 mmol) ) In a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, and 185.5 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) is added and dissolved. For 2 hours. Then, it was made to react at 75 degreeC for 12 hours using the oil bath. Next, 5.9 g (34.6 mmol) of 5-ethynyl-isobenzofuran-1,3-dione dissolved in 11.5 g of NMP was added and stirred for 2 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was put into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and polyamide resin (a- 2) was obtained (content of nitrogen-containing cyclic compound 0.0% by weight).

１．銅配線との密着性
シリコンウエハー上にＴｉを５００Åの厚みでスパッタ膜を形成し、続いてＣｕを３，０００Åの厚さでスパッタ膜を形成した。各実施例および各比較例で得られたポジ型感光性樹脂組成物を上記のＣｕ上に硬化後５μｍになるようにスピンコーターを用いて塗布した後、ホットプレートにて１２０℃で４分間乾燥し、次にクリーンオーブンを用いて酸素濃度１，０００ｐｐｍ以下で、２５０℃／９０分で硬化を行い、硬化膜（保護膜）を得た。この硬化膜にカッターナイフにて１×１（ｍｍ）サイズの正方形が縦横１０列ずつ計１００個の碁盤目になるように作成した。このサンプルをＰＣＴ（プレッシャークッカー）試験；１２５℃１００％０．２ＭＰａの条件下５００時間連続処理した後、先の碁盤目を粘着テープで密着させ、一気に引き上げその剥がれた数を数えた。 The following evaluation was performed about the photosensitive resin composition obtained by each Example and each comparative example. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.

1. Adhesion with copper wiring A sputtered film with a thickness of 500 mm Ti was formed on a silicon wafer, and subsequently a sputtered film with a thickness of 3000 mm Cu was formed. The positive photosensitive resin composition obtained in each example and each comparative example was applied on the above Cu using a spin coater so as to have a thickness of 5 μm, and then dried on a hot plate at 120 ° C. for 4 minutes. Next, curing was performed at 250 ° C./90 minutes at an oxygen concentration of 1,000 ppm or less using a clean oven to obtain a cured film (protective film). A 1 × 1 (mm) size square was formed on this cured film with a cutter knife so as to form a total of 100 grids of 10 rows in length and width. This sample was subjected to a PCT (pressure cooker) test; continuous treatment for 500 hours under conditions of 125 ° C. and 100% 0.2 MPa, and then the previous grid was brought into close contact with an adhesive tape, and then the number of pieces peeled off was counted.

2. Mechanical properties The positive photosensitive resin compositions obtained in each Example and each Comparative Example were applied on a 6-inch silicon wafer using a spin coater so as to be 10 μm after curing, and then at 120 ° C. on a hot plate. The film was dried for 4 minutes, and then cured using a clean oven at an oxygen concentration of 1,000 ppm or less at 250 ° C./90 minutes to obtain a cured film. The obtained cured film was cut into a 10 mm strip with a dicing saw for each wafer, and then immersed in 2% hydrogen fluoride water to obtain a strip-like film peeled from the wafer. Next, the strip-like film was subjected to tensile measurement with a tensile tester at a speed of 5 mm / min, and the tensile elongation was evaluated.

3. Developability After coating the positive photosensitive resin composition obtained in each example and each comparative example on a silicon wafer using a spin coater, it was dried on a hot plate at 120 ° C. for 4 minutes to obtain a film thickness. A protective film of about 5 μm was obtained. Through this protective film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a left pattern and a blank pattern with a width of 0.88 to 50 μm are drawn) is irradiated with ultraviolet light using a high-pressure mercury lamp, and the exposure amount is changed. And irradiated.
Next, the exposed portion was dissolved and removed by immersing in an aqueous 2.38% tetramethylammonium hydroxide solution for 80 seconds, rinsed with pure water for 30 seconds, and then a 50 μm wide extraction pattern was observed (evaluation was n = 10). Each code is as follows.
A: All samples were patterned without scum.
A: 7 to 9 samples were patterned without scum.
Δ: Some scum was observed around the opening, but patterning was performed.
X: Very much scum or not patterned.

4). Flux resistance The patterned silicon wafer was cured in a clean oven at an oxygen concentration of 1,000 ppm or less at 250 ° C./90 minutes. Next, Tamura Kaken Co., Ltd. flux and BF-30 were apply | coated to this wafer on the conditions of 500 rpm / 5 second +1,000 rpm / 30 second with a spinner. In a reflow furnace, it was continuously passed twice under the conditions of 140 to 160 ° C./100 seconds (preheating) and 250 ° C./10 seconds. Next, after washing with xylene heated to 40 ° C. for 10 minutes, it was rinsed with isopropyl alcohol and dried. The film surface from which the flux was removed was observed with a metal microscope (evaluation was performed at n = 10). Each code is as follows.
A: All samples were free of wrinkles on the entire surface.
A: In 7 to 9 samples, there was no wrinkle on the entire surface.
Δ: Wrinkles were partly present.
X: Wrinkles were present on the entire surface.

As is clear from Table 1, in Examples 1 to 7, the protective film was peeled off, indicating that the adhesiveness with copper was excellent.
Moreover, Examples 1-7 were excellent also in the tensile elongation rate, and were excellent also in the film | membrane physical property.
In addition, Examples 1 to 7 were particularly excellent in developability.
Moreover, Examples 1-7 were excellent also in flux tolerance, and even if it hardened | cured at the low temperature of 250 degreeC, it was shown that there is no generation | occurrence | production of a wrinkle etc. in a protective film and it is excellent in low-temperature curability.

Moreover, the photosensitive resin composition obtained in each Example was apply | coated on the semiconductor element. The coated photosensitive resin composition was pre-baked at 60 to 130 ° C., dried the coating film, and then irradiated with ultraviolet rays in a desired pattern shape. Next, after a relief pattern was obtained by dissolving and removing the ultraviolet irradiation portion with a developer, heat treatment was performed to obtain a protective film (also functioning as an insulating film). After forming the protective film, solder balls were formed, and a semiconductor device was obtained through a chip dicing process, a chip mounting process, and a semiconductor sealing molding process.
The electronic device equipped with the semiconductor device obtained in this way operated normally.

  The photosensitive resin composition of the present invention can be suitably used for a protective film, an insulating film, and the like in the field of display elements represented by the semiconductor field or liquid crystal.

FIG. 1 is a cross-sectional view illustrating an example of a semiconductor device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Silicon wafer 2 Aluminum pad 3 Protective film 31 Passivation film 32 Buffer coat film 33 Recessed part 4 Conductor part 41 Metal film 42 Pad part 5 Barrier metal 6 Insulating film 7 Solder bump 10 Semiconductor device

Claims (11)

A photosensitive resin composition comprising a polyamide resin (A) and a photosensitive agent (B),
The polyamide resin (A) has a polybenzoxazole precursor structure represented by the following general formula (1), and has at least one nitrogen-containing cyclic compound at the side chain and terminal of the polyamide resin (A). A photosensitive resin composition characterized by the above.

(In the formula, A represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —
NHCO-, a single bond, -C (CF _{3) 2} - is an organic group selected from, B is an organic group. R ¹ is any ^one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. R ² 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. n is 2 to 500. )   The photosensitive resin composition according to claim 1, wherein the nitrogen-containing cyclic compound includes a tetrazole group. The photosensitive resin composition according to claim 2, wherein the nitrogen-containing cyclic compound having a tetrazole group includes at least one of compounds represented by formula (2-1) and formula (2-2).

  4. The photosensitive resin composition according to claim 1, wherein the content of the nitrogen-containing compound is 1.0 to 10.0% by weight of the entire polyamide resin (A).   The photosensitive resin composition according to any one of claims 1 to 4, wherein any one of the ends of the polyamide resin (A) is an organic group having a triple bond. The photosensitive resin composition according to any one of claims 1 to 5, wherein R ¹ of the polyamide resin (A) is an alkyl group or an alkoxy group, and R ² is an alkyl group or an alkoxy group.   An insulating film comprising a cured product of the photosensitive resin composition according to claim 1.   A protective film comprising a cured product of the photosensitive resin composition according to claim 1.   The protective film according to claim 8, which is used as a protective film for a semiconductor element or a liquid crystal display element.   An electronic apparatus comprising the protective film according to claim 8.   An electronic apparatus comprising the insulating film according to claim 7.

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