JP2011043573A - Photosensitive resin composition, cured film, protective film, insulating film and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which has high sensitivity and high resolution to g-line and i-line, can be developed with a general-purpose generator, and satisfies excellent strong alkali resistance. <P>SOLUTION: The positive photosensitive resin composition contains 100 pts.wt. of a resin (A) having a benzoxazole precursor structure, 0.1-100 pts.wt. of a polyamide resin constituted of a structure represented by general formula (1), and 1-50 pts.wt. of a photosensitizer (C), wherein X<SP>1</SP>and Y<SP>1</SP>are an organic group; R<SP>1</SP>and R<SP>2</SP>are independently H or a 1-15C organic group; and a denotes a polymerization degree and is 1-500. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protective films and interlayer insulating films of semiconductor elements.
Here, in order to simplify the process when a polybenzoxazole resin or a polyimide resin is used, a positive photosensitive resin composition in which a diazoquinone compound of a photosensitive material is combined with these resins is also used (for example, patents). Reference 1).
When these positive photosensitive resins are used in an actual process, the problem is exposure characteristics, and the exposure time is particularly important among them. That is, in order to improve the throughput, a positive photosensitive resin that is highly sensitive and can be exposed to g-line and i-line in a short time is desired. In addition, since a fine pattern needs to be formed with the miniaturization of a semiconductor, a positive photosensitive resin having a high resolution is desired.
Further, it is strongly desired that development can be performed with a 2.38% tetramethylammonium hydroxide aqueous solution that is generally widely used as a developer.
Furthermore, in recent years, from the viewpoint of short delivery time and low cost, surface mounting type semiconductor wafers in which Ni and Au layers are formed on the pad portion of a semiconductor wafer using electroless plating and solder balls are mounted with a laser are increasing. Yes. In this electroless plating step, there is a zincate treatment in which a pH is 13 or more, and a positive photosensitive resin composition excellent in resistance to a strong alkaline aqueous solution is required.
However, the conventional positive photosensitive resin composition can be developed with a general-purpose developer with high sensitivity and high resolution for g-line and i-line, and at the same time satisfying the performance excellent in strong alkaline aqueous solution resistance. It was difficult.

JP-A-1-46862

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a general-purpose developer having high sensitivity and high resolution for g-line and i-line when applied to a positive photosensitive resin composition. It is an object of the present invention to provide a positive-type photosensitive resin composition that can be developed in the above-described manner and that simultaneously satisfies the performance excellent in resistance to a strong alkaline aqueous solution.

（２）一般式（１）中のＸ^１が、炭素数１〜２０の脂肪族基及び／または下記一般式（２）の構造単位を有するものである、（１）に記載のポジ型感光性樹脂組成物。

（３）一般式（１）中のＹ^１が、炭素数１〜１５の脂肪族基を含むものである、（１）または（２）に記載の感光性樹脂組成物。
（４）前記ベンゾオキサゾール前駆体構造を有する樹脂（Ａ）が、一般式（３）で示される樹脂である（１）ないし（３）のいずれか記載のポジ型感光性樹脂組成物、

（５）一般式（３）で示される樹脂中のＸ^２が、下記式（４）および／又は下記式（５）の構造単位を有する、（４）に記載のポジ型感光性樹脂組成物、

（６）前記ベンゾオキサゾール前駆体構造を含む樹脂（Ａ）が、一般式（６）で示される樹脂である、（１）ないし（５）のいずれかに記載のポジ型感光性樹脂組成物、

（式中、Ｙ^４およびＹ^５は、独立に有機基であり、Ｒ^１７およびＲ^１８は、独立に水酸基、カルボキシル基、Ｏ−Ｒ^１９、ＣＯＯ−Ｒ^１９のいずれかである。ｆ、ｈは０〜８の整数である。Ｒ^１９は、炭素数１〜１５の有機基である。ｐは０．６以上０．９５以下である。ｔは重合度を示し、１〜５００である。）
（７）前記一般式（６）中のＹ^４およびＹ^５が、下記式（７）からなる群より選ばれる構
造単位を含むものである、（６）に記載のポジ型感光性樹脂組成物、

（８）前記一般式（６）で示される樹脂の少なくとも一方の末端のアミノ基に、アルケニル基またはアルキニル基を少なくとも１個有する脂肪族基、または環式化合物基を含む酸無水物を反応させ、前記一般式（６）で示される樹脂の末端に不飽和基を導入したものである、（６）または（７）に記載のポジ型感光性樹脂組成物、
（９）前記一般式（６）で示される樹脂の側鎖および他方の末端の少なくとも一方に窒素含有環状化合物を含む酸無水物を反応させ、前記一般式（６）で示される樹脂に窒素含有環状化合物を導入したものである、（６）ないし（８）のいずれかに記載のポジ型感光性樹脂組成物、
（１０）さらに、フェノール性水酸基を有する化合物（Ｄ）を含むものである、（１）ないし（９）のいずれかに記載のポジ型感光性樹脂組成物、
（１１）前記フェノール性水酸基を有する化合物（Ｄ）が、下記式（８）からなる群より選ばれる少なくとも１種以上を含む、（１０）に記載のポジ型感光性樹脂組成物、

（１２）（１）ないし（１１）のいずれかに記載のポジ型感光性樹脂組成物の硬化物で構成されていることを特徴とする硬化膜、
（１３）（１２）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、
（１４）（１２）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、
（１５）（１２）に記載の硬化膜を有することを特徴とする半導体装置、
（１６）（１２）に記載の硬化膜を有することを特徴とする表示体装置。 Such an object is achieved by the following (1) to (16).
(1) 100 parts by weight of a resin (A) having a benzoxazole precursor structure;
0.1 to 100 parts by weight of a polyamide resin (B) including a structure represented by the following general formula (1), 1 to 50 parts by weight of a photosensitive agent (C),
A positive photosensitive resin composition, comprising:

(2) The positive photosensitive film according to (1), wherein X ¹ in the general formula (1) has an aliphatic group having 1 to 20 carbon atoms and / or a structural unit represented by the following general formula (2). Resin composition.

(3) ^{Y 1} in formula (1) is intended to include an aliphatic group having 1 to 15 carbon atoms, a photosensitive resin composition according to (1) or (2).
(4) The positive photosensitive resin composition according to any one of (1) to (3), wherein the resin (A) having the benzoxazole precursor structure is a resin represented by the general formula (3),

(5) The positive photosensitive resin composition according to (4), wherein X ² in the resin represented by the general formula (3) has a structural unit represented by the following formula (4) and / or the following formula (5). ,

(6) The positive photosensitive resin composition according to any one of (1) to (5), wherein the resin (A) containing the benzoxazole precursor structure is a resin represented by the general formula (6),

(Wherein Y ⁴ and Y ⁵ are independently an organic group, and R ¹⁷ and R ¹⁸ are each independently a hydroxyl group, a carboxyl group, O—R ¹⁹ or COO—R ¹⁹ ; f, h Is an integer of 0 to 8. R ¹⁹ is an organic group having 1 to 15 carbon atoms, p is 0.6 or more and 0.95 or less, t indicates a degree of polymerization, and 1 to 500. )
(7) The positive photosensitive resin composition according to (6), wherein Y ⁴ and Y ⁵ in the general formula (6) include a structural unit selected from the group consisting of the following formula (7):

(8) reacting at least one terminal amino group of the resin represented by the general formula (6) with an acid anhydride containing an aliphatic group having at least one alkenyl group or alkynyl group, or a cyclic compound group; The positive photosensitive resin composition according to (6) or (7), wherein an unsaturated group is introduced at the terminal of the resin represented by the general formula (6),
(9) The resin represented by the general formula (6) is reacted with an acid anhydride containing a nitrogen-containing cyclic compound at least one of the side chain and the other end of the resin, and the resin represented by the general formula (6) contains nitrogen. A positive photosensitive resin composition according to any one of (6) to (8), wherein a cyclic compound is introduced;
(10) The positive photosensitive resin composition according to any one of (1) to (9), further comprising a compound (D) having a phenolic hydroxyl group,
(11) The positive photosensitive resin composition according to (10), wherein the compound (D) having a phenolic hydroxyl group contains at least one selected from the group consisting of the following formula (8):

(12) A cured film comprising a cured product of the positive photosensitive resin composition according to any one of (1) to (11),
(13) A protective film comprising the cured film according to (12),
(14) An insulating film comprising the cured film according to (12),
(15) A semiconductor device comprising the cured film according to (12),
(16) A display device having the cured film according to (12).

  According to the present invention, when applied to a positive-type photosensitive resin composition, development with a general-purpose developer is possible with high sensitivity and high resolution for g-line and i-line, and resistance to strong alkaline aqueous solution. Provided is a positive photosensitive resin composition that simultaneously satisfies excellent performance.

The positive photosensitive resin composition of the present invention comprises 100 parts by weight of a resin (A) having a benzoxazole precursor structure and a polyamide resin (B) 0.1-100 containing a structure represented by the following general formula (1) It contains 1 part by weight and 1 to 50 parts by weight of a photosensitive agent (C).

  In addition, the protective film and the insulating film of the present invention are a cured film composed of a cured product of the positive photosensitive resin composition. Furthermore, the semiconductor device and display device of the present invention are characterized by having the cured film.

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

The positive photosensitive resin composition of the present invention is a polyamide resin (B) 0.1 to 0.1 containing a structure represented by the general formula (1) with respect to 100 parts by weight of the resin (A) having a benzoxazole precursor structure. By including 100 parts by weight, the carboxyl group (—COOR ¹ , —COOR ² ) of the polyamide resin (B) represented by the general formula (1) strongly interacts with the metal on the surface of the semiconductor wafer. The tolerance with respect to the strong alkaline aqueous solution of the cured film comprised with the cured | curing material of a resin composition can be improved.

  When the content of the polyamide resin (B) having the structure represented by the general formula (1) is less than 0.1 parts by weight, the strongly alkaline aqueous solution resistance of the cured product of the positive photosensitive resin composition is improved. When the amount is larger than 100 parts by weight, the sensitivity and resolution of the positive photosensitive resin composition are lowered.

X ¹ of the polyamide resin (B) including the structure represented by the general formula (1) according to the present invention is not particularly limited, but an aliphatic group having 1 to 20 carbon atoms and / or the following general formula ( It is preferable to have the structural unit represented by 2), and one or more structural units may be included. Thereby, the tolerance with respect to the strong alkaline aqueous solution of the cured film comprised with the hardened | cured material of positive type photosensitive resin composition can be improved more effectively.

Y ¹ of the polyamide resin (B) including the structure represented by the general formula (1) according to the present invention is not particularly limited, but is preferably an aliphatic group having 1 to 15 carbon atoms. You may have a seed or two or more. Thereby, the tolerance with respect to the strong alkaline aqueous solution of the cured film comprised with the hardened | cured material of positive type photosensitive resin composition can be improved more effectively.

R ¹ and R ² of the polyamide resin (B) including the structure represented by the general formula (1) according to the present invention are:
Although it is a hydrogen atom and a C1-C15 organic group independently, the hydrogen atom and C1-C10 organic group which are excellent in the tolerance with respect to strong alkaline aqueous solution are preferable.

  The degree of polymerization a of the polyamide resin (B) including the structure represented by the general formula (1) according to the present invention is 1 to 500, but 2 to 400 which is excellent in resistance to a strong alkaline aqueous solution is preferable.

  The resin (A) having a benzoxazole precursor structure according to the present invention is not particularly limited, but is represented by the general formula (3) from the viewpoint of the heat resistance of the cured product of the positive photosensitive resin composition. It preferably includes a structure.

The resin (B) having the benzoxazole precursor structure is, as shown by the general formula (3), a tetracarboxylic acid anhydride having a structure of silicone diamine represented by Z and Y ³ , trimellitic acid, if necessary. A structure obtained by reacting a compound selected from an anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative and the like can be included. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

In the resin represented by the general formula (3), R ³ and R ⁴ are each independently a hydrogen atom, an organic group having 1 to 15 carbon atoms, but 2.38% tetramethylammonium hydroxide as a developer. A hydrogen atom and an organic group having 1 to 10 carbon atoms that are excellent in solubility in an aqueous solution are preferable.

In the resin represented by the general formula (3), R ⁵ and R ⁶ are independently a hydroxyl group, a carboxyl group, O—R ⁷ , and COO—R ⁷ . Here, R ⁷ is independently an organic group having 1 to 15 carbon atoms, and is introduced for the purpose of adjusting the solubility of a hydroxyl group and a carboxyl group in an alkaline aqueous solution. Examples of R ⁷ 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.

Further, X ² in the resin represented by the general formula (3) is an organic group and is not particularly limited, but is preferably a structural unit of the following formula (4) and / or the following formula (5). These may be used, and these may be used alone or in combination of two or more.

In the resin represented by the general formula (3), Y ² and Y ³ are not particularly limited as long as they are organic groups. For example, aromatic compounds such as benzene ring and naphthalene ring, bisphenols, Heterocyclic compounds such as pyrroles, pyridines and furans are exemplified, and more specifically, those represented by the following formula (9) can be preferably exemplified. These may be used alone or in combination of two or more.

Among these, those represented by the following formulas (10) and (11) are preferable from the viewpoint of solubility in a developer, dielectric properties after curing, heat resistance, electrical properties, mechanical properties, and the like. Regarding the structure derived from tetracarboxylic dianhydride in the following formula (10), the position where the C═O group is bonded to both is in the meta position, and both are in the para position. A structure including each of the para positions may be used.

The resin (A) having a benzoxazole precursor structure according to the present invention is not particularly limited, but is represented by the general formula (6) from the viewpoint of the heat resistance of the cured product of the positive photosensitive resin composition. It is particularly preferred to include a structure. That is, the resin (A) having a benzoxazole precursor structure according to the present invention includes 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3′-diamino- which are bisaminophenols. 4-4'-
Those having a structural unit obtained by reacting biphenyldiol with a carboxylic acid derivative such as dicarboxylic acid or dicarboxylic acid chloride are particularly preferred. At this time, when dicarboxylic acid is used, an active ester type carboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like. .

In the general formula (6), the substituents Y ⁴ and Y ⁵ , O—R ¹⁹ , and COO—R ¹⁹ are a hydroxyl group and a carboxyl group having 1 to 15 carbon atoms for the purpose of adjusting solubility in an alkaline aqueous solution. It is a group protected by R ¹⁹ which is an organic group. Examples of R ¹⁹ 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.

  P in the general formula (6) represents a ratio of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in bisaminophenol constituting the polyamide resin, and is 0.6 to 0.95. Is preferable, and 0.7 to 0.9 is particularly preferable. By setting the above range, the positive photosensitive resin composition has high sensitivity to g-line and i-line and high resolution, can be developed with a general-purpose developer, and has all the performances excellent in strong alkali resistance at the same time. It becomes possible to satisfy.

  1-500 are preferable and, as for repeating unit t in the said General formula (6), 3-370 are especially preferable. By setting it as the said range, it becomes possible to make workability and a cured film physical property compatible.

Further, the resin (A) having a benzoxazole precursor structure according to the present invention undergoes dehydration and ring closure when heated at about 200 to 400 ° C. to obtain a heat-resistant resin in the form of a polybenzoxazole resin.

Y ⁴ and Y ⁵ in the general formula (6) are not particularly limited, and examples thereof are the same as Y ² and Y ³ in the general formula (3).

Y ⁴ and Y ⁵ in the general formula (6) preferably have a structural unit represented by the following formula (7). By having the structural unit, the positive photosensitive resin composition of the present invention is highly sensitive to g-line and i-line, can be developed with a general-purpose developer, and is excellent in strong alkali resistance. It becomes possible to satisfy all the performances simultaneously.

  The benzoxazole resin (A) represented by the general formula (1) according to the present invention is an acid anhydride containing a terminal amino group, an aliphatic group having at least one alkenyl group or alkynyl group, or a cyclic compound group. You may seal using. Thereby, the mechanical characteristics of the cured film can be further 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 (12) and formula (13). ) And the like. These may be used alone or in combination of two or more.

  Among these, a group selected from the formula (14) is particularly preferable. Thereby, especially storability can be improved.

Further, the method is not limited, and the terminal acid contained in the benzoxazole resin (A) represented by the general formula (1) is an aliphatic group or cyclic group having at least one alkenyl group or alkynyl group. An amine derivative containing a compound group can be used to seal the end as an amide.

  The benzoxazole resin (A) represented by the general formula (1) according to the present invention may have a nitrogen-containing cyclic compound in at least one of the side chain and the other end. Thereby, adhesiveness with a metal wiring (especially copper wiring) etc. can be improved. The reason for this is that when one end of the resin (A) having a benzoxazole precursor structure is an organic group having an unsaturated group, the resin reacts, so the mechanical properties such as tensile elongation of the cured film are excellent, This is because when the nitrogen-containing cyclic compound is present in at least one of the side chain and the other end, the nitrogen-containing cyclic compound reacts with the metal wiring of copper and copper alloy, so that the adhesion is excellent.

  Examples of the nitrogen-containing cyclic compound include 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazoyl) amino group, 4- (1H-pyrazoyl) amino group, and 5- (1H-pyrazoyl). Amino group, 1- (3-1H-pyrazoyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazoyl) methylamino group, (1H-tetrazol-5-yl) ) Amino group, 1- (1H-tetrazol-5-yl) methyl-amino group, 3- (1H-tetrazol-5-yl) benz-amino group and the like. Among these, the compound selected by the formula (15) is preferable. Thereby, especially adhesiveness with the metal wiring of copper and a copper alloy can be improved more.

本発明のポジ型感光性樹脂組成物は、感光剤（Ｃ）を含む。これにより、化学線の照射により化学反応を生じ、化学線照射部（以下、露光部とする。）は、アルカリ水溶液に溶解しやすくなり、化学線未照射部（以下、未露光部とする。）との溶解度の差異を設けることができる。

The positive photosensitive resin composition of the present invention contains a photosensitive agent (C). Thereby, a chemical reaction is caused by irradiation with actinic radiation, and the actinic radiation irradiated part (hereinafter referred to as an exposed part) is easily dissolved in an alkaline aqueous solution, and is referred to as an actinic radiation non-irradiated part (hereinafter referred to as an unexposed part). ) And a difference in solubility.

  Examples of the photosensitive agent (C) 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 (16) to formula (21). Two or more of these may be used. Q in the formulas (16) to (21) represents a hydrogen atom, a 1,2-naphthoquinone-2-diazide-5-sulfonyl group, or a 1,2-naphthoquinone-2-diazide-4-sulfonyl group.

式中Ｑは、水素原子、式（２０）、式（２１）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（２０）、式（２１）である。

In the formula, Q is selected from a hydrogen atom, formula (20), and formula (21). Here, at least one of Q of each compound is represented by formula (20) or formula (21).

  The addition amount of the photosensitizer (C) according to the present invention is 1 to 50 parts by weight with respect to 100 parts by weight of the resin (A) having the benzoxazole precursor structure. Preferably it is 10-40 weight part. By setting the addition amount within the above range, it is possible to achieve both high sensitivity and high resolution of the positive photosensitive resin composition.

  Furthermore, the positive photosensitive resin composition of the present invention can be used in combination with a compound (D) having a phenolic hydroxyl group so that it can be patterned with high sensitivity and without scum.

  Specific examples of the structure include those represented by the following formula (8). These may be used alone or in combination of two or more.

  Although content of the compound (D) which has the said phenolic hydroxyl group is not specifically limited, 1-35 weight part is preferable with respect to 100 weight part of resin (A) which has the said benzoxazole precursor structure, More preferably 1 to 25 parts by weight. When the addition amount is in the above range, the occurrence of scum is further suppressed during development, and the sensitivity is improved by promoting the solubility of the exposed area.

  If necessary, the positive photosensitive resin composition of the present invention may contain additives such as a leveling agent, a silane coupling agent, a coupling agent such as a titanate coupling agent, and their respective reactants.

  The positive photosensitive resin composition of the present invention is preferably dissolved in a solvent and used in the form of a varnish. Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypro Pionate etc. are mentioned, You may use individually or in mixture.

Next, the manufacturing method of the cured film of this invention is demonstrated.
The cured film of this invention can be obtained through the following processes, for example.
The positive photosensitive composition described above is applied to a support (for example, a silicon wafer, a ceramic substrate, an aluminum substrate, etc.) (application step). When applied on the semiconductor element, the applied amount is applied so that the thickness of the cured film is, for example, 0.1 to 30 μm. If the thickness of the film is less than the lower limit, it may be difficult to fully function as a protective (surface) film of a semiconductor element. If the upper limit is exceeded, a fine processing pattern may be obtained. It can be difficult. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like.

Next, for example, after pre-baking at 60 to 130 ° C. to dry the coating film, actinic radiation is irradiated to a desired pattern shape (exposure process). As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used, but those having a wavelength of, for example, 200 to 500 nm are preferable.

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

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

Next, heat treatment is performed to form a closed ring structure (for example, an oxazole ring, an imide ring, etc.) to obtain a patterned cured film rich in heat resistance (heating step).
Although heat processing temperature is not specifically limited, 150-380 degreeC is preferable and 250-380 degreeC is especially preferable.

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

  Examples of the use of the semiconductor device 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 on the passivation film. A protective film such as a buffer coat film formed; 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; , Α-ray blocking film, planarization film, protrusion (resin post), partition wall, and the like.

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

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

Example 1
[Synthesis of Resin (A) Having Benzoxazole Precursor Structure]
Dicarboxylic acid obtained by reacting 21.43 g (0.083 mol) of diphenyl ether-4,4′-dicarboxylic acid with 22.43 g (0.166 mol) of 1-hydroxy-1,2,3-benzotriazole 40.87 g (0.083 mol) of a mixture of derivatives, 32.96 g (0.090 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane and 3,3′-diamino-4 , 4'-biphenyldiol 2.16 g (
0.010 mol) was put into a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and 296.96 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, 6.98 g (0.0425 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added. The reaction was terminated by stirring for a period of time. After the reaction mixture is filtered, the reaction mixture is put into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the target benzoxazole precursor. A resin (A-1) having a body structure was obtained.

[Synthesis of Polyamide Resin (B)]
23.80 g (0.096 mol) of 3,3′-diaminodiphenylsulfone, 26.20 g (0.132 mol) of 1,2,3,4-butanetetracarboxylic dianhydride and N-methyl-2-pyrrolidone 200.00 g was placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, dissolved, and then reacted at 35 ° C. for 5 hours using an oil bath. It was. Let the obtained polyamide solution be (B-1).

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

[Preparation of positive photosensitive resin resin composition]
After dissolving 10 g of synthesized pobenzoxazole precursor (A-1) 10 g, synthesized polyamide solution (B-1) 1.25 g, synthesized photosensitizer (C-1) 2 g in γ-butyrolactone 70 g And filtering with a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition.

<< Example 2 >>
In the synthesis of the resin (A) having the benzoxazole precursor structure of Example 1, 25.64 g (0.070 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was added. ), The amount of 3,3′-diamino-4,4′-biphenyldiol added was changed to 6.49 g (0.030 mol) to synthesize a resin (A) having a benzoxazole precursor structure (A -2). Further, except for the synthesis of the resin (A) having a benzoxazole precursor structure, the synthesis of the polyamide resin (B), the synthesis of the photosensitizer, and the production of the positive photosensitive resin composition were performed in the same manner as in Example 1. .

Example 3
Resin having a benzoxazole precursor structure (A) in the same manner as in Example 1 except that 0.5 g of phenol compound (D-1) was further added in the production of the positive photosensitive resin resin composition of Example 1. ), A polyamide resin (B), a photosensitizer, and a positive photosensitive resin composition.

Example 4
Resin having a benzoxazole precursor structure in the same manner as in Example 3 except that 2.5 g of the synthesized polyamide solution (B-1) was added in the production of the positive photosensitive resin resin composition of Example 3. Synthesis of A), synthesis of polyamide resin (B), synthesis of photosensitive agent, and preparation of a positive photosensitive resin composition were performed.

Example 5
In the synthesis of the polyamide resin (B) of Example 3, 23.80 g (0.096 mol) of 3,3′-diaminodiphenylsulfone was converted to 24.00 g (0.082 g) of 1,3-bis (3-aminophenoxy) benzene. Mol) was changed from 26.20 g (0.132 mol) of 1,2,3,4-butanetetracarboxylic dianhydride to 26.00 g (0.084 mol) of 4,4′-oxydiphthalic anhydride. Thus, a polyamide solution (B-2) was synthesized. Moreover, except the synthesis | combination of the polyamide resin (B), the synthesis | combination of resin (A) which has a benzoxazole precursor structure, the synthesis | combination of a photosensitizer, and preparation of the positive photosensitive resin composition were performed like Example 3. .

≪Comparative example 1≫
Synthesis of a resin (A) having a benzoxazole precursor structure and photosensitivity in the same manner as in Example 1 except that the polyamide solution (B-1) is not added in the production of the positive photosensitive resin composition of Example 1. Synthesis of the agent and preparation of a positive photosensitive resin composition were performed.

≪Comparative example 2≫
In the synthesis of the resin (A) having the benzoxazole precursor structure of Example 1, the amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane added was 36.63 g (0.100 mol). ), 3,3′-diamino-4,4′-biphenyldiol was changed to no addition, and a resin (A) having a benzoxazole precursor structure was synthesized (A-3), and a polyamide solution (B-1 ) Was added in the same manner as in Example 1 except that a photosensitizer was synthesized and a positive photosensitive resin composition was prepared.

The following evaluation was performed about the positive photosensitive resin composition obtained by each Example and the comparative example. The evaluation items are shown together with the contents. The obtained results are shown in Tables 1 and 2.
1. g-Line Sensitivity and Resolution The positive photosensitive resin composition obtained in each Example and Comparative Example was applied on a silicon wafer using a spin coater, and then dried on a hot plate at 120 ° C. for 4 minutes to form a film. Thickness about 1
A 0 μm coating film was obtained. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: remaining pattern and blank pattern with a width of 0.88 to 50 μm are drawn), Nikon g-line stepper NSR-1505G3A The exposure was performed by increasing the exposure amount in steps of 100 mJ / cm ² to 10 mJ / cm ² . Next, the exposed portion was dissolved and removed by immersing in an aqueous 2.38% tetramethylammonium hydroxide solution for 60 seconds, then rinsed with pure water for 30 seconds, and the amount of exposure (g (Line sensitivity) and the pattern width (i-line resolution) that was satisfactorily opened with the exposure amount at which the pattern was formed in the unexposed area were calculated.

2. i-line sensitivity and resolution The positive photosensitive resin composition obtained in each Example and Comparative Example was applied on a silicon wafer using a spin coater, and then dried on a hot plate at 120 ° C. for 4 minutes to form a film. A coating film having a thickness of about 10 μm was obtained. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a left pattern and a blank pattern having a width of 0.88 to 50 μm are drawn), and Nikon's i-line stepper NSR-4425i The exposure was performed by increasing the exposure amount in steps of 100 mJ / cm ² to 10 mJ / cm ² . Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, followed by rinsing with pure water for 30 seconds, and the exposure amount (i (Line sensitivity) and the pattern width (i-line resolution) that was satisfactorily opened with the exposure amount at which the pattern was formed in the unexposed area were calculated.

3. Resistance to zincate treatment solution A sputtered film having a thickness of 500 mm Ti was formed on a silicon wafer, and subsequently a sputtered film having a thickness of 3,000 mm Al was formed. The positive photosensitive resin composition obtained in each example and each comparative example was applied on the silicon wafer using a spin coater, and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a film thickness of about 10 μm. A coating film was obtained. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: remaining pattern and blank pattern with a width of 0.88 to 50 μm are drawn), Nikon g-line stepper NSR-1505G3A The exposure was performed with the exposure amount fixed at 320 mJ / cm ² . Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then rinsed with pure water for 30 seconds. The patterned silicon wafer was cured in a clean oven at an oxygen concentration of 1,000 ppm or less at 150 ° C./30 minutes and 320 ° C./30 minutes. Next, this silicon wafer was immersed in a zincate treatment solution (Meltex FZ-7350, manufactured by Meltex Co., Ltd.) at 25 ° C./15 minutes. Next, after washing with pure water for 5 minutes, it was dried and the film surface was observed with a metallographic microscope (evaluation was performed at n = 10). Each code is as follows.
A: No peeling was observed in all samples.
○: No peeling was observed in 7 to 9 samples.
Δ: Slight peeling was observed in all samples.
X: Violent peeling was observed in all samples.

  In parentheses in Tables 1 and 2, the amount of the polyamide resin (B) added relative to 100 parts by weight of the resin (A) having a benzoxazole precursor structure is shown in parts by weight.

  As shown in Table 1 and Table 2, the positive photosensitive resin compositions obtained in Examples 1 to 5 are excellent in sensitivity to g-line and i-line, exhibit high resolution, and have a cured film. It was confirmed that the zincate treatment solution was excellent in resistance.

Claims (16)

100 parts by weight of a resin (A) having a benzoxazole precursor structure;
0.1 to 100 parts by weight of a polyamide resin (B) including a structure represented by the following general formula (1), 1 to 50 parts by weight of a photosensitive agent (C),
A positive photosensitive resin composition comprising:

The positive photosensitive resin composition according to claim 1, wherein X ¹ in the general formula (1) has an aliphatic group having 1 to 20 carbon atoms and / or a structural unit represented by the following general formula (2). object.

Y ¹ in formula (1) is intended to include an aliphatic group having 1 to 15 carbon atoms, a photosensitive resin composition according to claim 1 or 2. The positive photosensitive resin composition according to claim 1, wherein the resin (A) having the benzoxazole precursor structure is a resin represented by the general formula (3).

X ² in the resin represented by the general formula (3) has a structural unit of the following formula (4) and / or the following formula (5), the positive photosensitive resin composition of claim 4.

The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the resin (A) containing the benzoxazole precursor structure is a resin represented by the general formula (6).

The positive photosensitive resin composition according to claim 6, wherein Y ⁴ and Y ⁵ in the general formula (6) contain a structural unit selected from the group consisting of the following formula (7).

The amino group at least one terminal of the resin represented by the general formula (6) is reacted with an aliphatic anhydride having at least one alkenyl group or alkynyl group, or an acid anhydride containing a cyclic compound group, The positive photosensitive resin composition according to claim 6 or 7, wherein an unsaturated group is introduced at the terminal of the resin represented by formula (6). At least one of the side chain and the other end of the resin represented by the general formula (6) is reacted with an acid anhydride containing a nitrogen-containing cyclic compound, and the resin represented by the general formula (6) is reacted with a nitrogen-containing cyclic compound. The positive photosensitive resin composition according to claim 6, which is introduced. Furthermore, the positive photosensitive resin composition in any one of Claim 1 thru | or 9 which contains the compound (D) which has a phenolic hydroxyl group. The positive photosensitive resin composition of Claim 10 in which the compound (D) which has the said phenolic hydroxyl group contains at least 1 or more types chosen from the group which consists of following formula (8).

  A cured film comprising a cured product of the positive photosensitive resin composition according to claim 1.   A protective film comprising the cured film according to claim 12.   An insulating film comprising the cured film according to claim 12.   A semiconductor device comprising the cured film according to claim 12. A display device comprising the cured film according to claim 12.