JP2013076748A - Photosensitive resin composition, cured film, protective film, insulator film, and semiconductor device and display body device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in storage stability and sensitivity which can be used for a protective film, an insulator film, and a semiconductor device and a display body device using the same.SOLUTION: A photosensitive resin composition includes at least (A) alkali-soluble resin, (B) photosensitive agent, (C) ketone compound, and (D) solvent. There are also provided a cured film, a protective film, an insulator film comprising a cured product using the photosensitive resin composition. There are also provided a semiconductor device and a display device having the cured film, the insulator film, and the protective film.

Description

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

Conventionally, a protective film and an insulating film of a semiconductor element include a polyimide resin having excellent heat resistance and excellent electrical characteristics and mechanical characteristics, and a polybenzoxazole resin which is considered to have good moisture resistance reliability in addition to the above characteristics. It was used. In addition, polyimide resin, polybenzoxazole resin, and their precursor resins themselves are given photosensitivity so that a part of the relief pattern creation process can be simplified. A photosensitive resin composition has been developed that has high performance, excellent electrical and mechanical properties, and is effective in shortening the process and improving yield (productivity). It also has potential as a composition.
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 and a diazoquinone compound as a photosensitizer as an alkali-soluble resin.

  The polyimide precursor resin and polybenzoxazole precursor resin in the photosensitive resin composition in which the relief pattern has been formed are finally dehydrated and ring-closed by curing at around 200 ° C. to 350 ° C., and a polyimide resin rich in heat resistance, It becomes a polybenzoxazole resin. In recent years, in addition to miniaturization and high integration of semiconductor elements, it has become important to improve production efficiency. A highly sensitive polyimide precursor resin composition and polybenzoxazole precursor that can form a fine pattern with a small exposure amount. The need for a body resin composition has been expected.

In order to form a fine pattern with a small exposure amount, several methods are known. For example, by improving the ultraviolet transmittance of polyimide precursor resins and polybenzoxazole precursor resins, it suppresses the absorption of ultraviolet rays into the resin, efficiently absorbs ultraviolet rays into the photosensitive agent, converts the photosensitive agent, and increases the sensitivity. Consideration has also been made. However, when an aliphatic structural unit is introduced in order to improve the transmittance of ultraviolet rays, the transmittance is certainly improved, but there is a problem that chemical resistance and heat resistance are lowered.
In addition, studies have been made to increase the sensitivity by using a compound having a low molecular weight phenolic hydroxyl group as a dissolution accelerator and adjusting the contrast between the unexposed area and the exposed area. However, the compound having a phenolic hydroxyl group is an aromatic compound, and there is a problem that the storage stability is lowered due to precipitation during storage in a frozen or refrigerated state because the molecular rigidity is increased.
Therefore, development of a highly sensitive photosensitive resin composition has been strongly desired recently, while maintaining chemical resistance and heat resistance and without causing deterioration in storage stability such as precipitation during storage.

Japanese Examined Patent Publication No. 1-46862

An object of the present invention is to provide a photosensitive resin composition excellent in storage stability and sensitivity, which can be used for a protective film, an insulating film, a semiconductor device using the protective film, and a display device.

Such an object is achieved by the present invention described in the following [1] to [12].
[1] A photosensitive resin composition comprising at least (A) an alkali-soluble resin, (B) a photosensitive agent, (C) a ketone compound, and (D) a solvent.
[2] The photosensitive resin composition according to [1], wherein the ketone compound is a compound that does not dissolve (A) the alkali-soluble resin.
[3] The photosensitive resin composition according to [1] or [2], wherein the ketone compound has a melting point of 90 ° C. or higher.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the ketone compound includes only a carbonyl group, carbon, and hydrogen.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the ketone compound has a structure represented by the following general formula (1).

式中、Ｒ１０、Ｒ１１は、水素又は有機基を表す。ただし、Ｒ１０の少なくとも１つは有機基であり、Ｒ１１の少なくとも２つは有機基であり、Ｒ１０とＲ１１が環を形成していてもよい。

In the formula, R10 and R11 represent hydrogen or an organic group. However, at least one of R10 is an organic group, at least two of R11 are organic groups, and R10 and R11 may form a ring.

[6] Any one of [1] to [5], wherein the alkali-soluble resin (A) has at least one selected from a benzoxazole precursor structure, an imide precursor structure, a hydroxystyrene resin, and a phenol resin. The photosensitive resin composition according to item.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the photosensitive agent (B) is a quinonediazide compound.
[8] A cured film composed of a cured product of the photosensitive resin composition according to any one of [1] to [7].
[9] A protective film composed of the cured film according to [8].
[10] An insulating film composed of the cured film according to [8].
[11] A semiconductor device having the cured film according to [8].
[12] A display device having the cured film according to [8].

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in especially storage stability and sensitivity which can be used for a protective film, an insulating film, a semiconductor device using the same, and a display body apparatus can be provided.

Hereinafter, the photosensitive resin composition, the cured film, the protective film, the insulating film, the semiconductor device using the same, and the display device of the present invention will be described.
The photosensitive resin composition of the present invention comprises at least (A) an alkali-soluble resin, (B) a photosensitive agent,
(C) a ketone compound, and (D) a solvent.
In addition, the protective film and the insulating film of the present invention are characterized by being composed of a cured film that is a cured product of the photosensitive resin composition.
In addition, a semiconductor device and a display device according to the present invention are configured by the cured film.

Below, each component of the photosensitive resin composition of this invention is demonstrated in detail. The following is an example, and the present invention is not limited to the following.
(A) The alkali-soluble resin has a hydroxyl group, particularly a phenolic hydroxyl group and / or a carboxyl group. For example, an acrylic resin such as a phenol resin, a hydroxystyrene resin, a methacrylic acid resin, or a methacrylic ester resin, a cyclic olefin Of these, phenol resins, hydroxystyrene resins, and polyamide resins are preferred.
As the phenol resin, a reaction product of a phenol compound typified by novolak and an aldehyde compound can be used. Examples of the phenol compound include phenol, cresol, and xylenol. Examples of the aldehyde compound include alkyl aldehydes such as formaldehyde and acetaldehyde, and aromatic aldehydes such as benzaldehyde, but are not limited thereto.
As the hydroxystyrene resin, there can be used a polymerization or copolymerization reaction product obtained by radical polymerization, cation polymerization or anion polymerization of hydroxystyrene, styrene or a derivative thereof.
In the present invention, the polyamide resin refers to a resin having a benzoxazole precursor structure and / or an imide precursor structure. In addition, the polyamide resin may have a benzoxazole structure or an imide structure generated by a ring-closing reaction of a part of the benzoxazole precursor structure or imide precursor structure, and also has an amic acid ester structure. May be.

  The benzoxazole precursor structure refers to a structure represented by the following formula (2), the imide precursor structure refers to a structure represented by the following formula (3), and the benzoxazole structure refers to the following The structure represented by Formula (4) is pointed out, the imide structure refers to the structure represented by the following Formula (5), and the amido ester structure refers to the structure represented by the following Formula (6).

  In addition, D and R in said formula (2)-(6) show an organic group. Among these polyamide resins, a polyamide resin having a structure represented by the following general formula (7) is preferable.

（式中、Ｘ、Ｙは有機基である。Ｒ_２は水酸基、−Ｏ−Ｒ_４、アルキル基、アシルオキシ基、シクロアルキル基であり、同一でも異なっても良い。Ｒ_３は水酸基、カルボキシル基、−Ｏ−Ｒ_４、−ＣＯＯ−Ｒ_４のいずれかであり、同一でも異なっても良い。ｍは０〜８の整数、ｎは０〜８の整数である。Ｒ_４は炭素数１〜１５の有機基である。ここで、Ｒ_２が複数ある場合は、それぞれ異なっていても同じでもよい。Ｒ_２として水酸基がない場合は、Ｒ_３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_３としてカルボキシル基がない場合、Ｒ_２は少なくとも１つは水酸基でなければならない。）

(Wherein X and Y are organic groups. R ₂ is a hydroxyl group, —O—R ₄ , an alkyl group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₃ is a hydroxyl group or a carboxyl group. , -O-R ₄ , or -COO-R ₄ , which may be the same or different, m is an integer of 0 to 8, n is an integer of 0 to 8. R ₄ is an integer of 1 to Here, when there are a plurality of R _{2 s} , they may be different or the same, and when R ₂ has no hydroxyl group, at least one R ₃ must be a carboxyl group. In addition, when R ₃ has no carboxyl group, at least one R ₂ must be a hydroxyl group.

In the polyamide resin containing the structure represented by the general formula _{(7), O-R 4} , COO-R 4 as a substituent of _O-R 4, Y as a substituent of X is a hydroxyl group, an alkaline aqueous solution of the carboxyl group Is a group protected by R ₄ , 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 ₄ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.

The polyamide resin containing the structure represented by the general formula (7) is, for example, a compound selected from diamine containing X or bis (aminophenol), 2,4-diaminophenol and the like, and tetracarboxylic dianhydride containing Y. , Trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, a compound selected from dicarboxylic acid derivatives 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.

When the polyamide resin containing the structure represented by the general formula (7) is heated at a high temperature, it is subjected to dehydration ring closure when treated at 280 ° C. to 380 ° C., and when heated at a low temperature at 150 ° C. to 280 ° C., a polyimide resin, or A heat-resistant resin can be obtained in the form of polybenzoxazole resin or copolymerization of both.
X of the polyamide resin having the structure represented by the general formula (7) is not particularly limited, and examples thereof include aromatic compounds such as a benzene ring and a naphthalene ring, bisphenols, pyrroles, and furans. A heterocyclic compound, a siloxane compound, etc. are mentioned, More specifically, what is shown by following (8) Formula can be mentioned preferably. These may be used alone or in combination of two or more.

（ここで、＊は、ＮＨ基に結合することを示す。Ａは、アルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−または単結合である。
Ｒ_５は、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを示し、それぞれ同じでも異なっても良い。Ｒ_６は、水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを示す。ｓ＝０〜２の整数である。Ｒ_７〜Ｒ_１０は、有機基である。）

(Here, * represents bonding to an NH group. A represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O). _{) -, - C (CF 3} ) 2 - or a single bond.
R ₅ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different. R ₆ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. s = 0 is an integer of 0-2. R _{7 to} R ₁₀ are organic groups. )

As shown in the above formula (7), 0 to 8 R ₂ are bonded to X (in formula (8), R ₂ is omitted).
Particularly preferable examples in the above formula (8) include those represented by the following formula (9) (some of which include R ₂ ).

（式中、＊はＮＨ基に結合することを示す。式中Ａは、アルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−ＣＨ_３−、−Ｃ（ＣＨ_３）Ｈ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_１１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。ｃ＝０〜３の整数である。）

(In the formula, * represents bonding to an NH group. In the formula, A represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (= O) —, —CH ₃ —, —C (CH ₃ ) H—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or a single bond, R ₁₁ represents an alkyl group, alkoxy A group, an acyloxy group, or a cycloalkyl group, which may be the same or different, and c = 0 to an integer of 3).

  Particularly preferred among the above formula (9) is the one represented by the following formula (10).

（ここで＊はＮＨ基に結合することを示す。Ｒ_１２はアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−、単結合から選ばれる有機基である。）

(Here, * represents bonding to an NH group. R ₁₂ represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) —). , —C (CF ₃ ) ₂ —, an organic group selected from a single bond.)

Specific examples of A in the above formula (8), A in the above formula (9), R ₁₂ alkylene in the above formula (10) 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 ) — and the like are mentioned. Among them, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — are not limited to the aqueous alkali solution but also to the solvent. It is preferable that a polyamide resin having sufficient solubility and excellent balance can be obtained.

  Y in the formula (7) is an organic group, and examples thereof include those similar to X. For example, aromatic compounds such as benzene ring and naphthalene ring, complex compounds such as bisphenols, pyrroles, pyridines and furans. A cyclic compound, a siloxane compound, etc. are mentioned, More specifically, what is shown by following formula (11) can be mentioned preferably. These may be used alone or in combination of two or more.

（ここで、＊は、Ｃ＝Ｏ基に結合することを示す。Ｊは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−または単結合である。
Ｒ_１３は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基、ハロゲン原子から選ばれた１つを示し、それぞれ同じでも異なっても良い。Ｒ_１４は、水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを示す。ｔ＝０〜２の整数である。Ｒ_１５〜Ｒ_１８は、有機基である。）

(Here, * indicates bonding to a C═O group. J represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —C). (= O) -, - NHC (= O) -, - C (CF 3) 2 - or a single bond.
R ₁₃ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, and may be the same or different. R ₁₄ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. t is an integer of 0-2. R _{15 to} R ₁₈ are organic groups. )

As shown in Formula (7), 0 to 8 R ₃ are bonded to Y (in Formula (11), R ₃ is omitted).
Among these, particularly preferred are those represented by the following formula (12) (some include R ₃ ).
Regarding the structure derived from tetracarboxylic dianhydride in the following formula (12), the position where both C═O groups are bonded to the meta position, and both the positions in the para position are listed. A structure including each of the para positions may be used.

（式中、＊はＣ＝Ｏ基に結合することを示す。Ｒ_１９は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。Ｒ_２０は、水素原子又は炭素数１〜１５の有機基から選ばれた１つを示し、一部が置換されていてもよい。ｕ＝０〜２の整数である。）

(In the formula, * indicates bonding to a C═O group. R ₁₉ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, R ₂₀ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted, and is an integer of u = 0 to 2. is there.)

（式中、＊はＣ＝Ｏ基に結合することを示す。Ｒ_２０は、水素原子又は炭素数１〜１５の有機基から選ばれた１つを示し、一部が置換されていてもよい。）

(In the formula, * represents bonding to a C═O group. R ₂₀ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted. .)

In the case of the polyamide resin represented by the above formula (7), the terminal amino group of the polyamide resin is replaced with another alkenyl group or alkynyl to the extent that it does not affect the mechanical properties and heat resistance when cured at low temperature. An acid anhydride containing an aliphatic group having at least one group or a cyclic compound group may be used to cap the amide.
Examples of the aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group include groups represented by formula (13) and formula (14). These may be used singly or in combination of two or more, and a part of the capped amide moiety may be dehydrated and closed.

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

Furthermore, in the case of the polyamide resin represented by the above formula (7), at least one of the terminals may have a nitrogen-containing cyclic compound to the extent that it does not affect the mechanical properties and heat resistance when cured at a low temperature. Thereby, adhesiveness with a metal wiring (especially copper wiring) etc. can be improved.
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-pyrazolyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazolyl) methylamino group, (1H-tetrazol-5-yl) An amino group, 1- (1H-tetrazol-5-yl) methyl-amino group, 3- (1H-tetrazol-5-yl) benz-amino group and the like can be mentioned.

(B) As the photosensitizer, a photosensitizer capable of positive patterning can be used, and a compound capable of generating an acid upon irradiation with actinic radiation having a wavelength of 200 to 500 nm, particularly preferably 350 to 450 nm is preferable. .
Specifically, photosensitive diazoquinone compounds, onium salts such as diaryl iodonium salts, triaryl sulfonium salts, sulfonium borate salts, 2-nitrobenzyl ester compounds, N-imino sulfonate compounds, imide sulfonate compounds, 2,6-bis (Trichloromethyl) -1,3,5-triazine compound, dihydropyridine compound and the like can be used. Among these, a photosensitive diazoquinone compound excellent in sensitivity and solvent solubility is preferable.
Examples of the photosensitive diazoquinone compound include esters of a phenol compound as a support and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid.
In the case of the positive type, it is considered that the photosensitizer remaining in the relief pattern in the unexposed area is decomposed by heat at the time of curing to generate an acid, and the photosensitizer plays an important role as a reaction accelerator. In the case of a photosensitive diazoquinone compound, an ester of 1,2-naphthoquinone-2-diazide-4-sulfonic acid that is more easily decomposed by heat is preferable.

  As the phenol compound which is a support for the photosensitive diazoquinone compound, a phenol compound having a phenol nucleus number of about 1 to 10 or a low molecular weight novolak resin can be used. Specifically, bisphenol, trisphenol, tetrakisphenol, a phenol compound in which about 3 to 6 phenol nuclei are linearly bonded via a methylene bond, and the like can be used. Specifically, formulas (15) to (16) are preferable.

式（１５）〜（１６）中Ｑは、水素原子、式（１７）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（１７）である。

In formulas (15) to (16), Q is selected from a hydrogen atom and formula (17). Here, at least one of Q of each compound is represented by formula (17).

（式中、Ｂは有機基である。Ｒ_２１〜Ｒ_２４は水素原子、水酸基、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、シクロアルキル基の中から選ばれる１つであり、同一でも異なっていても良い。ｏ〜ｒは、それぞれ０〜４の整数である。）

(In the formula, B is an organic group. R _{21 to} R ₂₄ are one selected from a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, and a cycloalkyl group, and may be the same or different. O to r are each an integer of 0 to 4.)

（式中、Ｒ_２５〜Ｒ_２７は水素原子、アルキル基であり、Ｒ_２８〜Ｒ_３０は水素原子、水酸基、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、シクロアルキル基の中から選ばれる１つであり、同一でも異なっていても良い。ｖ〜ｘは、それぞれ０〜２の整数である。ｙは０または１の整数である。）

(Wherein R _{25 to} R ₂₇ are a hydrogen atom and an alkyl group, and R _{28 to} R ₃₀ are 1 selected from a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, and a cycloalkyl group. And may be the same or different. V to x are each an integer of 0 to 2. y is an integer of 0 or 1.)

B in the above formula (18) is an organic group. Specific examples of the organic group include alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) —, aryl, cycloalkyl, or a single bond. It may be in the form of a combination of two or more of the above organic groups.
Specific examples of alkylene and substituted alkylene of B in the above formula (18) include —CH ₂ —, — (CH ₂ ) ₂ —, —CH (CH ₃ ) —, — (CH ₂ ) ₃ —, —C ( _{CH 3) 2 -, - CH} (CH 2 CH 3) -, - (CH 2) 4 -, - 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) -, and the like. Among them, —CH ₂ —, —CH (CH ₃ ) —, and —C (CH ₃ ) ₂ — suitable for solubility in an aqueous alkali solution and solubility in a solvent are preferable.
A specific example of the form in which two or more organic groups of B in the above formula (18) are combined includes the structure shown in the formula (20).

（式中、Ｒ_３１〜Ｒ_３８は水素原子、アルキル基である。Ｋは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、または単結合である。ｄは０または１の整数である。）

(Wherein R _{31 to} R ₃₈ are a hydrogen atom and an alkyl group. K is —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—). _{, -SO 2 -, - C (} = O) -, - NHC (= O) -, or a single bond .d is an integer of 0 or 1).

In addition, R _{21 to} R _{24 in} the general formula (18) and R _{28 to} R ₃₀ in the general formula (19) are each a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, or a cycloalkyl group. It is one selected from among them, and when there are a plurality of them, they may be the same or different. Examples of the halogen atom include chlorine and bromine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and an undecyl group. , Dodecyl groups, etc., alkoxy groups include methoxy group, ethoxy group, propoxy group, butoxy group, etc., alkenyl groups include ethenyl group, propenyl group, butenyl group, etc., cycloalkyl group Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like, and a hydrogen atom, a methyl group, and an ethyl group, which are excellent in sensitivity and resolution of the positive photosensitive resin composition, are particularly preferable.

In addition, R _{25 to} R _{27 in} the general formula (19) and R _{31 to} R ₃₈ in the general formula (20) are hydrogen atoms or alkyl groups, and are not particularly limited. A methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dosyl group, which may be the same or different. Among these, a hydrogen atom, a methyl group, and an ethyl group, which are excellent in sensitivity and resolution of the photosensitive resin composition, are particularly preferable.
Although it does not specifically limit as a phenolic compound shown by the said General formula (18), What is shown by following formula (21) is illustrated.

  Although it does not specifically limit as a phenolic compound shown by the said General formula (19), What is shown by following formula (22) is illustrated.

  Furthermore, in the present invention, a phenolic compound can be added so that patterning can be performed with high sensitivity and without resin residue (scum) after development.

  The resin composition and the photosensitive resin composition in the present invention include an oxirane compound, an oxirane resin, a methylol group-containing compound, an alkoxyalkyl group-containing compound, an N-alkoxyalkyl group-containing compound, and a bifunctional or more unsaturated double as necessary. Bonding agent such as a bond or triple bond-containing compound, leveling agent such as acrylic, silicone, fluorine and vinyl, silane coupling agent, antioxidant, compound that generates acid by heat, dissolution inhibitor for aqueous alkali solution An additive such as a plasticizer may be included.

  The (C) ketone compound is not used as a so-called solvent for the purpose of dissolving the (A) alkali-soluble resin because it is used as an additive contributing to high sensitivity. That is, the ketone compound (C) is a compound that does not dissolve the (A) alkali-soluble resin.

In addition, the positive photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer and then subjected to a heat treatment at about 100 ° C. to 130 ° C. for about 2 to 10 minutes to volatilize the solvent and handle it. Processing that can be easily performed. Therefore, in the case of a ketone compound that volatilizes during heat treatment, the ketone compound hardly remains at the time of exposure, and the contribution to high sensitivity is reduced. In view of these, it is preferable to use a ketone compound having a melting point of 90 ° C. or higher as a measure of difficulty in volatilization. Specific examples include camphor, norbornanone and adamantanone. Of these, camphor, norbornanone, and adamantanone are preferable, and examples include camphor, adamantanone, and a compound represented by formula (23).

The ketone compound (C) is more preferably a compound having one or more carbonyl groups having a carbon atom at the adjacent position. The adjacent carbon atom is preferably a compound having no double bond, triple bond or aromaticity. When the adjacent carbon atom is a double bond, triple bond, or aromatic, there is a high tendency to absorb ultraviolet light from the exposure light source, and the contribution to higher sensitivity is reduced.
Moreover, as said ketone compound (C), the compound comprised only from a carbonyl group, carbon, and hydrogen is preferable. Specifically, it is a compound having a structure represented by the general formula (1).
In said formula (1), R10 and R11 represent hydrogen or an organic group. However, at least one of R10 is an organic group, at least two of R11 are organic groups, and R10 and R11 may form a ring. Preferably, R10 and R11 are each independent.
Furthermore, it has been found that the larger the steric hindrance of the carbon atom adjacent to the carbonyl of the ketone compound, the better the storage stability at room temperature. It is presumed that stability is expressed by suppressing the nucleophilic attack on the carbonyl carbon of alkali-soluble resin, photosensitizer, and other additives.
Examples of the ketone compound (C) include camphor, norbornanone and adamantanone. Among them, camphor, norbornanone and adamantanone are preferable, and camphor and adamantanone are more preferable.

(D) As a solvent, 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.

As components other than (A), (B), (C), and (D), an adhesion aid and a dissolution accelerator may be included.
(Adhesion aid)
The photosensitive resin composition of the present invention may contain an adhesion assistant.
The adhesion assistant is a component having a function of improving the bonding strength between the coating film obtained by curing the photosensitive resin composition and the substrate on which the coating film is formed.
Examples of such adhesion assistants include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Methoxysi 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanate Examples include, but are not limited to, propyltriethoxysilane and silicon compounds obtained by reacting amino compounds with silicon compounds and acid dianhydrides or acid anhydrides.

The silicon compound having an amino group is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyl. Examples include methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane.
The acid dianhydride or acid anhydride is not particularly limited, and examples thereof include maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, and phthalic anhydride. Moreover, in using, it can be used individually or in combination of 2 or more types.
The addition amount of the adhesion assistant is not particularly limited, but is preferably 0.05 to 50 parts by weight, and 0.1 to 20 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. Is more preferable. When the addition amount is within the above range, it is possible to suitably achieve both adhesion to the substrate and storage stability of the photosensitive resin composition.

(Dissolution promoter)
In addition, a dissolution accelerator may be included in the photosensitive resin composition of the present invention.
The dissolution accelerator is a component capable of improving the solubility of the exposed portion of the coating film formed using the photosensitive resin composition in the developer and improving scum during patterning.
Examples of such a dissolution accelerator include compounds having a phenolic hydroxyl group, and specific examples include those represented by the following formulas (24) to (30).

  Among these compounds having a phenolic hydroxyl group, those selected from the formula (31) are preferable. Two or more of these may be used. Thereby, especially sensitivity can be improved.

  The content of the compound having a phenolic hydroxyl group is not particularly limited, but is preferably 1 part by weight or more and 30 parts by weight or less, and preferably 1 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin. It is more preferable that Thereby, generation | occurrence | production of a scum at the time of image development can be suppressed more effectively, and a sensitivity improves more by promoting the solubility of an exposure part.

Further, in the photosensitive resin composition of the present invention, additives such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a crosslinking agent, a terminal blocking agent, and a sensitizer are added as necessary. May be.

In the method of using the 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 in which an appropriate amount of a water-soluble organic solvent or a surfactant such as an alcohol such as methanol or ethanol is added thereto can be suitably 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 (curing) is performed to form an oxazole ring, or an oxazole ring and an imide ring, and a cured product having excellent 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 280 ° C. to 380 ° C.
° C is preferred, 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. An oven, a hot plate, an electric furnace (furnace), infrared rays, microwaves, etc. are used for the heat treatment.

  The cured film formed using the photosensitive resin composition of the present invention is used not only for semiconductor devices such as semiconductor elements, but also for display device devices such as TFT-type liquid crystals and organic EL, interlayer insulating films for flexible circuits and flexible films. It is also useful as a copper clad 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 photosensitive resin composition formed on the passivation film. A protective film such as a buffer coat 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, and an α ray Examples thereof include a 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 photosensitive resin composition of the present invention on a display element, an insulating film or a flattening film for TFT elements, color filters, etc., MVA type Examples thereof include protrusions for liquid crystal display devices, partition walls for organic EL element cathodes, and the like.
The use method is based on forming the 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, but by introducing a post-exposure step before curing the coating film of the photosensitive resin composition of the present invention, it is transparent. A resin layer having excellent properties can be obtained, which is more preferable in practical use.
As a semiconductor device, a semiconductor chip (element) is formed on a semiconductor substrate and sealed with an airtight seal or a molding material. Specific examples include transistors, solar cells, diodes, solid-state imaging devices, various semiconductor packages in which semiconductor chips are stacked and sealed, and wafer level chip size packages (WLP).
Examples of the display device include a TFT liquid crystal, an organic EL, and a color filter.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to this.
Synthesis of alkali-soluble resin (A-1) Dicarboxylic acid obtained by reacting 0.085 mol of diphenyl ether-4,4′-dicarboxylic acid with 0.170 mol of 1-hydroxy-1,2,3-benzotriazole 41.82 g (0.085 mol) of a derivative (active ester), 11.50 g (0.050 mol) of bis (3-amino-4-hydroxyphenyl) methane, and bis (3-amino-4-hydroxy-2) , 5-dimethylphenyl) methane (14.30 g, 0.050 mol) was placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, and N-methyl-2- Pyrrolidone 500 g was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath.
Next, 6.88 g (0.040 mol) of 4-ethynylphthalic anhydride and 100 g of N-methyl-2-pyrrolidone were added, and the mixture was further stirred for 3 hours to complete the reaction. After filtering the reaction mixture, the reaction solution is poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, dried under vacuum, and the desired alkali-soluble resin. (A-1) was obtained.
The obtained alkali-soluble resin (A-1) was a polyamide resin and had the structure of the general formula (7).

Synthesis of alkali-soluble resin (A-2) 0.070 mol of diphenyl ether-4,4′-dicarboxylic acid and 1-hydroxy-1,
34.44 g (0.070 mol) of a dicarboxylic acid derivative (active ester) obtained by reacting 0.140 mol of 2,3-benzotriazole with 0.010 mol of isophthalic acid and 1-hydroxy-1,2 , 3-benzotriazole (0.020 mol) was reacted with a dicarboxylic acid derivative (active ester) (4.00 g, 0.010 mol) and 2,2-bis (3-amino-4-hydroxyphenyl). Add 36.6 g (0.100 mol) of hexafluoropropane to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, and add 500 g of N-methyl-2-pyrrolidone. And dissolved. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath.
Next, 8.20 g (0.050 mol) of norbornene dicarboxylic acid anhydride and 100 g of N-methyl-2-pyrrolidone were added, and the reaction was terminated by further stirring for 3 hours. After filtering the reaction mixture, the reaction solution is poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, dried under vacuum, and the desired alkali-soluble resin. (A-2) was obtained.
The obtained alkali-soluble resin (A-2) was a polyamide resin and had the structure of the general formula (7).

Synthesis of alkali-soluble resin (A-3) Dicarboxylic acid obtained by reacting 0.085 mol of diphenyl ether-4,4′-dicarboxylic acid with 0.170 mol of 1-hydroxy-1,2,3-benzotriazole 41.82 g (0.085 mol) of the derivative (active ester), 11.50 g (0.050 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) methane, and 2,2-bis (3 -Amino-4-hydroxyphenyl) hexafluoropropane (18.30 g, 0.050 mol) was placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. 500 g of methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath.
Next, 8.20 g (0.050 mol) of norbornene dicarboxylic acid anhydride and 100 g of N-methyl-2-pyrrolidone were added, and the reaction was terminated by further stirring for 3 hours. After filtering the reaction mixture, the reaction solution is poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, dried under vacuum, and the desired alkali-soluble resin. (A-3) was obtained. The obtained alkali-soluble resin (A-3) was a polyamide resin and had the structure of the general formula (7).

Synthesis of Alkali-Soluble Resin (A-4) A 500 mL round bottom flask was charged with 30.0 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 400 mL of acetone, Stir until 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is dissolved. Thereto, 12.4 g (0.18 mol) of para-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise over 30 minutes while cooling so that the temperature was less than 20 ° C. to obtain a mixture. After the dropwise addition, the temperature of the mixture was heated to 40 ° C. and stirred for 2 hours, and 30.0 g (0.218 mol) of potassium carbonate was gradually added thereto and further stirred for 2 hours. Heating was stopped and the mixture was further stirred at room temperature for 18 hours. Thereafter, an aqueous sodium hydroxide solution was gradually added while vigorously stirring the mixture. After the addition, the mixture was heated to 55 ° C. and further stirred for 30 minutes. After completion of the stirring, the mixture was cooled to room temperature, and a 37 wt% hydrochloric acid aqueous solution and 500 mL of water were added to adjust the pH to be in the range of 6.0 to 7.0. The obtained precipitate was filtered off, washed with water and dried at 60 to 70 ° C., and bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl). ) A propane solid was obtained. To 51.0 g of the obtained solid, 316 g of acetone and 158 g of methanol were added and heated to 50 ° C. for complete dissolution. 300 mL of 50 ° C. pure water was added thereto over 30 minutes and heated to 65 ° C. Thereafter, the crystals which have been slowly cooled to room temperature are filtered, and the crystals are purified by drying at 70 ° C., and bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis ( 4-Hydroxyphenyl) propane was obtained.
20 g of the obtained bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane was placed in a 1 L flask and 1.0 g of 5% palladium-carbon and ethyl acetate 180 were added. .4 g was added to make a suspension. Hydrogen gas was purged there, and the mixture was shaken for 35 minutes while being heated to 50 to 55 ° C. to carry out a reduction reaction. After completion of the reaction, it was cooled to 35 ° C. and the suspension was purged with nitrogen. After removing the catalyst by filtration, the filtrate was subjected to an evaporator to evaporate the solvent. The obtained product was dried at 90 ° C. to obtain bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.

  In a 300 mL flask, 14.27 parts by weight (0.024 mol) of bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane and 40 parts by weight of γ-butyrolactone were added. In addition, the mixture was cooled to 15 ° C. with stirring. Thereto were added 6.86 parts by weight (0.022 mol) of 4,4′-oxydiphthalic anhydride and 12.0 parts by weight of γ-butyrolactone, and the mixture was stirred at 20 ° C. for 1.5 hours. Thereafter, the mixture was heated to 50 ° C. and stirred for 3 hours, and then 5.27 g (0.044 mol) of N, N-dimethylformamide dimethylacetal and 10.0 g of γ-butyrolactone were added, and the mixture was further stirred at 50 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and then poured into a solution of water / isopropyl alcohol = 3/1. The precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum. A polyamide resin (A-4) (resin that undergoes dehydration and ring closure when heated at 300 to 400 ° C. to become polyimide benzoxazole), which is the target alkali-soluble resin, was obtained. The obtained alkali-soluble resin (A-4) had the structure of the general formula (7).

Synthesis of Photosensitizer (Q-1) 12.70 g (0.022 mol) of phenol of formula (B-1) and 17.49 g (0.065 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride And 170 g of acetone were stirred and dissolved in a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, a mixed solution of 7.24 g (0.072 mol) of triethylamine and 6.1 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 0.98 g (0.016 mol) of acetic acid was added, and the mixture was further reacted for 30 minutes. After filtration of the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and of formula (Q-1). A photosensitizer represented by the structure was obtained.

Synthesis of photosensitizer (Q-2) 11.00 g (0.026 mol) of phenol of formula (B-1) and 18.78 g (0.070 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride And acetone 1
70 g 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 stirred and dissolved. Next, while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C., a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting for 3 hours at room temperature, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. After filtration of the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and dried according to formula (Q-2). A photosensitizer represented by the structure was obtained.

Preparation of photosensitive resin composition Synthesized (A) alkali-soluble resins (A-1) to (A-4), synthesized (B) photosensitive agents (B1) to (B-3), (C) ketone compounds After mixing in the ratio of Table 1 and dissolving in (D) γ-butyrolactone (denoted as GBL) or N-methyl-2-pyrrolidone (denoted as NMP) as a solvent to a viscosity of 1000 mPa · s, 0. The mixture was filtered through a 2 μm Teflon (registered trademark) filter to obtain a photosensitive resin composition.

Processability evaluation The photosensitive resin composition was applied on an 8-inch 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 7.5 μm. An i-line stepper (manufactured by Nikon Corporation, NSR-) was passed through this mask through 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). 4425i) was used for irradiation with varying exposure.
Next, using a 2.38% tetramethylammonium hydroxide aqueous solution as the developer, the development time is adjusted so that the difference between the film thickness after pre-baking and the film thickness after development is 1.0 μm, and paddle development is performed twice. Then, the exposed portion was dissolved and removed, and then rinsed with pure water for 10 seconds. The value of the minimum exposure amount at which a 100 μm square via hole pattern was formed was evaluated as sensitivity.
Stability evaluation The state of the varnish after the photosensitive resin composition was allowed to stand at room temperature for 1 day was observed to evaluate whether the solution state was maintained or gelled.
Fabrication of Semiconductor Device Using a simulated element wafer having an aluminum circuit on the surface, the photosensitive resin compositions of Examples 1 to 7 were applied so as to have a final thickness of 5 μm, followed by patterning and final baking. After that, each chip size is divided and mounted on a 16-pin DIP (Dual Inline Package) lead frame using a conductive paste, and then molded with an epoxy resin for semiconductor encapsulation (EME-6300H, manufactured by Sumitomo Bakelite Co., Ltd.). Thus, a semiconductor device was manufactured. These semiconductor devices (semiconductor packages) are treated at 85 ° C./85% humidity for 168 hours, then immersed in a 260 ° C. solder bath for 10 seconds, and then subjected to a high temperature and high humidity pressure cooker treatment (125 ° C., 2.3 atm). 100% RH) to check the open failure of the Al circuit, it is expected that the semiconductor device can be used without any problem without corrosion.

  Table 1 below shows examples and comparative examples.

As shown in Table 1, it was found that Examples 1 to 7 to which the ketone compound was added were excellent in storage stability without increasing gelation and increased in sensitivity. Accordingly, it is considered that a pattern can be formed with a short exposure time, which contributes to an improvement in production efficiency in the manufacturing process of the semiconductor device.

Claims (12)

  A photosensitive resin composition comprising at least (A) an alkali-soluble resin, (B) a photosensitive agent, (C) a ketone compound, and (D) a solvent.   The photosensitive resin composition according to claim 1, wherein the ketone compound is a compound that does not dissolve the alkali-soluble resin (A).   The photosensitive resin composition according to claim 1, wherein the ketone compound has a melting point of 90 ° C. or higher.   The photosensitive resin composition according to claim 1, wherein the ketone compound is composed of only a carbonyl group, carbon, and hydrogen. The photosensitive resin composition according to claim 1, wherein the ketone compound has a structure represented by the following general formula (1).

In formula (1), R10 and R11 represent hydrogen or an organic group. However, at least one of R10 is an organic group, at least two of R11 are organic groups, and R10 and R11 may form a ring.   The photosensitivity according to any one of claims 1 to 5, wherein the alkali-soluble resin (A) has at least one selected from a benzoxazole precursor structure, an imide precursor structure, a hydroxystyrene resin, and a phenol resin. Resin composition.   The photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) is a quinonediazide compound.   The cured film comprised with the hardened | cured material of the photosensitive resin composition of any one of Claims 1 thru | or 7.   A protective film comprising the cured film according to claim 8.   The insulating film comprised with the cured film of Claim 8.   A semiconductor device comprising the cured film according to claim 8. The display body apparatus which has the cured film of Claim 8.