JP2014041264A - 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 which can be utilized for a protective film, an insulator film, and a semiconductor device and a display body device using the same, and is without aperture residues and excellent in adhesion.SOLUTION: The photosensitive resin composition comprises an alkali-soluble resin (A), a photoacid generator (B), and a silane coupling agent (C). The silane coupling agent (C) is represented by the specified general formula (1). (In the formula, Ris a hydrogen atom or methyl group, Ris a C1-C6 alkoxy group or isocyanate group, Ris a C1-C6 hydrocarbon, m is an integer from 1 to 3 inclusive, and n is an integer from 4 to 20 inclusive.)

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 polybenzoxazole resin, a polyimide resin, or the like that has excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. On the other hand, in order to simplify the film production process, a positive photosensitive resin composition in which a polybenzoxazole resin, a polyimide resin, or the like is combined with a diazoquinone compound as a photosensitive agent is also used (see, for example, Patent Document 1). ).
This photosensitive resin composition becomes hardly soluble in an alkaline aqueous solution due to the effect of inhibiting dissolution of a diazoquinone compound in a resin such as polybenzoxazole resin or polyimide resin in an unexposed portion. On the other hand, in the exposed area, the diazoquinone compound undergoes a chemical change, and the photosensitive resin composition becomes soluble in an alkaline aqueous solution. By utilizing the difference in solubility between the exposed area and the unexposed area, and dissolving and removing the exposed area with an aqueous alkaline solution, it becomes possible to produce a coating film pattern of only the unexposed area. Here, addition of a specific silane coupling agent to the photosensitive resin composition is also studied so that the coating film does not peel from the substrate during patterning (see, for example, Patent Document 2).
The polybenzoxazole resin precursor in the positive photosensitive resin composition having a coating film pattern formed as described above is finally dehydrated and ring-closed by curing at a high temperature close to 300 ° C., and has high heat resistance. It becomes resin.

  However, when a high-resolution pattern is formed, there is a problem that a residue is attached around the pattern opened at the time of development, and the pattern opening size is smaller than a desired size due to the influence of the residue. There is also a problem that a predetermined film thickness cannot be maintained after curing due to heat shrinkage during curing.

JP-A-56-27140 JP 2004-170611 A

  The objective of this invention is providing the photosensitive resin composition excellent in the adhesiveness which is usable for a protective film, an insulating film, a semiconductor device using the same, and a display body apparatus without an opening part residue. .

（式中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は炭素数１以上６以下のアルコキシ基又はイソシアネート基であり、Ｒ^３は炭素数１以上６以下の炭化水素であり、ｍは１以上３以下の整数であり、ｎは４以上２０以下の整数である。）
［２］ 前記シランカップリング剤（Ｃ）は、一般式（１）におけるｎが６以上１２以下の整数である前記［１］に記載の感光性樹脂組成物。
［３］ 前記シランカップリング剤（Ｃ）は、一般式（１）におけるＲ^２が炭素数１以上６以下のアルコキシ基である前記［１］または２に記載の感光性樹脂組成物。
［４］ 前記アルカリ可溶性樹脂（Ａ）が、フェノール樹脂、ヒドロキシスチレン樹脂及びポリアミド樹脂から選ばれる少なくとも１つの樹脂である前記［１］乃至［３］のいずれか１項に記載の感光性樹脂組成物。
［５］ 前記シランカップリング剤（Ｃ）は、アルカリ可溶性樹脂（Ａ）１００質量部に対して０．１質量部以上２０質量部以下を含むものである前記［１］乃至［４］のいずれか１項に記載の感光性樹脂組成物。
［６］ 前記光酸発生剤（Ｂ）が、キノンジアジド化合物である前記［１］乃至［５］のいずれか１項に記載の感光性樹脂組成物。
［７］ 前記［１］乃至［６］のいずれか１項に記載の感光性樹脂組成物の硬化物で構成されている硬化膜。
［８］ 前記［７］に記載の硬化膜で構成されている保護膜。
［９］ 前記［７］に記載の硬化膜で構成されている絶縁膜。
［１０］ 前記［７］に記載の硬化膜を有している半導体装置。
［１１］ 前記［７］に記載の硬化膜を有している表示体装置。 Such an object is achieved by the present invention described in the following [1] to [11].
[1] A photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a silane coupling agent (C), wherein the silane coupling agent (C) is represented by the following general formula ( A photosensitive resin composition characterized by being represented by 1).

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkoxy group having 1 to 6 carbon atoms or an isocyanate group, R ³ is a hydrocarbon having 1 to 6 carbon atoms, and m is (It is an integer from 1 to 3, and n is an integer from 4 to 20.)
[2] The photosensitive resin composition according to [1], wherein the silane coupling agent (C) is an integer of 6 to 12 in the general formula (1).
[3] The photosensitive resin composition according to [1] or 2, wherein R ² in the general formula (1) is an alkoxy group having 1 to 6 carbon atoms.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the alkali-soluble resin (A) is at least one resin selected from a phenol resin, a hydroxystyrene resin, and a polyamide resin. object.
[5] Any one of [1] to [4], wherein the silane coupling agent (C) includes 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). The photosensitive resin composition according to item.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the photoacid generator (B) is a quinonediazide compound.
[7] A cured film composed of a cured product of the photosensitive resin composition according to any one of [1] to [6].
[8] A protective film composed of the cured film according to [7].
[9] An insulating film composed of the cured film according to [7].
[10] A semiconductor device having the cured film according to [7].
[11] A display device having the cured film according to [7].

  According to the present invention, a photosensitive resin composition that can be used in a protective film, an insulating film, a semiconductor device using the protective film, and a display device, has no shrinkage after curing without an opening residue residue, and has excellent adhesion. A product photosensitive resin composition 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 is a photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a silane coupling agent (C), wherein the silane coupling agent ( C) is a photosensitive resin composition characterized by being represented by the following general formula (1). Thereby, when the photosensitive resin composition of this invention is apply | coated to a board | substrate and the cured film which has an opening part is produced, affinity with a cured film and its base surface improves, and in this photosensitive resin composition By inhibiting the interaction between the alkali-soluble resin (A) contained therein and the metal (wiring portion) in the substrate, it is possible to reduce the residue (scum) in the opening.
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.
[Alkali-soluble resin (A)]
The alkali-soluble resin (A) used in the present invention has a hydroxyl group, particularly a phenolic hydroxyl group and / or a carboxyl group, in the main chain or side chain. For example, a phenol resin, a hydroxystyrene resin, a methacrylic acid resin, Examples thereof include acrylic resins such as methacrylic ester resins, cyclic olefin resins, and polyamide resins. Among these, phenol resin, hydroxystyrene resin, and polyamide resin are preferable. These alkali-soluble resins can be used alone or in combination.

  As the phenol resin used in the present invention, it is possible to use a reaction product of a phenol compound and an aldehyde compound typified by a novolak type phenol resin, a reaction product of a phenol compound and a dimethanol compound typified by a phenol aralkyl resin, or the like. it can.

  Examples of the phenol compound used for the novolac type phenol resin include cresols such as phenol, o-cresol, m-cresol and p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, Xylenols such as 2,6-xylenol, 3,4-xylenol and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; isopropylphenol, butylphenol and p-tert -Alkylphenols such as butylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, pyrogallol and phloroglucinol, but not limited thereto. These phenol compounds can be used alone or in combination of two or more.

  Examples of the aldehyde compound used for the novolak type phenol resin include, but are not limited to, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, and the like. These aldehydes can also be used alone or in combination of two or more.

  As the phenol compound used for the phenol aralkyl resin, the same phenol compound as the phenol compound used for the novolac type phenol resin can be used.

  Examples of the dimethanol compound used in the phenol aralkyl resin include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4′-biphenyldimethanol, 3,4′-biphenyldimethanol, 3,3 ′. -Dimethanol compounds such as biphenyldimethanol and 2,6-naphthalenediethanol, 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) Bis (alkoxymethyl) compounds such as biphenyl, 3,4′-bis (methoxymethyl) biphenyl, 3,3′-bis (methoxymethyl) biphenyl and methyl 2,6-naphthalenedicarboxylate, 1,4-bis (chloro Methyl) benzene, 1,3-bis (chloromethyl) benzene, 1,4-bis (bromome L) benzene, 1,3-bis (bromomethyl) benzene, 4,4'-bis (chloromethyl) biphenyl, 3,4'-bis (chloromethyl) biphenyl, 3,3'-bis (chloromethyl) biphenyl, Examples include, but are not limited to, bis (hargenoalkyl) compounds such as 4,4′-bis (bromomethyl) biphenyl, 3,4′-bis (bromomethyl) biphenyl, and 3,3′-bis (bromomethyl) biphenyl. . These dimethanol compounds can be used alone or in combination of two or more.

  As the hydroxystyrene resin, a polymerization reaction product or a copolymerization reaction product obtained by radical polymerization, cation polymerization, or anion polymerization of hydroxystyrene, styrene, or a derivative thereof can be used.

  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 is produced by a ring-closing reaction of a part of a benzoxazole structure, an imide precursor structure, a part of a benzoxazole precursor structure, a part of a benzoxazole structure or an imide precursor structure. It may have an imide structure or may have an amic acid ester structure.

  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 structure represented by the following formula (4), the imide structure refers to the structure represented by the following formula (5), and the amido ester structure is represented by the following formula (6). Refers to the structure.

なお、上記式（２）〜（６）中のＤおよびＲは有機基を示す。

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 from the viewpoint of heat resistance of the cured product of the photosensitive resin composition of the present invention.

（式（７）中、Ｘ、Ｙは有機基である。Ｒ_２は水酸基、−Ｏ−Ｒ_４、アルキル基、アシルオキシ基又はシクロアルキル基であり、Ｒ_２が複数ある場合、それぞれ同じ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又は−ＣＯＯ−Ｒ_４であり、Ｒ_３が複数ある場合、それぞれ同じでも異なっても良い。Ｒ_４は炭素数１以上１５以下の有機基である。ここで、Ｒ_２が水酸基でない場合は、Ｒ_３の少なくとも１つはカルボキシル基である。また、Ｒ_３がカルボキシル基でない場合、Ｒ_２の少なくとも１つは水酸基である。ｍは０以上８以下の整数、ｎは０以上８以下の整数である。また、ａは重合度を示し、２以上５００以下の整数である。

(Equation (7) in, X, Y is an organic radical .R ₂ is a hydroxyl group, _{-O-R 4,} an alkyl group, an acyloxy group or a cycloalkyl group, _{when R 2} are a plurality, same or different R ₃ is a hydroxyl group, a carboxyl group, —O—R ₄ or —COO—R ₄ , and when there are a plurality of R _{3 s} , they may be the same or different, and R ₄ has 1 to 15 carbon atoms. is an organic radical. here the, if R ₂ is not hydroxy group, at least one of R ₃ is carboxyl group. also, if R ₃ is not a carboxyl group, at least one of R ₂ is a hydroxyl group. m is an integer of 0 to 8, and n is an integer of 0 to 8. Further, a represents the degree of polymerization and is an integer of 2 to 500.

In the polyamide resin having the structure represented by the general formula (7), _-O-R 4 as _-O-R 4, R ₃ as _{R 2, -COO-R 4} is an alkali aqueous solution of the polyamide resin For the purpose of adjusting solubility, the hydroxyl group and the carboxyl group are groups protected with R ₄ which is an organic group having 1 to 15 carbon atoms. Examples of such 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 and tetrahydropyranyl group. Etc.

  The organic group as X of the polyamide resin having the structure represented by the general formula (7) is not particularly limited, but for example, an aromatic group having a structure such as a benzene ring, a naphthalene ring, and a bisphenol structure. , A heterocyclic organic group having a structure such as a pyrrole ring and a furan ring, a siloxane group, and the like. More specifically, those represented by the following formula (8) are preferable. These may be used alone or in combination of two or more.

（式（８）中、＊は、一般式（７）におけるＮＨ基に結合することを示す。Ａは、アルキレン基、置換アルキレン基、−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及び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及びハロゲン原子から選ばれた１つを示す。ｓは０以上２以下の整数である。Ｒ_７〜Ｒ_１０は、それぞれ有機基である。
なお、上記式（８）において、上記一般式（７）におけるＸの置換基Ｒ_２は省略している。）

(In formula (8), * represents bonding to the NH group in general formula (7). A represents an alkylene group, a substituted alkylene group, —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; R ₆ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom, s is an integer of 0 or more and 2 or less, R _{7 to} R ₁₀ are , Each is an organic group.
In the above formula (8), the substituent R ₂ of X in the above general formula (7) is omitted. )

Particularly preferable among the groups represented by the above formula (8) include those represented by the following formula (9) (some of them have R ₂ in the general formula (7)).

（式（９）中、＊は一般式（７）におけるＮＨ基に結合することを示す。式中Ａは、アルキレン基、置換アルキレン基、−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、アシルオキシ基及びシクロアルキル基から選ばれた１つであり、Ｒ_１１が複数ある場合、それぞれ同じでも異なっても良い。ｃは０以上３以下の整数である。）

(In the formula (9), * represents bonding to the NH group in the general formula (7). In the formula, A represents an alkylene group, a substituted alkylene group, —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 is one selected from an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and when there are a plurality of R _{11 s} , they may be the same or different, and c is 0 or more and 3 or less. (It is an integer.)

Particularly preferred among the groups represented by the above formula (9) are those represented by the following formula (10) (some of them have R ₂ in the general formula (7)).

（式（１０）中、＊は一般式（７）におけるＮＨ基に結合することを示す。Ｒ_１２はアルキレン基、置換アルキレン基、−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。）

(In the formula (10), * indicates bonding to the NH group in the general formula (7). R ₁₂ is an alkylene group, a substituted alkylene group, —O—, —S—, —SO ₂ —, —C ( ═O) —, —NHC (═O) —, —C (CF ₃ ) ₂ —, an organic group selected from a single bond.

Specific examples of the alkylene group and substituted alkylene group as A in the above formula (8) and formula (9) and R ₁₂ in the above formula (10) 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) - and -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) — and the like. Among these, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — has sufficient solubility in not only an alkaline aqueous solution but also a solvent, and a polyamide having a better balance. A resin can be obtained, which is preferable.

  Further, Y in the polyamide resin having the structure represented by the general formula (7) is an organic group, and examples of such an organic group include the same as those described above for X. Examples include aromatic groups composed of structures such as benzene rings, naphthalene rings and bisphenol structures, heterocyclic organic groups composed of structures such as pyrrole rings and furan rings, and siloxane groups. What is represented by 11) is preferable. These may be used alone or in combination of two or more.

（式（１１）中、＊は、一般式（７）における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及び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及びハロゲン原子から選ばれた１つを示す。ｔは０以上２以下の整数である。Ｒ_１５〜Ｒ_１８は、有機基である。
なお、上記式（１１）において、上記一般式（７）におけるＹの置換基Ｒ_３は省略している。）

(In formula (11), * indicates that it is bonded to the C═O group in general formula (7). 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 an alkyl group, an alkyl ester group, an alkyl ether. R ₁₄ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, each of which may be the same or different. t is an integer from 0 to 2. R _{15 to} R ₁₈ are organic groups.
In the formula (11), the Y substituent R ₃ in the general formula (7) is omitted. )

Among these groups represented by the formula (11), particularly preferred are those represented by the following formula (12) (some of them have R ₃ in the general formula (7)).
Regarding the structure derived from tetracarboxylic dianhydride in the following formula (12), mention is made of those in which both the positions bonded to the C═O group in the general formula (7) are in the meta position and both are in the para position. However, it may have a structure including a meta position and a para position.

（式（１２）中、＊は一般式（７）における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及び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以上１５以下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は０以上２以下の整数である。）

(In the formula (12), * represents bonding to the C═O group in the general formula (7). R ₁₉ represents an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom. Each of which may be the same or different, and R ₂₀ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted. U is an integer from 0 to 2.

  Further, in the case of the polyamide resin represented by the general formula (7), the terminal amino group of the polyamide resin is replaced with an alkenyl group or an amount not affecting the mechanical properties and heat resistance of the cured product cured at low temperature. It is also possible to use an acid anhydride or monocarboxylic acid containing an aliphatic group having at least one alkynyl group or a cyclic compound group, or end-capping as an amide.

  Examples of the acid anhydride or monocarboxylic acid containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group include maleic anhydride, citraconic anhydride, and 2,3-dimethylmaleic anhydride. 4-cyclohexene-1,2-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, methyl -5-norbornene-2,3-dicarboxylic acid anhydride, itaconic acid anhydride, het acid anhydride, 5-norbornene-2-carboxylic acid, 4-ethynylphthalic acid anhydride, 4-phenylethynylphthalic acid anhydride, etc. Can be mentioned. These may be used alone or in combination of two or more, and a part of the end-capped amide moiety may be dehydrated and closed.

  Further, the present invention is not limited to this method, and an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group as a terminal carboxylic acid residue contained in the polyamide-based resin. Can also be used to end-cleave as amides.

  Furthermore, in the case of the polyamide resin represented by the general formula (7), at least one end is blocked with a nitrogen-containing cyclic compound so as not to affect the mechanical properties and heat resistance of the cured product cured at low temperature. It may have a stopped group. 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.

The polyamide resin having the structure represented by the general formula (7) is, for example, a compound selected from diamine, bis (aminophenol), 2,4-diaminophenol, and the like containing X in the general formula (7) Can be synthesized by reacting Y and a compound selected from tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid, dicarboxylic acid dichloride, dicarboxylic acid derivative, and the like.
In the case of using dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like with dicarboxylic acid in advance in order to increase the reaction yield of the polyamide resin. May be used.

  The polyamide resin having the structure represented by the general formula (7) is dehydrated and closed by heating to obtain a heat resistant resin in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both. In addition, as temperature which performs dehydration ring closure, when heating at high temperature, it can process at 280 to 380 degreeC, and when heating at low temperature, it can process at 150 to 280 degreeC.

[Photoacid generator (B)]
The photoacid generator (B) used in the present invention is a compound that generates an acid by light. For example, a photosensitizer capable of positive patterning can be used, and a wavelength of 200 to 500 nm is particularly preferable. Is preferably a compound that generates an acid upon irradiation with actinic radiation having a wavelength of 350 to 450 nm.
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 compounds, dihydropyridine compounds, 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 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 photosensitive agent remaining in the relief pattern in the unexposed area is decomposed by heat at the time of curing to generate an acid, and the photosensitive agent plays an important role as a reaction accelerator. In the case of such a photosensitive diazoquinone compound, an ester of 1,2-naphthoquinone-2-diazide-4-sulfonic acid which is more easily decomposed by heat is preferable.

  Although content of the photo-acid generator (B) in the photosensitive resin composition of this invention is not specifically limited, 1 mass part or more and 50 mass parts with respect to 100 mass parts of alkali-soluble resin (A). The following is preferable, and 5 parts by mass and 20 parts by mass are more preferable. When the addition amount is within the above range, good patterning performance can be exhibited.

[Silane coupling agent (C)]
The photosensitive resin composition of this invention contains the silane coupling agent (C) represented by following General formula (1). In the chemical structure of the silane coupling agent (C), a spacer with a specific alkyl chain is inserted between the alkenyl moiety involved in crosslinking and the alkoxysilane or isocyanate group acting on adhesion, whereby the polymerization activity of the alkenyl group And a high residual film at the time of curing becomes possible.

R ¹ in the general formula (1) is a hydrogen atom or a methyl group, and R ² is an alkoxy group having 1 to 6 carbon atoms or an isocyanate group.
R ³ is a hydrocarbon having 1 to 6 carbon atoms, and examples of such a hydrocarbon group include:
In addition, m is an integer of 1 to 3, and n is an integer of 4 to 20 for increasing the polymerization activity of the alkenyl group as the spacer and enabling a high residual film upon curing. The preferred lower limit is 6.

  Specific examples of such silane coupling agents (C) include 6-methacryloxyhexyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 10-methacryloxydecyltrimethoxysilane, 11-methacryloxyundecyltri. Methoxysilane, 8-acryloxyoctyltrimethoxysilane, 12-acryloxydodecyltrimethoxysilane, 8-methacryloxyoctyltriethoxysilane, 12-methacryloxydecyltriethoxysilane, 10-methacryloxydecyltriisocyanatosilane, 10 -Methacryloxydecyl monomethyldimethoxysilane and the like, but are not limited thereto. Moreover, these can be used 1 type or in mixture of 2 or more types.

  Although content of the silane coupling agent (C) in the photosensitive resin composition of this invention is not specifically limited, 0.05 to 50 mass parts with respect to 100 mass parts of alkali-soluble resin (A). The amount is preferably not more than mass parts, more preferably not less than 0.1 parts by mass and not more than 20 parts by mass. 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 while exhibiting an effect on scum removal.

  In order to further improve the characteristics of the photosensitive resin composition of the present invention, a second silane coupling agent can be added in combination with the silane coupling agent (C). Examples of the second silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyl Trime Xysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanate Examples thereof include, but are not limited to, propyltriethoxysilane and silicon compounds obtained by reacting an amino group-containing silicon compound with an acid dianhydride or acid anhydride.

  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. For example, maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, phthalic anhydride, pyromellitic anhydride, Examples include 4,4′-biphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, 4,4′-carbonyldiphthalic anhydride, and the like. Moreover, in using, it can be used individually or in combination of 2 or more types.

[solvent]
In the photosensitive resin composition of the present invention, the above components are dissolved in a solvent and used in the form of a varnish. Examples of such a 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 and methyl-3- Examples thereof include methoxypropionate and may be used alone or in combination.

  Although content of the solvent in the photosensitive resin composition of this invention is not specifically limited, It is preferable that it is 50 to 300 mass parts with respect to 100 mass parts of alkali-soluble resin (A). 100 parts by mass or more and 200 parts by mass or less is more preferable. When the addition amount is within the above range, the resin can be sufficiently dissolved and a varnish with high handling properties can be produced.

[Solution Accelerator]
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.
As the dissolution accelerator, a compound having a phenolic hydroxyl group is particularly preferable.

  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.

[Curing film]
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 applying on a semiconductor element, the application amount is generally applied so that the final film thickness after curing is 0.1 to 30 μm. By setting it as such a numerical value range, the function as a protective film of a semiconductor element and an insulating film is fully exhibited, and a fine relief pattern can be obtained.
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, when a relief pattern is formed after pre-baking at 60 to 130 ° C. and drying the coating film, the desired pattern shape is irradiated with actinic radiation. 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 obtained by adding an appropriate amount of a water-soluble organic solvent or a surfactant such as an alcohol such as methanol and ethanol to the aqueous solution can be preferably used.
As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment (curing) is performed to obtain a cured film as a cured product having excellent heat resistance.
The heat treatment can be performed at a high temperature or a low temperature, and the heat treatment temperature at a high temperature is preferably 280 ° C to 380 ° C, more preferably 290 ° C to 350 ° C. The heat treatment temperature at low temperature is preferably 150 ° C. to 280 ° C., more preferably 180 ° C. to 260 ° C. 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 photosensitive resin composition on a semiconductor element, and a buffer formed by forming a cured film of the above-described photosensitive resin composition on the passivation film. A protective film such as a coating film, an insulating film such as an interlayer insulating film formed by forming a cured film of the above-described photosensitive resin composition on a circuit formed on a semiconductor element, an α-ray blocking film, a flat surface Examples thereof include a chemical 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 demonstrates this invention concretely, this invention is not limited to these Examples.
Example 1
<Synthesis of polyamide resin (A-1)>
In a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube, 21.43 g (0.083 mol) of diphenyl ether-4,4′-dicarboxylic acid and 1-hydroxy-1 were added. , 2,3-benzotriazole monohydrate 22.43 g (0.166 mol) obtained by reacting with 40.87 g (0.083 mol) of a mixture of dicarboxylic acid derivatives, hexafluoro-2, 2-Bis (3-amino-4-hydroxyphenyl) propane (36.62 g, 0.100 mol) was added, and N-methyl-2-pyrrolidone (296.96 g) was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the 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 3 hours.

  After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-1) was obtained. In addition, the weight average molecular weight of the obtained compound was 13,040.

<Synthesis of Photosensitive Agent (Q-1)>
In a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 11.04 g (0.026 mol) of phenol represented by the formula (C-1), 18.81 g (0.070 mol) of 2-naphthoquinone-2-diazide-4-sulfonyl chloride and 170 g of acetone were added and stirred and dissolved.

  Next, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 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, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. Next, after filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), and then the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum. A photosensitizer represented by the structure of formula (Q-1) was obtained.

<Preparation of photosensitive resin composition>
10 g of the polyamide resin (A-1) synthesized above, 1.5 g of the photosensitive agent (Q-1) synthesized above, and 0.5 g of 6-methacryloxyhexyltrimethoxysilane (D-1) were added to γ-butyrolactone. After mixing and dissolving in 12 g, the mixture was filtered with a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Example 1.

<< Example 2 >>
In the production of the photosensitive resin composition of Example 1, Example was used except that 8-methacryloxyoctyltrimethoxysilane (D-2) was used instead of 6-methacryloxyhexyltrimethoxysilane (D-1). As in Example 1, the photosensitive resin composition of Example 2 was prepared.

Example 3
In the preparation of the photosensitive resin composition of Example 1, Example was used except that 8-acryloxyoctyltrimethoxysilane (D-3) was used instead of 6-methacryloxyhexyltrimethoxysilane (D-1). In the same manner as in Example 1, the photosensitive resin composition of Example 3 was produced.

Example 4
In the production of the photosensitive resin composition of Example 1, Example 10 was used except that 10-methacryloxydecyl monomethyldimethoxysilane (D-4) was used instead of 6-methacryloxyhexyltrimethoxysilane (D-1). As in Example 1, the photosensitive resin composition of Example 4 was prepared.

Example 5
In the production of the photosensitive resin composition of Example 1, except that 8-methacryloxyoctyltriisocyanatosilane (D-5) was used instead of 6-methacryloxyhexyltrimethoxysilane (D-1) In the same manner as in Example 1, the photosensitive resin composition of Example 5 was prepared.

Example 6
<Synthesis of polyamide resin (A-2)>
Into a four-necked separable flask equipped with a thermometer, a stirrer, a raw material charging port and a dry nitrogen gas inlet tube, 30.0 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0. 082 mol) was added, and 400 ml of acetone was added and dissolved.

  Next, 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 addition, the temperature of the mixture was heated to 40 ° C. and stirred for 2 hours, and then 30.0 g (0.218 mol) of potassium carbonate was gradually added and further stirred for 2 hours. Heating was stopped and the mixture was further stirred at room temperature for 18 hours. Thereafter, while vigorously stirring the mixture, an aqueous sodium hydroxide solution was gradually added. 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, 37% by weight hydrochloric acid aqueous solution and 500 ml of water were added to adjust the pH of the solution to be in the range of 6.0 to 7.0. Next, the obtained precipitate was filtered off, the filtrate was washed with water and dried at 60 to 70 ° C., and bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2 A solid of bis (4-hydroxyphenyl) propane 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. to be completely dissolved. Thereto, 300 mL of pure water at 50 ° C. was added 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. to obtain bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis. (4-Hydroxyphenyl) propane was obtained.

  Into a 1 L flask, 20 g of the bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above was put, and 1.0 g of 5% palladium-carbon and 180.4 g of ethyl acetate 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.

  Into a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube, the bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2- 14.5 g (0.024 mol) of bis (4-hydroxyphenyl) propane was added, 40 g of γ-butyrolactone was added and dissolved, and the mixture was cooled to 15 ° C. with stirring. Thereto, 6.8 parts by weight (0.022 mol) of 4,4′-oxydiphthalic anhydride and 12.0 parts by weight of γ-butyrolactone were added and stirred at 20 ° C. for 1.5 hours. Thereafter, the mixture was heated to 50 ° C. and stirred for 3 hours. Then, 5.2 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 to obtain the target polyamide resin (A-2). In addition, the weight average molecular weight of the obtained compound was 13,200.

<Preparation of photosensitive resin composition>
The photosensitive resin of Example 6 was prepared in the same manner as in Example 2 except that the polyamide resin (A-2) was used instead of the polyamide resin (A-1) in the production of the photosensitive resin composition of Example 2. A composition was prepared.

Example 7
<Synthesis of Novolak Resin (A-3)>
In a four-necked separable flask equipped with a thermometer, a stirrer, a raw material charging port and a dry nitrogen gas inlet tube, 64.9 g (0.60 mol) of m-cresol and 43.3 g of p-cresol in a dry nitrogen stream. (0.40 mol), 30 wt% aqueous formaldehyde solution 65.1 g (formaldehyde 0.65 mol), and oxalic acid dihydrate 0.63 g (0.005 mol) were immersed in an oil bath, A polycondensation reaction was carried out at 100 ° C. for 4 hours while refluxing the reaction solution. Thereafter, the temperature of the oil bath is raised to 200 ° C. over 3 hours, and then the pressure in the flask is reduced to 50 mmHg or less to remove moisture and volatile components. A novolak-type phenol resin (A-3) having an average molecular weight of 3000 was obtained.

<Preparation of photosensitive resin composition>
In the production of the photosensitive resin composition of Example 2, the same as Example 2 except that cresol novolac type phenol resin (A-3) was used instead of polyamide resin (A-1). A photosensitive resin composition was prepared.

Example 8
<Synthesis of Novolak Resin (A-4)>
In a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet tube, 73.3 g (0.60 mol) of 2,3-xylenol, o-cresol 43 under a dry nitrogen stream .3 g (0.40 mol), 116.0 g (0.95 mol) of salicylaldehyde, and 3.4 g (0.02 mol) of paratoluenesulfonic acid were immersed in an oil bath, and the reaction solution was refluxed. The polycondensation reaction was carried out at 100 ° C. for 4 hours. Thereafter, 100 g of acetone and 2.0 g (0.02 mol) of triethylamine were added and stirred for 30 minutes while cooling the flask, and then 200 g of pure water was further added and stirred for 30 minutes. After cooling to room temperature, the stirring was stopped, the separated aqueous layer was removed, 20 g of triethylene glycol monomethyl ether was added, and the temperature of the oil bath was increased to 200 ° C. over 3 hours. After reducing the pressure to 50 mmHg or less and removing volatile components, the resin was cooled to room temperature to obtain an aromatic novolak phenol resin (A-4) having a weight average molecular weight of 3000.

<Preparation of photosensitive resin composition>
In the production of the photosensitive resin composition of Example 2, Example 8 was carried out in the same manner as in Example 2 except that the aromatic novolak type phenol resin (A-4) was used instead of the polyamide resin (A-1). A photosensitive resin composition was prepared.

Example 9
In the preparation of the photosensitive resin composition of Example 2, a phenol aralkyl resin having a weight average molecular weight of 1,000 (trade name: Milex XLC-4L, manufactured by Mitsui Chemicals, Inc.) instead of the polyamide resin (A-1) ( A photosensitive resin composition of Example 9 was produced in the same manner as Example 2 except that A-5) was used.

Example 10
In the production of the photosensitive resin composition of Example 2, a polyhydroxystyrene / styrene copolymer resin having a weight average molecular weight of 3,500 (manufactured by Maruzen Petrochemical Co., Ltd., trade name) instead of the polyamide resin (A-1). A photosensitive resin composition of Example 10 was produced in the same manner as in Example 2 except that Marca Linker CST-70) (A-6) was used.

≪Comparative example 1≫
10 g of polyamide resin (A-1) and 1.5 g of the photosensitive agent (Q-1) synthesized above were mixed and dissolved in 12 g of γ-butyrolactone, and then filtered through a fluororesin filter having a pore size of 0.2 μm. The photosensitive resin composition of Comparative Example 1 was obtained.

≪Comparative example 2≫
10 g of polyamide resin (A-1), 1.5 g of the photosensitive agent (Q-1) synthesized above, and 0.5 g of 3-methacryloxypropyltrimethoxysilane (D-6) were mixed with 12 g of γ-butyrolactone. Then, the mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Comparative Example 2.

<Development adhesion evaluation>
The photosensitive resin compositions of Examples 1 to 10 were 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 form a coating film having a thickness of about 7.5 μm. Obtained. Through this coating film, a photomask (made by Toppan Printing Co., Ltd., test chart No. 1: remaining pattern and blanking pattern with a width of 0.88 to 50 μm is drawn), i-line stepper (manufactured by Nikon Corporation) NSR-4425i) was used for irradiation with varying exposure.
Next, using a 2.38% tetramethylammonium hydroxide aqueous solution as the developer, the development time was adjusted so that the difference between the film thickness after pre-baking and the film thickness of the unexposed area after development was 1.0 μm. Then, the exposed portion was dissolved and removed by performing paddle development twice, and then rinsed with pure water for 10 seconds. The exposure amount from when the 100 μm square via hole pattern was formed until the continuous pattern of 5 μm peeled was quantified as the adhesion during development. The larger this value, the better the adhesion during development.

<Scum evaluation>
Create a 100 μm via hole pattern in the same way as the development adhesion evaluation, and the residue in the opening is good (no residue), somewhat good (some residue is confirmed, but practically no problem), bad ( Residues were observed in the entire opening, and the evaluation was made at three levels.

<Evaluation of cured film ratio>
The photosensitive resin compositions of Examples 1 to 10 were 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 form a coating film having a thickness of about 7.5 μm. Obtained. The coating film was heated in an oven at 150 ° C. for 30 minutes and then at 300 ° C. for 30 minutes while keeping the oxygen concentration at 1000 ppm or less, and the film thickness after returning to room temperature was measured. The film thickness change rate of the film thickness after hardening and the film thickness before hardening was computed from the following formula, and it evaluated as a hardening residual film rate.
Cured residual film ratio = film thickness after curing / film thickness before curing * 100
The higher the residual film rate, the better in order to maintain a sufficient film thickness for protecting the semiconductor element.

<Base adhesion evaluation>
The cured film prepared by measurement of the cured residual film rate was cut 11 times in the vertical and horizontal directions at 1 mm intervals with a cutter to prepare 100 independent films. Then, after processing for 300 hours under the conditions of 125 ° C. and 100% relative humidity with a pressure cooker tester device, a peel test was performed with cello tape (registered trademark), and the number of peels was recorded. The smaller the number of peels, the better the reliability as a semiconductor.

<Fabrication of semiconductor device>
Using a simulated element wafer having an aluminum circuit on the surface, the photosensitive resin compositions of Examples 1 to 10 were applied so as to have a final thickness of 5 μm, followed by patterning and curing. After that, each chip size is divided and mounted on a lead frame for 16 Pin DIP (Dual Inline Package) using a conductive paste, and then an epoxy resin for semiconductor encapsulation (EME-6300H manufactured by Sumitomo Bakelite Co., Ltd.) is used. The semiconductor device was manufactured by sealing. 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% relative humidity) was checked for open defects in the aluminum circuit, and no corrosion or the like was observed, and it is expected that the semiconductor device can be used without problems.

Table 1 below shows examples and comparative examples.

Claims (11)

A photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a silane coupling agent (C), wherein the silane coupling agent (C) is represented by the following general formula (1): A photosensitive resin composition characterized by being represented.

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkoxy group having 1 to 6 carbon atoms or an isocyanate group, R ³ is a hydrocarbon having 1 to 6 carbon atoms, and m is (It is an integer from 1 to 3, and n is an integer from 4 to 20.)   The photosensitive resin composition according to claim 1, wherein in the silane coupling agent (C), n in the general formula (1) is an integer of 6 or more and 12 or less. The photosensitive resin composition according to claim 1, wherein R ² in the general formula (1) is an alkoxy group having 1 to 6 carbon atoms in the silane coupling agent (C).   The photosensitive resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin (A) is at least one resin selected from a phenol resin, a hydroxystyrene resin, and a polyamide resin.   The photosensitive property according to any one of claims 1 to 4, wherein the silane coupling agent (C) contains 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). Resin composition.   The photosensitive resin composition according to claim 1, wherein the photoacid generator (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 6.   A protective film comprising the cured film according to claim 7.   The insulating film comprised with the cured film of Claim 7.   A semiconductor device comprising the cured film according to claim 7.   A display device having the cured film according to claim 7.