JP6645424B2 - Photosensitive resin composition, cured film, protective film, insulating film, and electronic device - Google Patents

Description

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

Conventionally, for a protective film and an insulating film in a semiconductor element, a photosensitive resin composition having excellent heat resistance, excellent electrical properties, mechanical properties, and the like, and containing a patternable alkali-soluble resin has been used. Was.
Here, when using a photosensitive resin composition containing an alkali-soluble resin, in order to simplify the process, a diazoquinone compound of a photoacid generator is combined with these resins to prepare a photosensitive resin composition. It has been made general purpose. For example, Patent Literature 1 describes a photosensitive resin composition containing an alkali-soluble phenol resin, a photosensitive resin composition, an organic solvent, and an alkoxysilyl group-containing adhesion aid.

JP 2008-164816 A

Usually, the production of a protective film or an insulating film of a semiconductor element using a photosensitive resin composition includes forming a resin film by applying the photosensitive resin composition to a support, exposing with actinic radiation, and developing with an alkali developing solution. Through a process such as patterning, cleaning with pure water, and curing by heating.
However, when the adhesion of the resin film to the support is not good, there is a concern that it is difficult to perform stable patterning. For this reason, it has been required to improve the adhesiveness of a resin film obtained using the photosensitive resin composition.
If the transparency of the resin film is not sufficient, there is a concern that the visibility of the pattern on the surface of the support decreases, thereby reducing the productivity in a post-process after patterning and curing. For this reason, it has been required to improve the transparency of a resin film obtained by using the photosensitive resin composition.

  Therefore, the present invention provides a photosensitive resin composition capable of forming a pattern with high adhesion and stably and obtaining a resin film having sufficient transparency. In addition, the present invention provides a cured film composed of a cured product of the photosensitive resin composition, a protective film and an insulating film composed of the cured film, and an electronic device having the cured film. I do.

  The present invention is achieved by the following [1] to [14].

[1]
An alkali-soluble resin (A),
A silane compound (B) represented by the following general formula (1),
A photoacid generator (C);
Including
The alkali-soluble resin (A) is selected from polybenzoxazole, polybenzoxazole precursor, polyimide, polyimide precursor,
The cyclic structure of A in the following general formula (1) and Si in the following general formula (1) are directly bonded ,
Shi A in the general formula (1) of the run compound (B) is an organic group selected from organic groups group represented by the following formula (3), the photosensitive resin composition.

（式中Ａは環状構造を有する（ｍ＋ｎ）価の有機基を示し、Ｒ１およびＲ３はそれぞれ独立に水素原子、置換若しくは無置換の炭素数１〜１０の飽和アルキル基を示し、Ｒ２およびＲ４は置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基を示し、ａ及びｂはａ＋ｂ＝３を満たす０〜３の整数を示し、ｃ及びｄはｃ＋ｄ＝３を満たす０〜３の整数を示し、ｍ及びｎは０〜２の整数を示しｍ＋ｎ≠０である。）

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b each represent an integer of 0 to 3 satisfying a + b = 3; c and d each represent an integer of 0 to 3 that satisfies c + d = 3, and m and n each represent an integer of 0 to 2 and m + n ≠ 0.)

[3] The photosensitive resin composition according to [1] or [2],
A in the photosensitive resin composition, wherein A in the general formula (1) of the silane compound (B) is an organic group selected from the organic group group represented by the following formula (2).

（式中Ｘ１は単結合、Ｃ（−Ｙ１）（−Ｙ２）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ１及びＹ２は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。）

(Wherein X1 represents a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing an amide group, and Y1 and Y2 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group.)

[5] The photosensitive resin composition according to [1] or [4],
A photosensitive resin composition wherein A in the general formula (1) of the silane compound (B) is an organic group selected from the organic group group represented by the following formula (3).

（式中Ｘ２は単結合、Ｃ（−Ｙ３）（−Ｙ４）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ３及びＹ４は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。）

(Wherein X2 represents a single bond, C (-Y3) (-Y4), a divalent organic group containing a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, and Y3 and Y4 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group.)

[7] The photosensitive resin composition according to any one of [1] to [6],
A photosensitive resin composition further comprising a phenol resin (D) obtained by reacting a phenol compound with an aromatic aldehyde compound.

[8] The photosensitive resin composition according to [7],
A photosensitive resin composition wherein the aromatic aldehyde compound contains an aromatic aldehyde compound represented by the following formula (4).

（式中Ｒ_１は水素、炭素数１以上２０以下のアルキル基、アルコキシ基及びヒドロキシ基から選ばれる有機基を示し、ｔは０以上３以下の整数である。）

(In the formula, R ₁ represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxy group, and t is an integer of 0 to 3 inclusive.)

[9] The photosensitive resin composition according to [7] or [8],
A photosensitive resin composition wherein the phenol compound contains a phenol compound represented by the following formula (5).

（式中Ｘ３は単結合、Ｃ（−Ｙ７）（−Ｙ８）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ７及びＹ８は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示し、Ｙ５及びＹ６は、それぞれ独立に置換若しくは無置換の炭素数１〜２０の飽和アルキル基、置換若しくは無置換の炭素数１〜２０の不飽和アルキル基、置換若しくは無置換の炭素数１〜２０のアルコキシ基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。ｐ及びｑは、それぞれ独立に１〜３の整数を示し、ｒ及びｓは、それぞれ独立に０〜３の整数を示す。）

(Wherein X3 represents a single bond, C (-Y7) (-Y8), a divalent organic group containing a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, and Y7 and Y8 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group; Y5 and Y6 each independently represent a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 20 carbon atoms, Represents an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group. Independently an integer of 1 to 3 is, r and s, each independently represent an integer of 0-3.)

[10] The photosensitive resin composition according to any one of [1] to [9],
A photosensitive resin composition further containing a thermal crosslinking agent (E).

[11] A cured film composed of a cured product of the photosensitive resin composition according to any one of [1] to [10].

[12] A protective film comprising the cured film according to [11].

[13] An insulating film composed of the cured film according to [11].

[14] An electronic device having the cured film according to [11].

  ADVANTAGE OF THE INVENTION According to this invention, while being able to form a pattern stably with high adhesion, the photosensitive resin composition which can obtain the resin film which has sufficient transparency can be provided.

  The above and other objects, features and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.

It is a sectional view showing an example of an electronic device concerning this embodiment. It is a sectional view showing an example of an electronic device concerning this embodiment.

  Hereinafter, embodiments will be described with reference to the drawings as appropriate. In all the drawings, the same components are denoted by the same reference numerals, and description thereof will not be repeated. "-" Means the following from the above unless otherwise specified.

  The photosensitive resin composition according to the present embodiment includes a photosensitive resin containing an alkali-soluble resin (A), a silane compound (B) represented by the following general formula (1), and a photoacid generator (C). It is a resin composition.

（式中Ａは環状構造を有する（ｍ＋ｎ）価の有機基を示し、Ｒ１およびＲ３はそれぞれ独立に水素原子、置換若しくは無置換の炭素数１〜１０の飽和アルキル基を示し、Ｒ２およびＲ４は置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基を示し、ａ及びｂはａ＋ｂ＝３を満たす０〜３の整数を示し、ｃ及びｄはｃ＋ｄ＝３を満たす０〜３の整数を示し、ｍ及びｎは０〜２の整数を示しｍ＋ｎ≠０である）

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b each represent an integer of 0 to 3 satisfying a + b = 3; c and d each represent an integer of 0 to 3 that satisfies c + d = 3, and m and n each represent an integer of 0 to 2 and m + n ≠ 0.

  As described above, the protective film and the insulating film are formed, for example, by forming a resin film by applying a photosensitive resin composition to a support, exposing with actinic radiation, patterning by developing with an alkali developer, washing with pure water, and heating. Formed through a process such as curing by However, when the adhesion of the resin film to the support is not good, there is a concern that it is difficult to perform stable patterning. For example, if the adhesion of the resin film is not good, the pattern may be lost or deformed during development with an alkaline developer. In addition, when the transparency of the resin film is not sufficient, the visibility of the pattern on the surface of the support is reduced, and there is a concern that productivity in a post-process after patterning and curing is reduced. For example, when assembling an electronic device by singulating the support in a subsequent step, an error may occur in recognition of the singulated support due to a decrease in pattern visibility on the surface of the support, and throughput may be reduced. There is. For this reason, in order to realize stable production of an electronic device, it is important to improve both adhesion and transparency.

  As a result of intensive studies, the present inventors have found that the inclusion of a specific silane compound improves both the adhesion and the transparency of the photosensitive resin composition. The present embodiment is based on such knowledge, and based on such knowledge, a photosensitive composition containing an alkali-soluble resin (A), a silane compound (B) represented by the following general formula (1), and a photoacid generator (C). This is to realize a conductive resin composition. Therefore, according to this embodiment, a photosensitive resin composition having excellent adhesion and transparency can be realized. Thereby, it is also possible to realize an electronic device having excellent manufacturing stability.

（式中Ａは環状構造を有する（ｍ＋ｎ）価の有機基を示し、Ｒ１およびＲ３はそれぞれ独立に水素原子、置換若しくは無置換の炭素数１〜１０の飽和アルキル基を示し、Ｒ２およびＲ４は置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基を示し、ａ及びｂはａ＋ｂ＝３を満たす０〜３の整数を示し、ｃ及びｄはｃ＋ｄ＝３を満たす０〜３の整数を示し、ｍ及びｎは０〜２の整数を示しｍ＋ｎ≠０である）

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b each represent an integer of 0 to 3 satisfying a + b = 3; c and d each represent an integer of 0 to 3 that satisfies c + d = 3, and m and n each represent an integer of 0 to 2 and m + n ≠ 0.

  Hereinafter, the configuration of an electronic device including the photosensitive resin composition according to the present embodiment and a permanent film formed using the photosensitive resin composition will be described in detail.

First, the photosensitive resin composition according to the present embodiment will be described.
The photosensitive resin composition is used, for example, for forming a permanent film. By curing the photosensitive resin composition, a resin film constituting a permanent film is obtained. In the present embodiment, a permanent film is formed by, for example, patterning a coating film made of a photosensitive resin composition into a desired shape by exposure and development, and then curing the coating film by heat treatment or the like.

Specific applications of the permanent film formed using the photosensitive resin composition include, for example, an interlayer film, a surface protection film, and a dam material. The use of the photosensitive resin composition is not limited to this.
The interlayer film refers to an insulating film provided in a multilayer structure, and the type is not particularly limited. Examples of the interlayer film include those used in semiconductor device applications such as an interlayer insulating film forming a multilayer wiring structure of a semiconductor element, a build-up layer or a core layer forming a wiring board. Further, as the interlayer film, for example, a flattening film covering a thin film transistor (TFT) in a display device, a liquid crystal alignment film, a projection provided on a color filter substrate of an MVA (Multi Domain Vertical Alignment) type liquid crystal display device Alternatively, those used in display devices such as partition walls for forming a cathode of an organic EL element may be used.

  The surface protective film is formed on the surface of an electronic component or an electronic device, and refers to an insulating film for protecting the surface, and its type is not particularly limited. Examples of such a surface protective film include a passivation film or a buffer coat layer provided on a semiconductor element, or a cover coat provided on a flexible substrate. Further, the dam material includes, for example, a spacer used for forming a hollow portion for disposing an optical element or the like on a substrate.

  Hereinafter, each component of the photosensitive resin composition according to the exemplary embodiment will be described 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 embodiment has a hydroxyl group, particularly a phenolic hydroxyl group and / or a carboxyl group, in its main chain or side chain. Examples thereof include a phenol resin, a phenol aralkyl resin, and a hydroxystyrene resin. And acrylic resins such as methacrylic acid resins and methacrylic acid ester resins, cyclic olefin resins, polyamide resins and the like. Among these, phenol resins, phenol aralkyl resins, hydroxystyrene resins, and polyamide resins are preferable, and polybenzoxazole, polybenzoxazole precursor, polyimide, and polyimide precursor, which are particularly excellent in heat resistance and film toughness, are particularly preferable. One or two or more selected from polyamide resins. These alkali-soluble resins can be used alone or in combination of two or more.

  Examples of the phenol resin in the alkali-soluble resin (A) include a reaction product of a phenol compound and an aldehyde compound represented by a novolak-type phenol resin and a reaction product of a phenol compound and a dimethanol compound represented by a phenol aralkyl resin. Can be used. However, a phenol resin different from the phenol resin (D) described later is used as the phenol resin in the alkali-soluble resin (A).

  Examples of the phenol compound used for the novolak type phenol resin in the alkali-soluble resin (A) include phenol; cresols such as o-cresol, m-cresol, p-cresol; 2,3-dimethylphenol; Dimethylphenols such as 4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol and 3,5-dimethylphenol; o-ethylphenol, m-ethylphenol, p- Ethylphenols such as ethylphenol; alkylphenols such as isopropylphenol, butylphenol and p-tert-butylphenol, and polyhydric phenols such as resorcinol, catechol, hydroquinone, pyrogallol, and phloroglucin. But not limited to these. These phenols can be used alone or in combination of two or more.

  Examples of the aldehyde compound used in the novolak type phenol resin in the alkali-soluble resin (A) include, but are not limited to, formaldehyde, paraformaldehyde, and acetaldehyde. These aldehydes can be used alone or in combination of two or more.

As the phenol compound used for the phenol aralkyl resin in the alkali-soluble resin (A), the same phenol compound as the phenol compound used for the novolak type phenol resin can be used.
A phenol aralkyl resin can be obtained by reacting this phenol compound with a compound such as a dimethanol compound shown below.

The dimethanol compounds used for the phenol aralkyl resin in the alkali-soluble resin (A) include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4′-biphenyldimethanol, and 3,4 ′. And dimethanol compounds such as -biphenyldimethanol, 3,3'-biphenyldimethanol and 2,6-naphthalenedimethanol.
In addition to the dimethanol compound, 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 4,4′-bis (methoxymethyl) biphenyl, and 3,4′-bis (methoxy) Bis (alkoxymethyl) compounds such as methyl) biphenyl, 3,3′-bis (methoxymethyl) biphenyl and methyl 2,6-naphthalenedicarboxylate; 1,4-bis (chloromethyl) benzene, 1,3-bis ( Chloromethyl) benzene, 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, 4,4′-bis (chloromethyl) biphenyl, 3,4′-bis (chloromethyl) biphenyl, , 3'-bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, 3,4'-bis (bromomethyl) biphenyl And 3,3'-bis (bromomethyl) bis biphenyl (haloalkyl) compounds to by reaction with a phenol compound, can be obtained phenol aralkyl resin. These compounds can be used alone or in combination of two or more.

  As the hydroxystyrene resin in the alkali-soluble resin (A), a polymerization reaction product or a copolymerization reaction product obtained by subjecting hydroxystyrene, styrene, and their derivatives to radical polymerization, cationic polymerization, or anionic polymerization can be used. .

  The polyamide resin in the alkali-soluble resin (A) refers to a resin having a benzoxazole precursor structure and / or an imide precursor structure. In addition, the polyamide resin is a benzoxazole precursor structure, an imide precursor structure, and a benzoxazole structure generated by a part of a benzooxazole precursor structure undergoing a ring-closing reaction. It may have an imide structure, or may have an amic acid ester structure.

  A specific benzoxazole precursor structure refers to a structure represented by the following formula (6), an imide precursor structure refers to a structure represented by the following formula (7), and a benzoxazole structure refers to the following. An imide structure refers to a structure represented by the following formula (9), and an amic acid ester structure refers to a structure represented by the following formula (10).

  D and R 'in the above formulas (6) to (10) represent a monovalent or divalent organic group. Among these polyamide resins, a polyamide resin having a repeating unit represented by the following general formula (11) is preferable from the viewpoint of the heat resistance of the cured product of the photosensitive resin composition of the present embodiment.

（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、アシルオキシ基又はシクロアルキル基であり、複数有する場合、それぞれ同一であっても異なってもよい。Ｒ_３は、水酸基、カルボキシル基、−Ｏ−Ｒ_４又は−ＣＯＯ−Ｒ_４であり、複数有する場合、それぞれ同一であっても異なってもよい。Ｒ_２及びＲ_３におけるＲ_４は、炭素数１〜１５の有機基である。ここで、式（１１）において、Ｒ_２に、水酸基がない場合は、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に、カルボキシル基がない場合は、Ｒ_２の少なくとも１つは水酸基である。ｋは０〜８の整数、ｌは０〜８の整数である。ｅは２〜１００の整数である。）

(In the formula, 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. R ₃ is a hydroxyl group, a carboxyl group, —OR ₄ or —COO—R ₄ , and when two or more are present, they may be the same or different, and R ₄ in R ₂ and R ₃ is is an organic group having 1 to 15 carbon atoms. here, in equation (11), the _{R 2,} when there is no hydroxyl group, at least one of _{R 3} is carboxyl group. Further, _{R 3,} carboxyl When there is no group, at least one of R ₂ is a hydroxyl group, k is an integer of 0 to 8, l is an integer of 0 to 8, and e is an integer of 2 to 100.)

In the polyamide resin having the structure represented by the general formula (11), as R ₂ and R ₃ , a hydroxyl group and a carboxyl group are protected by a protecting group R ₄ in adjusting the solubility of the polyamide resin in an aqueous alkali solution. The groups described above can be used, and specifically, -OR ₄ as R ₂ , -OR ₄ and -COO-R ₄ as R ₃ can be used. Examples of such an organic group having 1 to 15 carbon atoms as R ₄ include a formyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a tert-butoxycarbonyl group, a phenyl group, a benzyl group, Examples thereof include a tetrahydrofuranyl group and a tetrahydropyranyl group.

  The organic group as X in the polyamide resin having the structure represented by the general formula (11) is not particularly limited, and examples thereof include 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; and a siloxane group. More specifically, a compound represented by the following formula (12) is preferable. These may be used alone or in combination of two or more as necessary.

（式（１２）中、＊は、一般式（１１）におけるＮＨ基に結合することを示す。Ｚは、アルキレン基、置換アルキレン基、−Ｏ−Ｃ_６Ｈ_４−Ｏ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−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、それぞれ同一であっても異なっていてもよい。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。ｕは０〜４の整数である。Ｒ_７〜Ｒ_１０はそれぞれ１価または２価の有機基である。
なお、上記式（１２）において、上記一般式（１１）におけるＸの置換基Ｒ_２は省略している。）

(In the formula (12), * indicates that the compound bonds to the NH group in the general formula (11). Z is an alkylene group, a substituted alkylene group, —O—C ₆ H ₄ —O—, —O—, —S—, —SO ₂ —, —C (＝ O) —, —NHC (＝ O) — or a single bond, and R ₅ is 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, and u is an integer of 0 to 4. _{7 to} R ₁₀ are each a monovalent or divalent organic group.
In the above formula (12), the substituent _{R 2} of X in the general formula (11) is omitted. )

Among the groups represented by the above formula (12), particularly preferred are groups represented by the following formula (13) (some having R ₂ in the general formula (11)).

（式（１３）中、＊は一般式（１１）におけるＮＨ基に結合することを示す。式中Ｚ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る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よい。ｖは０以上３以下の整数である。）

(In the formula (13), * during formula Z denotes a bond to the NH group in formula (11) is an alkylene group, 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 , they may be the same or different, and v is an integer of 0 or more and 3 or less. Is.)

Among the groups represented by the above formula (13), particularly preferred are groups represented by the following formula (14) (some having R ₂ in the general formula (11)).

（式（１４）中、＊は一般式（１１）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 (14), * is _{.R 12} indicating that it binds to the NH group in formula (11) is an alkylene group, substituted alkylene group, -O -, - S -, - SO 2 -, - C ( = O) -, - NHC ( = O) -, - C (CF 3) 2 -, an organic group selected from a single bond).

The formula (12) and an alkylene group as _{R 12} Z and the formula in (14) in equation (13), specific examples of substituted alkylene _{group, -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 C _{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 - is not only an alkaline aqueous solution, also having sufficient solubility in solvent, more excellent balance polyamide It is preferable because a resin can be obtained.

  Further, in the polyamide resin having the structure represented by the general formula (11), Y is an organic group, and examples of such an organic group include those similar to the above-mentioned X. Examples thereof include 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, a pyridine ring and a furan ring; a siloxane group, and the like. Preferred are those represented by the following formula (15). These may be used alone or in combination of two or more.

（式（１５）中、＊は、一般式（１１）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よい。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。ｗは０以上２以下の整数である。Ｒ_１５〜Ｒ_１８はそれぞれ１価または２価の有機基である。
なお、上記式（１５）において、上記一般式（１１）におけるＹの置換基Ｒ_３は省略している。）

(In the formula (15), * is, .J is indicating that it binds to a C = O group in the general formula _{(11), -CH 2 -,} - C (CH 3) 2 -, - O -, - S —, —SO ₂ —, —C (＝ O) —, —NHC (＝ O) —, —C (CF ₃ ) ₂ — or a single bond, and R ₁₃ is an alkyl group, an alkyl ester group, or 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. w is an integer of 0 to 2. R _{15 to} R ₁₈ are each a monovalent or divalent organic group.
In the formula (15), the substituent R ₃ for Y in the formula (11) is omitted. )

Of these groups represented by the formula (15), particularly preferred are those represented by the following formula (16) (some having R ₃ in the general formula (11)).
Regarding the structure derived from tetracarboxylic dianhydride in the following formula (16), those where the positions bonded to the CＣO group in the general formula (11) are both meta-positions and those where both are para-positions are listed. However, a structure including each of the meta position and the para position may be used.

(In the formula (16), * indicates that the compound is bonded to the CＯO group in the general formula (11). R ₁₉ is an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, or 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. Good, x is an integer of 0 or more and 2 or less.)

Further, in the case of the polyamide resin represented by the general formula (11), the terminal amino group of the polyamide resin is changed to an alkenyl group or an alkenyl group so as not to affect the mechanical properties and heat resistance of the cured product cured at a low temperature. The terminal can also be capped as an amide using an acid anhydride or a monocarboxylic acid containing an aliphatic group or a cyclic compound group having at least one organic group selected from an alkynyl group and a hydroxyl group.
Examples of the acid anhydride or monocarboxylic acid containing an aliphatic group or a cyclic compound group having at least one organic group selected from among the alkenyl group, alkynyl group and hydroxyl group include maleic anhydride and citraconic anhydride. Product, 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene -2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, hetanoic anhydride, 5-norbornene-2-carboxylic acid, 4-ethynylphthalic anhydride And 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and the like. Rukoto can. These may be used alone or in combination of two or more kinds, and a part of the terminal-blocked amide moiety may be dehydrated and ring-closed.

  The method is not limited to this method, and the terminal carboxylic acid residue contained in the polyamide resin may be an aliphatic having at least one organic group selected from alkenyl groups, alkynyl groups and hydroxyl groups. The terminal can also be capped as an amide using an amine derivative containing a group or a cyclic compound group.

Furthermore, in the case of the polyamide resin represented by the general formula (11), at least one of the terminals 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 a low temperature. It may have a stopped group. Thereby, the adhesion to metal wiring (particularly copper wiring) and the like can be improved.
Examples of the nitrogen-containing cyclic compound include a 1- (5-1H-triazoyl) methylamino group, a 3- (1H-pyrazolyl) amino group, a 4- (1H-pyrazolyl) amino group, and a 5- (1H-pyrazolyl) amino group. Group, 1- (3-1H-pyrazolyl) methylamino group, 1- (4-1H-pyrazolyl) methylamino group, 1- (5-1H-pyrazolyl) methylamino group, (1H-tetrazol-5-yl) Examples include an amino group, a 1- (1H-tetrazol-5-yl) methyl-amino group, and a 3- (1H-tetrazol-5-yl) benz-amino group.

The polyamide resin having the structure represented by the general formula (11) is, for example, a compound containing X in the general formula (11) and selected from diamine, bis (aminophenol), 2,4-diaminophenol, and the like. And a compound containing Y, such as tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid, dicarboxylic dichloride, or a dicarboxylic acid derivative.
When a dicarboxylic acid is used, an active ester-type dicarboxylic acid derivative obtained by preliminarily reacting 1-hydroxy-1,2,3-benzotriazole or the like with the dicarboxylic acid in order to increase the reaction yield and the like of the polyamide resin. May be used.

  The polyamide resin having the structure represented by the general formula (11) is dehydrated and ring-closed by heating to obtain a heat-resistant resin in the form of a polyimide resin, a polybenzoxazole resin, or a copolymer of both. The temperature at which the dehydration ring closure is performed may be 280 to 380 ° C when heating at a high temperature, and 150 to 280 ° C when heating at a low temperature.

[Silane compound (B)]
The silane compound (B) used in the present embodiment is represented by the following general formula (1).

（式中Ａは環状構造を有する（ｍ＋ｎ）価の有機基を示し、Ｒ１およびＲ３はそれぞれ独立に水素原子、置換若しくは無置換の炭素数１〜１０の飽和アルキル基を示し、Ｒ２およびＲ４は置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基を示し、ａ及びｂはａ＋ｂ＝３を満たす０〜３の整数を示し、ｃ及びｄはｃ＋ｄ＝３を満たす０〜３の整数を示し、ｍ及びｎは０〜２の整数を示しｍ＋ｎ≠０である）

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b each represent an integer of 0 to 3 satisfying a + b = 3; c and d each represent an integer of 0 to 3 that satisfies c + d = 3, and m and n each represent an integer of 0 to 2 and m + n ≠ 0.

  The silane compound (B) represented by the formula (1) improves adhesion and transparency in the photosensitive resin composition since A in the formula (1) is an organic group having a cyclic structure. Can be. That is, since A in the formula (1) is an organic group having a rigid cyclic structure, the adhesion to the support can be improved, and since the organic group has a bulky cyclic structure, The transparency of the conductive resin composition can be improved.

  The silane compound (B) is not particularly limited, but is preferably a compound in which the cyclic structure in A in Formula (1) and Si in Formula (1) are directly bonded. With such a structure, the effect of improving the adhesion and the transparency by the annular structure can be more effectively realized.

  The silane compound (B) is not particularly limited, but a and c are preferably 0 or more and 1 or less, and b and d are preferably 2 or more and 3 or less. By being in the said range, adhesiveness can be improved more.

  The silane compound (B) is not particularly limited, but R1 and R3 are preferably an organic group selected from a hydrogen atom, a methyl group, and an ethyl group. By having such an organic group, the effect of improving adhesion and transparency can be further improved.

  The silane compound (B) is not particularly limited, but R2 and R4 are preferably an organic group selected from a hydrogen atom, a methyl group, and an ethyl group. By having such an organic group, the effect of improving adhesion and transparency can be further improved.

  The silane compound (B) is not particularly limited, but from the viewpoint of further improving the adhesion, m and n are preferably 1 or more and 2 or less, and from the viewpoint of further improving the transparency, m and n are each 0 or more. It is preferably at least 1.

  The silane compound (B) is not particularly limited, but for example, a compound represented by the following formula (17) is preferably used from the viewpoint of improving the adhesion and the transparency in a well-balanced manner.

（式中Ａ'は環状構造を有する２価の有機基を示し、当該環状構造がＳｉ原子と直接結合している。Ａ"は環状構造を有する１価の有機基を示し、当該環状構造がＳｉ原子と直接結合している。Ｒ１およびＲ３はそれぞれ独立に水素原子、置換若しくは無置換の炭素数１〜１０の飽和アルキル基を示し、Ｒ２およびＲ４は置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基を示し、ａ及びｂはａ＋ｂ＝３を満たす０〜３の整数を示し、ｃ及びｄはｃ＋ｄ＝３を満たす０〜３の整数を示す。）

(In the formula, A ′ represents a divalent organic group having a cyclic structure, and the cyclic structure is directly bonded to a Si atom. A ″ represents a monovalent organic group having a cyclic structure, and the cyclic structure is R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 each represent a substituted or unsubstituted 1 to 10 carbon atoms. A, b represents an integer of 0 to 3 that satisfies a + b = 3, and c and d represent 0 that satisfies c + d = 3. Represents an integer of 3 to 3)

  The silane compound (B) is not particularly limited, but is preferably an organic group having an aromatic ring in A in the formula (1) from the viewpoint of further improving adhesion. Although it does not specifically limit as an aromatic ring, A benzene ring, a naphthalene ring, a biphenylene ring, a fluorene ring, a phenalene ring, an anthracene ring, etc. are mentioned. From the viewpoint of further improving the adhesion, it is considered that the structure containing a plurality of aromatic rings has a more rigid structure, and the adhesion is further improved. Among them, an organic group selected from the organic group group represented by the following formula (2) is preferable, and the adhesion and the transparency can be improved in a well-balanced manner.

（式中Ｘ１は単結合、Ｃ（−Ｙ１）（−Ｙ２）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ１及びＹ２は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。）

(Wherein X1 represents a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing an amide group, and Y1 and Y2 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group.)

  When the silane compound (B) represented by the formula (1) includes an organic group having an aromatic ring in A in the formula (1), the silane compound (B) is not particularly limited, but is preferably a monovalent or divalent compound represented by the following formula (18). Valent organic groups are preferred.

（式中Ｘ１は単結合、Ｃ（−Ｙ１）（−Ｙ２）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ１及びＹ２は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。）

(Wherein X1 represents a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing an amide group, and Y1 and Y2 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group.)

  The silane compound (B) is not particularly limited, but is preferably an organic group having an aliphatic ring in A in the formula (1) from the viewpoint of further improving transparency. Examples of the aliphatic ring include, but are not particularly limited to, a monocyclic ring such as cyclohexane, a bicyclic ring such as bicyclopentane, and a polycyclic ring such as adamantane. By having a plurality of aliphatic rings, adhesion and transparency can be improved in a well-balanced manner. Among them, an organic group selected from the organic group group represented by the following formula (3) is preferable, and the adhesion and the transparency can be further improved.

（式中Ｘ２は単結合、Ｃ（−Ｙ３）（−Ｙ４）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ３及びＹ４は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。）

(Wherein X2 represents a single bond, C (-Y3) (-Y4), a divalent organic group containing a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, and Y3 and Y4 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group.)

  The silane compound (B) represented by the formula (1) is not particularly limited when it contains an organic group having an aliphatic ring in A in the formula (1). Divalent organic groups are preferred.

（式中Ｘ２は単結合、Ｃ（−Ｙ３）（−Ｙ４）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ３及びＹ４は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。）

(Wherein X2 represents a single bond, C (-Y3) (-Y4), a divalent organic group containing a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, and Y3 and Y4 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group.)

  The silane compound (B) is not particularly limited, and for example, a silane compound represented by the following formula (20) can be used.

  The content of the silane compound (B) in the photosensitive resin composition of the present embodiment is not particularly limited, but is 0.1 parts by mass with respect to 100 parts by mass of the total weight of the alkali-soluble resin (A). It is preferably at least 50 parts by mass and more preferably at least 0.5 part by mass and up to 20 parts by mass. When the amount is within the above range, sufficient adhesion and transparency can be exhibited.

[Photoacid generator (C)]
The photoacid generator (C) used in the present embodiment is a compound that generates an acid by light. For example, a photosensitizer capable of performing positive patterning can be used, and a wavelength of 200 to 500 nm, particularly Compounds that generate an acid by irradiation with actinic radiation having a wavelength of preferably 350 to 450 nm are preferred.
Specifically, onium salts such as photosensitive diazoquinone compounds, diaryliodonium salts, triarylsulfonium salts, sulfonium / borate salts, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imidosulfonate compounds, 2,6-bis (Trichloromethyl) -1,3,5-triazine compounds, dihydropyridine compounds and the like can be used. Among them, a photosensitive diazoquinone compound excellent in sensitivity and solvent solubility is preferable.

The photosensitive diazoquinone compound is, for example, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid.
In the case of the positive type, the photoacid generator remaining in the relief pattern of the unexposed portion is considered to be decomposed by heat during curing to generate an acid, and the photoacid generator also plays an important role as a reaction accelerator. Play. In the case of such a photosensitive diazoquinone compound, an ester of 1,2-naphthoquinone-2-diazido-4-sulfonic acid, which is more easily decomposed by heat, is preferable.

  The content of the photoacid generator (C) in the photosensitive resin composition of the present embodiment is not particularly limited, but is 1 part by mass with respect to 100 parts by mass of the total weight of the alkali-soluble resin (A). It is preferably at least 50 parts by mass and more preferably at least 5 parts by mass and up to 20 parts by mass. When the amount is within the above range, good patterning performance can be exhibited.

[Phenol resin (D)]
The photosensitive resin composition of the present embodiment can include a phenol resin (D) obtained by reacting a phenol compound with an aromatic aldehyde compound, if necessary. By using an aromatic aldehyde compound in the phenolic resin (D), intramolecular rotation can be suppressed, and high heat resistance can be imparted to the cured film in the present embodiment. Further, even if the dimer and trimer remain, the molecular weight of the dimer and trimer is higher than that of the phenol resin obtained by reacting formaldehyde, and the heat resistance of the cured film can be kept high. As described above, by containing the phenolic resin (D), the heat resistance and mechanical properties of the obtained cured film are improved, and more excellent heat resistance and mechanical properties as a protective film and an insulating film can be realized.

  As the aromatic aldehyde compound, an aromatic aldehyde compound represented by the following general formula (4) is preferable.

（式中Ｒ_１は水素、炭素数１以上２０以下のアルキル基、アルコキシ基、ヒドロキシ基から選ばれる有機基を示し、ｔは０以上３以下の整数である。）

(In the formula, R ₁ represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxy group, and t is an integer of 0 to 3 inclusive.)

As the aromatic aldehyde compound, an unsubstituted or an aromatic aldehyde compound having 3 or less substituents is used. Examples of the substituent include an organic group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group and a hydroxy group. The alkyl group and alkoxy group having 1 to 20 carbon atoms specifically include a methyl group, an ethyl group, a propyl group, a methoxy group, and an ethoxy group. Such aromatic aldehyde compounds include, for example, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2,3-dimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 2,3,4-trimethylbenzaldehyde, 2,3,5-trimethylbenzaldehyde, 2,3,6-trimethylbenzaldehyde, 2, 4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 3,4,5-trimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-i Butylbenzaldehyde, 4-methoxybenzaldehyde, salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3-methylsalicylaldehyde, 4-methylsalicylaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, , 5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, and the like can be used without limitation. Among these, an aromatic aldehyde compound in which R ₁ in the general formula (4) is hydrogen, a methyl group, or a hydroxy group is preferable, and those selected from aromatic aldehyde compounds represented by the following formula (21) are preferred. More preferred. Furthermore, these aldehydes can be used alone or in combination of two or more.

  As the phenol compound used in the phenol resin (D), the same phenol compound as used in the novolak type phenol resin in the alkali-soluble resin (A) can be used. For example, phenol; cresols such as o-cresol, m-cresol, p-cresol; 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3, Dimethylphenols such as 4-dimethylphenol and 3,5-dimethylphenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; alkylphenols such as isopropylphenol, butylphenol and p-tert-butylphenol And polyhydric phenols such as resorcin, catechol, hydroquinone, pyrogallol, and phloroglucin, but are not particularly limited. These phenols can be used alone or in combination of two or more.

  The phenol compound used for the phenol resin (D) is not particularly limited, but preferably contains a phenol resin obtained by reacting a phenol compound represented by the following general formula (5) with an aromatic aldehyde compound. With such a configuration, it is possible to provide a photosensitive resin composition having more excellent heat resistance and mechanical properties for use as a protective film and an insulating film.

（式中Ｘ３は単結合、Ｃ（−Ｙ７）（−Ｙ８）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ７及びＹ８は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示し、Ｙ５及びＹ６は、それぞれ独立に置換若しくは無置換の炭素数１〜２０の飽和アルキル基、置換若しくは無置換の炭素数１〜２０の不飽和アルキル基、置換若しくは無置換の炭素数１〜２０のアルコキシ基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。ｐ及びｑは、それぞれ独立に１〜３の整数を示し、ｒ及びｓは、それぞれ独立に０〜３の整数を示す。）

(Wherein X3 represents a single bond, C (-Y7) (-Y8), a divalent organic group containing a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, and Y7 and Y8 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group; Y5 and Y6 each independently represent a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 20 carbon atoms, Represents an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group. Independently an integer of 1 to 3 is, r and s, each independently represent an integer of 0-3.)

  The substituents Y5 and Y6 of the bisphenol compound represented by the general formula (5) are each independently a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms. It is an organic group selected from a saturated alkyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted cyclohexyl group. Such a bisphenol compound is not particularly limited, but is preferably selected from bisphenols represented by the following formula (22). Further, these bisphenols can be used alone or in combination of two or more. By using the above bisphenol compound, the phenol resin which suppresses intramolecular rotation, has sufficient heat resistance required for the photosensitive resin composition, and provides sufficient elongation properties by having flexibility in the molecular structure at the same time. Obtainable.

  In the synthesis reaction of the phenolic resin (D), the aldehyde compound is preferably reacted at 0.5 mol or more and 2 mol or less, and more preferably at 0.6 mol or more and 1.2 mol or less with respect to 1 mol of the phenol compound. Is more preferable, and the reaction is particularly preferably performed at 0.7 mol or more and 1.0 mol or less. With the above molar ratio, a molecular weight that can exhibit sufficient characteristics as a photosensitive resin composition can be obtained.

  It is preferable to use an acid catalyst in the synthesis reaction of the phenol resin (D). By using an acid catalyst, a novolak-type phenol resin can generally be synthesized, and the novolak-type phenol resin can be easily adjusted in molecular weight and hydroxyl group concentration. As the acid catalyst used in the synthesis reaction of the phenol resin (D), for example, oxalic acid, nitric acid, sulfuric acid, diethyl sulfate, acetic acid, p-toluenesulfonic acid, phenolsulfonic acid, benzenesulfonic acid, xylenesulfonic acid and the like are used. But not limited thereto. Among these, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, and sulfuric acid are preferred in terms of reactivity. The addition amount is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 8 parts by mass, based on 100 parts by mass of the phenol charge.

  The polycondensation reaction in the synthesis of the phenolic resin (D) proceeds by stirring under heating for several hours. The reaction temperature is preferably from 50 ° C to 160 ° C. Further, at the time of the reaction, a solvent can be added and the reaction can be carried out in the solvent. Examples of the reaction solvent include alcohols such as methanol, ethanol, isopropanol, diethylene glycol monomethyl ether and diethylene glycol; ketone solvents such as acetone, methyl ethyl ketone and methyl amyl ketone; ethers such as diethylene glycol monomethyl ether acetate; cyclic ethers such as tetrahydrofuran and dioxane Lactones such as γ-butyrolactone; pure water; and the like. The addition amount of the solvent is preferably 10 parts by mass or more and 200 parts by mass or less based on 100 parts by mass of the phenol charge.

  After completion of the reaction, the acid catalyst is neutralized with a base such as pyridine, triethylamine, and sodium hydroxide, and if necessary, the neutralized salt is removed by extracting it into an aqueous layer. Is collected.

After the synthesis of the phenol resin (D), a step of removing the monomer is usually performed. As a method for removing the monomer, a solvent fractionation method of adding a solvent and water to remove a water layer, a method of volatilizing the monomer by heating under reduced pressure, and the like can be selected. In the above solvent fractionation method, a solvent such as acetone, methanol, isopropanol, and butanol, which is a solvent having good solubility in the phenol resin, and a solvent such as pure water, which is a poorly soluble solvent in the phenol resin. Is added and stirred at a fixed ratio, and the aqueous layer separated after standing is removed, whereby the monomer that has moved to the aqueous layer side can be removed. In the above method of volatilizing the monomer, the monomer can be volatilized and removed by heating and stirring from 150 ° C. to 250 ° C. while reducing the pressure to 50 mmHg or less. When the monomer is removed by volatilization, a solvent, pure water, steam, N ₂ gas, or the like may be added to increase the monomer removal efficiency. The solvent at this time is not particularly limited as long as it does not affect the phenolic resin.For example, ethylene glycol, ethylene glycol alkyl ether, propylene glycol alkyl ether, propylene glycol alkyl ether acetate, diethylene glycol, diethylene glycol alkyl ether, Glycols such as triethylene glycol and triethylene glycol alkyl ether, lactones such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N- Examples include polar aprotic solvents such as dimethylformamide, N, N-diethylformamide, dimethylsulfoxide, dimethylimidazolidinone, and the like. In both the fractionation method and the monomer volatilization method, the operation is repeated according to the remaining amount of the monomer, whereby the efficiency of removing the monomer can be increased.

  The phenolic resin (D) thus obtained has a polystyrene-equivalent weight average molecular weight of preferably 500 to 10,000, more preferably 700 to 7000, as measured by gel permeation chromatography. When the weight average molecular weight is at least the lower limit, the heat resistance and the film toughness of the photosensitive resin composition can be further improved. Further, when the weight average molecular weight is equal to or less than the upper limit, residues generated in the openings by patterning can be further suppressed.

  Further, the phenolic resin (D) thus obtained can be finally recovered as a flake or a solvent-soluble product. Examples of the solvent that can be recovered as a solvent-dissolved product 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, methyl pyruvate And methyl-3-methoxypropionate. These may be used alone or in combination.

  When the photosensitive resin composition of the present embodiment contains a phenol resin (D), the content of the phenol resin (D) is not particularly limited, but the total weight of the alkali-soluble resin (A) is 100 mass. 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 25 parts by mass or more with respect to parts. Further, it is preferably 1900 parts by mass or less, more preferably 400 parts by mass or less, and still more preferably 150 parts by mass or less. Further, it is preferably from 5 parts by mass to 400 parts by mass, more preferably from 25 parts by mass to 400 parts by mass, further preferably from 25 parts by mass to 150 parts by mass. When the amount is within the above range, good patterning performance and curability can be exhibited in a well-balanced manner.

  The weight ratio (A / D) of the alkali-soluble resin (A) to the phenol resin (D) is preferably 5/95 or more, more preferably 20/80 or more, and further preferably 40/60 or more. And it is preferably 95/5 or less, more preferably 90/10 or less, and further preferably 80/20 or less. Moreover, it is preferably 20/80 or more and 95/5 or less, more preferably 20/80 or more and 80/20 or less, and still more preferably 40/60 or more and 80/20 or less. By using together within this range, good characteristics as a photosensitive resin composition can be realized. When the weight ratio (A / D) is at least the above lower limit, the heat resistance and film properties required for the photosensitive resin composition can be further improved. When the weight ratio (A / D) is equal to or less than the upper limit, the sensitivity at the time of patterning can be improved, and the throughput can be further improved.

[solvent]
The photosensitive resin composition of the present embodiment can be used by dissolving each of the above-described components in a solvent and forming 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, and 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, methyl pyruvate and methyl-3- Methoxypropionate, etc., may be used alone or in combination.

  Although the content of the solvent in the photosensitive resin composition of the present embodiment is not particularly limited, it is 50 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). Is preferably 100 parts by mass or more and 200 parts by mass or less. When the addition amount is within the above range, the resin is sufficiently dissolved, and a varnish having high handleability can be produced.

[Thermal crosslinking agent (E)]
The photosensitive resin composition of the present embodiment can further contain a thermal crosslinking agent (E). Such a thermal crosslinking agent (E) is not particularly limited as long as it is a compound having a group capable of reacting with the alkali-soluble resin (A) and / or phenol resin (D) by heat. -Benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,3,5-benzenetrimethanol, 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6 Compounds having a methylol group represented by -bis (hydroxymethyl) -p-cresol, 4,4'-methylenebis (2,6-dialkoxymethylphenol); 1,4-bis (methoxymethyl) benzene, , 3-Bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl Compounds having an alkoxymethyl group represented by 1,3,3-bis (methoxymethyl) biphenyl, methyl 2,6-naphthalenedicarboxylate, 4,4′-methylenebis (2,6-dimethoxymethylphenol); Methylol melamine compounds represented by hexamethylol melamine, hexabutanol melamine and the like; alkoxymelamine compounds represented by hexamethoxy melamine and the like; alkoxymethyl glycol uryl compounds represented by tetramethoxymethyl glycol uryl and the like; methylol benzoguanamine compounds and dimethylol Methylol urea compounds represented by ethylene urea and the like; cyano compounds represented by dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid, and the like; 1,4-phenylene diisocyanate And isocyanate compounds represented by 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate; ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, Epoxy group-containing compounds represented by bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, phenol novolak resin epoxy resin, and the like; N, N'-1,3-phenylenedimaleimide, N, N'- Maleimide compounds represented by methylene dimaleimide and the like are exemplified, but not limited thereto. These thermal crosslinking agents can be used alone or in combination of two or more.

  The content of the thermal crosslinking agent (E) in the photosensitive resin composition of the present embodiment is not particularly limited, but is not less than 1 part by mass and not more than 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). It is preferably at most 2 parts by mass and more preferably at most 20 parts by mass. When the amount is within the above range, a cured film having excellent residual film ratio and heat resistance during curing can be formed.

[Silane coupling agent (F)]
In the photosensitive resin composition of the present embodiment, a silane coupling agent different from the silane compound (B) can be used in a range that does not impair the transparency from the viewpoint of further improving the adhesion (hereinafter, silane compound). Also shown as coupling agent (F).) Examples of such a silane coupling agent (F) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 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 -Aminopro Having tri-methoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and an amino group Examples include, but are not limited to, silicon compounds obtained by reacting a silicon compound with an acid dianhydride or an acid anhydride.

Examples of the silicon compound having an amino group include, but are not particularly limited to, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyl Examples include methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and the like.
The acid dianhydride or acid anhydride is not particularly limited, for example, maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, phthalic anhydride, pyromellitic anhydride, 4,4'-biphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-carbonyldiphthalic anhydride and the like can be mentioned. In use, they can be used alone or in combination of two or more.
When the silane coupling agent (F) is contained in the photosensitive resin composition, the amount of the silane coupling agent (F) to be added is not particularly limited, but the weight of the alkali-soluble resin (A) is 100% by mass. The amount is preferably from 0.05 to 50 parts by mass, more preferably from 0.1 to 20 parts by mass, per part. When the addition amount is within the above range, it is possible to suitably balance the adhesion to the substrate and the storage stability of the photosensitive resin composition.

[Dissolution promoter]
Further, the photosensitive resin composition of the present embodiment may contain a dissolution promoter.
The dissolution accelerator is a component capable of improving the solubility of a coating film formed using the photosensitive resin composition in a developer in an exposed portion and improving scum during patterning.
As the dissolution promoter, a compound having a phenolic hydroxyl group is particularly preferable.

[Other ingredients]
Further, in the photosensitive resin composition of the present embodiment, if necessary, additives such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a terminal sealing agent, and a sensitizer are added. Is also good.

In the above photosensitive resin composition, the ratio of each component is, for example, as follows.
When the total solid content of the photosensitive resin composition (that is, the components excluding the solvent) is 100% by mass, preferably, the proportion of the alkali-soluble resin (A) is 20% by mass or more and 95% by mass or less, and the silane compound The ratio of (B) is 0.1% by mass or more and 30% by mass or less, and the ratio of the photoacid generator (C) is 1% by mass or more and 30% by mass or less.
More preferably, the ratio of the alkali-soluble resin (A) is 30% by mass to 90% by mass, the ratio of the silane compound (B) is 0.5% by mass to 20% by mass, and the photoacid generator ( The proportion of C) is 5% by mass or more and 20% by mass or less.
When the composition further contains a phenol resin (D), the proportion of the alkali-soluble resin (A) is 30% by mass or more and 90% by mass or less, and the ratio of the silane compound (B) is 0.1% by mass or more and 30% by mass or less. And the ratio of the photoacid generator (C) is 1% by mass or more and 30% by mass or less, and the ratio of the phenol resin (D) is 1% by mass or more and 30% by mass or less.

  The photosensitive resin composition is obtained by mixing and dissolving an alkali-soluble resin (A), a silane compound (B), a photoacid generator (C), and other components as necessary. Prepared by In the present embodiment, for example, a photosensitive resin composition can be prepared by mixing and dissolving each component in an organic solvent under a nitrogen flow. Also, for example, the synthesis of the alkali-soluble resin (A) can be performed under a nitrogen flow. Thus, by suppressing the amount of oxygen or moisture mixed in the photosensitive resin composition, the characteristics of the photosensitive resin composition can be improved.

[Curing film]
An example of a method for using the photosensitive resin composition of the present embodiment will be described below.
The photosensitive resin composition of the present embodiment can be cured to form a cured film. Specifically, the composition is first applied to a suitable support, for example, a silicon wafer, a ceramic substrate, an aluminum substrate, or the like. When applying on a semiconductor element, the amount of application is generally such that the final film thickness after curing is 0.1 to 30 μm. With such a numerical range, the function as a protective film and an insulating film of the semiconductor element can be sufficiently exhibited, and a fine relief pattern can be obtained.
Examples of the coating method include spin coating using a spin coater, spray coating using a spray coater, dipping, printing, and roll coating.
Next, when forming a relief pattern 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. Examples of the developer 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-amine. secondary amines such as n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; secondary amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of an alkali such as a quaternary ammonium salt; and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol and ethanol or a surfactant thereto can be preferably used. As a developing method, a system such as spray, paddle, immersion, and ultrasonic wave can be used.

Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinsing 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. The heat treatment temperature at the high temperature is preferably from 280 ° C to 380 ° C, more preferably from 290 ° C to 350 ° C. The heat treatment temperature at a low temperature is preferably from 150 ° C to 280 ° C, and more preferably from 180 ° C to 260 ° C. An oven, a hot plate, an electric furnace (furnace), infrared rays, microwaves, and the like are used for the heat treatment.

  The cured product obtained by heating and curing the photosensitive resin composition has a light transmittance T (%) in terms of a film thickness of 10 μm with respect to light having a wavelength of 630 nm of preferably 75% or more, more preferably 78% or more. And more preferably at least 80%, particularly preferably at least 82%, particularly preferably at least 85%. The upper limit of the light transmittance T (%) in terms of the film thickness of 10 μm with respect to the light having a wavelength of 630 nm is not particularly limited, but is, for example, 99% or less. When the light transmittance T (%) of the cured product with respect to a light having a wavelength of 630 nm in terms of a film thickness of 10 μm is within the above range, the visibility of an adherend, such as a semiconductor element or a display element, which is a support, is reduced. Thus, productivity of a semiconductor device, a display device, or the like can be improved. The light transmittance is measured using, for example, a general UV spectrophotometer, for example, UV-160A manufactured by Shimadzu Corporation. Further, the measured light transmittance can be converted into a value of a film thickness of 10 μm according to, for example, Lambert-Beer's law.

  The glass transition temperature of the cured product obtained by heating and curing the photosensitive resin composition by differential scanning calorimetry (heating rate 5 ° C./min) is preferably 200 ° C. or more, more preferably 220 ° C. or more. And particularly preferably at least 250 ° C. The upper limit of the glass transition temperature is not particularly limited, but is, for example, 400 ° C. or less. When the glass transition temperature of the cured product is within the above range, the heat resistance and mechanical properties of the obtained cured film can be further improved.

The elongation of a cured product (dimensions: 10 mm × 60 mm × 10 μm thickness) obtained by heating and curing the photosensitive resin composition is preferably 20% or more in a tensile test (stretching speed: 5 mm / min). It is preferably at least 30%. The upper limit of the tensile elongation is not particularly limited, but is, for example, 300% or less. When the elongation percentage of the cured product is within the above range, the risk of cracks due to stress at the time of film deformation is reduced, and the reliability as a protective film can be further improved.
The cured product (dimensions: 10 mm × 60 mm × 10 μm thickness) obtained by heating and curing the photosensitive resin composition has a tensile modulus of preferably 0.5 GPa or more and 10 GPa or less in a tensile test (stretching speed: 5 mm / min). And more preferably 1.0 GPa or more and 8.0 GPa or less. When the tensile modulus of the cured product is within the above range, the cured film obtained can have sufficient strength, and the reliability as a protective film can be further improved.

<Application>
Next, applications of the photosensitive resin composition will be described.

  The cured film formed using the photosensitive resin composition of the present embodiment is used not only for semiconductor devices such as semiconductor elements, but also for display devices such as TFT-type liquid crystal and organic EL, interlayer insulating films for multilayer circuits and the like. It is also useful as a cover coat for a flexible copper clad board, a solder resist film or a 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 a passivation film. A protective film such as a coat 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 planarizing film, and protrusions (Resin post), partition walls, and the like.

Examples of display device applications include a protective film formed by forming a cured film of the photosensitive resin composition of the present embodiment on a display element, an insulating film or a flattening film for TFT elements and color filters, and MVA. And projections for a liquid crystal display device and partition walls for an organic EL element cathode.
The method of use is based on the formation of a patterned photosensitive resin composition layer on a substrate on which a display element or a color filter is formed by the above-described method in accordance with the application of a semiconductor device. For display device applications, especially for insulating films and flattening film applications, high transparency is required, but before curing of the coating film of the photosensitive resin composition of the present embodiment, by introducing a post-exposure step, A resin layer having excellent transparency 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 hermetically sealed or sealed using a molding material. Specific examples include a transistor, a solar cell, a diode, a solid-state imaging device, various semiconductor packages in which semiconductor chips are stacked and sealed, a wafer level chip size package (WLP), and the like.
Examples of the display device include a TFT type liquid crystal, an organic EL, and a color filter.
Hereinafter, an example of an electronic device having a film formed using the photosensitive resin composition of the present embodiment will be described.

<Electronic device>
FIG. 1 and FIG. 2 are cross-sectional views each showing an example of the electronic device 100 according to the present embodiment. In each case, a part of the electronic device 100 including the insulating film is shown.
In the electronic device 100 according to the present embodiment, for example, the insulating film is formed by a cured film formed of the photosensitive resin composition of the present embodiment.

  As an example of the electronic device 100 according to the embodiment, FIG. 1 illustrates a liquid crystal display device. However, the electronic device 100 according to the embodiment is not limited to the liquid crystal display device, and includes another electronic device including a permanent film made of the photosensitive resin composition of the embodiment.

  As shown in FIG. 1, an electronic device 100 as a liquid crystal display device includes, for example, a substrate 10, a transistor 30 provided on the substrate 10, and an insulating film 20 provided on the substrate 10 so as to cover the transistor 30. , And a wiring 40 provided on the insulating film 20.

The substrate 10 is, for example, a glass substrate.
The transistor 30 is, for example, a thin film transistor that forms a switching element of a liquid crystal display device. On the substrate 10, for example, a plurality of transistors 30 are arranged in an array. The transistor 30 according to the present embodiment includes, for example, a gate electrode 31, a source electrode 32, a drain electrode 33, a gate insulating film 34, and a semiconductor layer 35. Gate electrode 31 is provided, for example, on substrate 10. Gate insulating film 34 is provided on substrate 10 so as to cover gate electrode 31. The semiconductor layer 35 is provided on the gate insulating film 34. The semiconductor layer 35 is, for example, a silicon layer. The source electrode 32 is provided on the substrate 10 so that a part thereof contacts the semiconductor layer 35. The drain electrode 33 is provided on the substrate 10 so as to be separated from the source electrode 32 and to be partially in contact with the semiconductor layer 35.

The insulating film 20 functions as a planarization film for eliminating a step due to the transistor 30 and the like and forming a flat surface on the substrate 10. The insulating film 20 is made of a cured product of the photosensitive resin composition of the present embodiment. The opening 22 penetrating the insulating film 20 is provided in the insulating film 20 so as to connect to the drain electrode 33.
A wiring 40 connected to the drain electrode 33 is formed on the insulating film 20 and in the opening 22. The wiring 40 functions as a pixel electrode forming a pixel together with the liquid crystal.
In addition, an alignment film 90 is provided on the insulating film 20 so as to cover the wiring 40.

An opposing substrate 12 is arranged above one surface of the substrate 10 on which the transistor 30 is provided so as to oppose the substrate 10. The wiring 42 is provided on one surface of the opposing substrate 12 facing the substrate 10. The wiring 42 is provided at a position facing the wiring 40. An alignment film 92 is provided on the one surface of the counter substrate 12 so as to cover the wiring 42.
Liquid crystal forming the liquid crystal layer 14 is filled between the substrate 10 and the counter substrate 12.

The electronic device 100 shown in FIG. 1 is formed, for example, as follows.
First, the transistor 30 is formed over the substrate 10. Next, a photosensitive resin composition is applied by a printing method or a spin coating method to one surface of the substrate 10 on which the transistor 30 is provided, and an insulating film 20 covering the transistor 30 is formed. Thus, a planarization film covering the transistor 30 provided over the substrate 10 is formed.
Next, the insulating film 20 is exposed and developed to form an opening 22 in a part of the insulating film 20. At this time, the unexposed portion is dissolved in the developer, and the exposed portion remains. This is the same in each example of the electronic device 100 described later.
Next, the insulating film 20 is cured by heating. Then, a wiring 40 connected to the drain electrode 33 is formed in the opening 22 of the insulating film 20. After that, the opposing substrate 12 is disposed on the insulating film 20, and liquid crystal is filled between the opposing substrate 12 and the insulating film 20 to form the liquid crystal layer 14.
Thus, the electronic device 100 shown in FIG. 1 is formed.

As an example of the electronic device 100 according to the present embodiment, FIG. 2 shows a semiconductor device in which a rewiring layer 80 is formed by a permanent film made of a photosensitive resin composition.
The electronic device 100 shown in FIG. 2 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer provided on the semiconductor substrate (not shown). In the uppermost layer of the multilayer wiring layers, an insulating film 50 as an interlayer insulating film and an uppermost layer wiring 72 provided on the insulating film 50 are provided. The uppermost layer wiring 72 is made of, for example, aluminum (Al).

Further, a redistribution layer 80 is provided on the insulating film 50. The rewiring layer 80 includes an insulating film 52 provided on the insulating film 50 so as to cover the uppermost wiring 72, a rewiring 70 provided on the insulating film 52, and an insulating film 52 and the rewiring 70. And an insulating film 54 provided.
The opening 24 connected to the uppermost layer wiring 72 is formed in the insulating film 52. The rewiring 70 is formed on the insulating film 52 and in the opening 24 and is connected to the uppermost wiring 72. The insulating film 54 has an opening 26 connected to the rewiring 70.
These insulating films 52 and 54 are formed of permanent films made of a photosensitive resin composition. The insulating film 52 is obtained by, for example, forming the opening 24 by exposing and developing the photosensitive resin composition applied on the insulating film 50 and then heating and curing the opening 24. The insulating film 54 is obtained, for example, by exposing and developing the photosensitive resin composition applied on the insulating film 52 to form the opening 26 and then heating and curing the opening 26.

  In the opening 26, for example, a bump 74 is formed. The electronic device 100 is connected to a wiring board or the like via the bump 74, for example.

  Further, the electronic device 100 according to the present embodiment may be an optical device in which a microlens is formed by a permanent film made of a photosensitive resin composition. Examples of the optical device include a liquid crystal display, a plasma display, a field emission display, an electroluminescence display, and the like.

（式中Ａは環状構造を有する（ｍ＋ｎ）価の有機基を示し、Ｒ１およびＲ３はそれぞれ独立に水素原子、置換若しくは無置換の炭素数１〜１０の飽和アルキル基を示し、Ｒ２およびＲ４は置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基を示し、ａ及びｂはａ＋ｂ＝３を満たす０〜３の整数を示し、ｃ及びｄはｃ＋ｄ＝３を満たす０〜３の整数を示し、ｍ及びｎは０〜２の整数を示しｍ＋ｎ≠０である。）
＜２＞
＜１＞に記載の感光性樹脂組成物において、
シラン化合物（Ｂ）の一般式（１）におけるＡは芳香環を有する有機基である感光性樹脂組成物。
＜３＞
＜１＞または＜２＞に記載の感光性樹脂組成物において、
シラン化合物（Ｂ）の一般式（１）におけるＡは下記式（２）に示す有機基群の中から選ばれる有機基である感光性樹脂組成物。

（式中Ｘ１は単結合、Ｃ（−Ｙ１）（−Ｙ２）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ１及びＹ２は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。）
＜４＞
＜１＞に記載の感光性樹脂組成物において、
シラン化合物（Ｂ）の一般式（１）におけるＡは脂肪族環を有する有機基である感光性樹脂組成物。
＜５＞
＜１＞または＜４＞に記載の感光性樹脂組成物において、
シラン化合物（Ｂ）の一般式（１）におけるＡは下記式（３）に示す有機基群の中から選ばれる有機基である感光性樹脂組成物。

（式中Ｘ２は単結合、Ｃ（−Ｙ３）（−Ｙ４）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ３及びＹ４は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。）
＜６＞
＜１＞ないし＜５＞のいずれか一に記載の感光性樹脂組成物において、
前記アルカリ可溶性樹脂（Ａ）が、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体、ポリイミド、及びポリイミド前駆体から選ばれる少なくとも一つ以上を含む感光性樹脂組成物。
＜７＞
＜１＞ないし＜６＞のいずれか一に記載の感光性樹脂組成物において、
フェノール化合物と芳香族アルデヒド化合物を反応させて得られるフェノール樹脂（Ｄ）をさらに含む感光性樹脂組成物。
＜８＞
＜７＞に記載の感光性樹脂組成物において、
前記芳香族アルデヒド化合物が下記式（４）で表される芳香族アルデヒド化合物を含む感光性樹脂組成物。

（式中Ｒ _１ は水素、炭素数１以上２０以下のアルキル基、アルコキシ基及びヒドロキシ基から選ばれる有機基を示し、ｔは０以上３以下の整数である。）
＜９＞
＜７＞または＜８＞に記載の感光性樹脂組成物において、
前記フェノール化合物が下記式（５）で表されるフェノール化合物を含む感光性樹脂組成物。

（式中Ｘ３は単結合、Ｃ（−Ｙ７）（−Ｙ８）、硫黄原子、エーテル基、カルボニル基、エステル基、またはアミド基を含む２価の有機基を示し、Ｙ７及びＹ８は、それぞれ独立に水素原子、トリフルオロメチル基、置換若しくは無置換の炭素数１〜１０の飽和アルキル基、置換若しくは無置換の炭素数１〜１０の不飽和アルキル基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示し、Ｙ５及びＹ６は、それぞれ独立に置換若しくは無置換の炭素数１〜２０の飽和アルキル基、置換若しくは無置換の炭素数１〜２０の不飽和アルキル基、置換若しくは無置換の炭素数１〜２０のアルコキシ基、置換若しくは無置換のフェニル基、または置換若しくは無置換のシクロヘキシル基を示す。ｐ及びｑは、それぞれ独立に１〜３の整数を示し、ｒ及びｓは、それぞれ独立に０〜３の整数を示す。）
＜１０＞
＜１＞ないし＜９＞のいずれか一に記載の感光性樹脂組成物において、
更に熱架橋剤（Ｅ）を含有する感光性樹脂組成物。
＜１１＞
＜１＞ないし＜１０＞のいずれか一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。
＜１２＞
＜１１＞に記載の硬化膜で構成されている保護膜。
＜１３＞
＜１１＞に記載の硬化膜で構成されている絶縁膜。
＜１４＞
＜１１＞に記載の硬化膜を有している電子装置。 Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than the above can be adopted.
Further, the present invention is not limited to the above-described embodiment, and includes modifications and improvements as long as the object of the present invention can be achieved.
Hereinafter, an example of a reference embodiment of the present invention will be described.
<1>
An alkali-soluble resin (A),
A silane compound (B) represented by the following general formula (1),
A photoacid generator (C);
A photosensitive resin composition containing:

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b each represent an integer of 0 to 3 satisfying a + b = 3; c and d each represent an integer of 0 to 3 that satisfies c + d = 3, and m and n each represent an integer of 0 to 2 and m + n ≠ 0.)
<2>
In the photosensitive resin composition according to <1>,
A in the general formula (1) of the silane compound (B), wherein A is an organic group having an aromatic ring.
<3>
In the photosensitive resin composition according to <1> or <2>,
A in the photosensitive resin composition, wherein A in the general formula (1) of the silane compound (B) is an organic group selected from the organic group group represented by the following formula (2).

(Wherein X1 represents a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing an amide group, and Y1 and Y2 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group.)
<4>
In the photosensitive resin composition according to <1>,
A in the general formula (1) of the silane compound (B), wherein A is an organic group having an aliphatic ring.
<5>
In the photosensitive resin composition according to <1> or <4>,
A photosensitive resin composition wherein A in the general formula (1) of the silane compound (B) is an organic group selected from the organic group group represented by the following formula (3).

(Wherein X2 represents a single bond, C (-Y3) (-Y4), a divalent organic group containing a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, and Y3 and Y4 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group.)
<6>
In the photosensitive resin composition according to any one of <1> to <5>,
A photosensitive resin composition in which the alkali-soluble resin (A) contains at least one selected from polybenzoxazole, polybenzoxazole precursor, polyimide, and polyimide precursor.
<7>
The photosensitive resin composition according to any one of <1> to <6>,
A photosensitive resin composition further comprising a phenol resin (D) obtained by reacting a phenol compound with an aromatic aldehyde compound.
<8>
In the photosensitive resin composition according to <7>,
A photosensitive resin composition wherein the aromatic aldehyde compound contains an aromatic aldehyde compound represented by the following formula (4).

(In the formula, R ₁ represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxy group, and t is an integer of 0 to 3 inclusive.)
<9>
In the photosensitive resin composition according to <7> or <8>,
A photosensitive resin composition wherein the phenol compound contains a phenol compound represented by the following formula (5).

(Wherein X3 represents a single bond, C (-Y7) (-Y8), a divalent organic group containing a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, and Y7 and Y8 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group; Y5 and Y6 each independently represent a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 20 carbon atoms, Represents an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group. Independently an integer of 1 to 3 is, r and s, each independently represent an integer of 0-3.)
<10>
The photosensitive resin composition according to any one of <1> to <9>,
A photosensitive resin composition further containing a thermal crosslinking agent (E).
<11>
A cured film composed of a cured product of the photosensitive resin composition according to any one of <1> to <10>.
<12>
A protective film composed of the cured film according to <11>.
<13>
An insulating film composed of the cured film according to <11>.
<14>
An electronic device having the cured film according to <11>.

  Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Synthesis of alkali-soluble resin (A-1)>
21.43 g (0.083 mol) of diphenyl ether-4,4'-dicarboxylic acid and 1-hydroxy-1 were placed in a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube. 40.87 g (0.083 mol) of a mixture of dicarboxylic acid derivatives obtained by reacting 22.43 g (0.166 mol) of 2,2,3-benzotriazole monohydrate with hexafluoro-2, 36.62 g (0.100 mol) of 2-bis (3-amino-4-hydroxyphenyl) propane was added, and 296.96 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the reaction was carried out at 75 ° C. for 15 hours using an oil bath.
Next, 6.98 g (0.0425 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added, and further, The reaction was completed 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), and the precipitate was collected by filtration, washed sufficiently with water, dried under vacuum, and dried under a vacuum to obtain the desired polyamide resin ( An alkali-soluble resin (A-1)) was obtained. The weight average molecular weight of the obtained compound was 13,040.

<Synthesis of alkali-soluble resin (A-2)>
In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 30.0 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0. 082 mol), and 400 ml of acetone was added to dissolve it.
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 lower 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. Then, 30.0 g (0.218 mol) of potassium carbonate was gradually added, and the mixture was further stirred for 2 hours. The heat was removed and the mixture was further stirred at room temperature for 18 hours. Thereafter, while the mixture was vigorously stirred, an aqueous sodium hydroxide solution was gradually added, and 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% by weight aqueous solution of hydrochloric acid and 500 ml of water were added to adjust the pH of the solution to a range of 6.0 to 7.0. Next, the obtained precipitate is separated by filtration, the filtrate is washed with water, 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 the mixture was heated to 50 ° C. and completely dissolved. Thereto, 300 mL of 50 ° C pure water was added over 30 minutes and heated to 65 ° C. Thereafter, the mixture was cooled slowly to room temperature, and the precipitated crystals were collected by filtration. The crystals were dried at 70 ° C. and purified to obtain bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis. (4-Hydroxyphenyl) propane was obtained.

  20 g of bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above was placed in a 1 L flask, and 1.0 g of a 5% palladium-carbon catalyst was added. And 180.4 g of ethyl acetate were added to form a suspension. There, hydrogen gas was purged, and the mixture was shaken for 35 minutes while heating to 50 to 55 ° C. to perform a reduction reaction. After the completion of the reaction, the mixture was cooled to 35 ° C., and the suspension was purged with nitrogen. After removing the catalyst by filtration, the filtrate was evaporated and the solvent was evaporated. The obtained product was dried at 90 ° C. to obtain bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.

  The bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2- obtained above was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. 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 g (0.022 mol) of 4,4'-oxydiphthalic anhydride and 12.0 g of γ-butyrolactone were added, 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. Then, 5.2 g (0.044 mol) of N, N-dimethylformamide dimethyl acetal and 10.0 g of γ-butyrolactone were added, and the mixture was further stirred at 50 ° C. for 1 hour. After the completion of the reaction, the resultant was cooled to room temperature to obtain a target polyamide resin (alkali-soluble resin (A-2)). The weight average molecular weight of the obtained compound was 13,200.

<Synthesis of alkali-soluble resin (A-3)>
Under a dry nitrogen stream, 64.9 g (0.60 mol) of m-cresol and 43.3 g of p-cresol were placed in a four-necked round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. 0.40 mol), 65.1 g (formaldehyde 0.65 mol) of a 30% by weight aqueous solution of formaldehyde, and 0.63 g (0.005 mol) of oxalic acid dihydrate, and then immersed in an oil bath to react. The polycondensation reaction was performed at 100 ° C. for 4 hours while refluxing the liquid. Thereafter, the temperature of the oil bath was raised to 200 ° C. over 3 hours. Thereafter, the pressure in the flask was reduced to 50 mmHg or less to remove water and volatile components, and then the resin was cooled to room temperature, and a novolak-type phenol resin having a weight average molecular weight of 3,200 (alkali-soluble resin (A-3)) I got

<Silane compound (B)>
Silane compounds (B-1), (B-2), (B-3) and (B-4) shown in the following formula (23) were prepared.

<Synthesis of photoacid generator (C-1)>
In a four-neck 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 the phenol compound represented by the formula (P-1) and 1 , 2-Naphthoquinone-2-diazido-4-sulfonyl chloride (18.81 g, 0.070 mol) and acetone (170 g) were 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 reach 35 ° C. or higher. After allowing the reaction to proceed at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added, followed by a further reaction for 30 minutes. Then, after filtering the reaction mixture, the filtrate was poured into a mixed solution of water / acetic acid (990 ml / 10 ml), and then the precipitate was collected by filtration, washed sufficiently with water, and then dried under vacuum, Thus, a photoacid generator (C-1) represented by the structure of the formula (Q-1) was obtained.

<Synthesis of phenolic resin (D-1)>
150.0 g (0.75 mol) of bisphenol F (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) in a four-neck round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube under a dry nitrogen gas flow. , 63.7 g (0.60 mol) of benzaldehyde, and 3.0 g (0.02 mol) of benzenesulfonic acid were immersed in an oil bath, and the polycondensation reaction was carried out at 100 ° C. for 2 hours while refluxing the reaction solution. Was done. Thereafter, while cooling the flask, 75 g of acetone and 3.0 g (0.03 mol) of triethylamine were added, and the mixture was stirred for 30 minutes. Then, 150 g of pure water was further added, and the mixture was stirred for 30 minutes. After cooling to room temperature, stirring was stopped, and the separated aqueous layer was removed. Then, 37.5 g of γ-butyrolactone was added, and the temperature of the oil bath was raised to 170 ° 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 a phenol resin (D-1) having a weight average molecular weight of 2,900.

<Synthesis of phenolic resin (D-2)>
Under a dry nitrogen stream, 171.0 g (0.75 g) of 2,2′-bis (4-hydroxyphenyl) propane was placed in a four-necked round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Mol), 63.7 g (0.60 mol) of benzaldehyde and 3.0 g (0.02 mol) of benzenesulfonic acid, and then immersed in an oil bath, and refluxed at 100 ° C. for 2 hours while refluxing the reaction solution. A condensation reaction was performed. Thereafter, while cooling the flask, 75 g of acetone and 3.0 g (0.03 mol) of triethylamine were added, and the mixture was stirred for 30 minutes. Then, 150 g of pure water was further added, and the mixture was stirred for 30 minutes. After cooling to room temperature, stirring was stopped, and the separated aqueous layer was removed. Then, 37.5 g of γ-butyrolactone was added, and the temperature of the oil bath was raised to 170 ° 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 a phenol resin (D-2) having a weight average molecular weight of 2540.

<Thermal crosslinking agent (E)>
1,4-benzenedimethanol was prepared as a thermal crosslinking agent (E-1).

<Silane coupling agent (F)>
3-Glycidoxypropyltrimethoxysilane was prepared as a silane coupling agent (F-1) and a silane coupling agent (F-2) represented by the following formula (24).

<< Example 1 >>
20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.5 g of the silane compound (B-1) was added and mixed over 30 minutes, and finally, the mixture was filtered through a fluorine resin filter having a pore diameter of 0.2 μm to obtain the photosensitive resin composition of Example 1. Was.

<< Example 2 >>
20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.5 g of the silane compound (B-2) was added and mixed over 30 minutes, and finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 2. .

Example 3
20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.5 g of the silane compound (B-3) was added over 30 minutes and mixed, and finally, the mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Example 3. Was.

Example 4
20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.5 g of the silane compound (B-4) was added over 30 minutes and mixed, and finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 4. Was.

Example 5
20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.8 g of the silane compound (B-3) was added and mixed over 30 minutes, and finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 5. Was.

Example 6
20 g of the alkali-soluble resin (A-2) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.5 g of the silane compound (B-3) was added over 30 minutes and mixed, and finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 6. Was.

Example 7
14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the alkali-soluble (A-3), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed with 25 g of γ-butyrolactone. Dissolved. Thereafter, 0.5 g of the silane compound (B-3) was added over 30 minutes and mixed, and finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 7. Was.

Example 8
14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed with 25 g of γ-butyrolactone. Dissolved. Thereafter, 0.5 g of the silane compound (B-3) was added over 30 minutes and mixed, and finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 8. Was.

Example 9
14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-2), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed with 25 g of γ-butyrolactone. Dissolved. Thereafter, 0.5 g of the silane compound (B-3) was added over 30 minutes and mixed, and finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 9. Was.

Example 10
14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed with 25 g of γ-butyrolactone. Dissolved. Thereafter, 0.5 g of the silane compound (B-3) is added and mixed over 30 minutes, and 0.1 g of the silane coupling agent (F-1) is further added over 30 minutes. The mixture was filtered with a fluororesin filter to obtain a photosensitive resin composition of Example 10.

<< Example 11 >>
14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed with 25 g of γ-butyrolactone. Dissolved. Thereafter, 0.5 g of the silane compound (B-3) is added and mixed over 30 minutes, and 0.4 g of the silane coupling agent (F-2) is further added over 30 minutes. The mixture was filtered with a fluororesin filter to obtain the photosensitive resin composition of Example 11.

Example 12
14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed with 25 g of γ-butyrolactone. Dissolved. Thereafter, 0.5 g of the silane compound (B-3) is added and mixed over 30 minutes, and 0.1 g of the silane coupling agent (F-1) is further added over 30 minutes, and then the fluorinated surfactant is added. 0.05 Megag F557 (manufactured by DIC Corporation) was added, and the mixture was finally filtered through a fluorine resin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Example 12.

Example 13
14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), 1.1 g of the thermal crosslinking agent (E-1), and the photoacid generator (C-1) synthesized above. ) 2.8 g was mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.5 g of the silane compound (B-3) is added and mixed over 30 minutes, and 0.1 g of the silane coupling agent (F-1) is further added over 30 minutes, and then the fluorinated surfactant is added. 0.05 g of Megafac F557 (manufactured by DIC Corporation) was added, and the mixture was finally filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Example 13.

<< Comparative Example 1 >>
20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. The mixture was filtered through a fluororesin filter to obtain a photosensitive resin composition of Comparative Example 1.

<< Comparative Example 2 >>
20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.4 g of a silane coupling agent (F-2) was added over 30 minutes, and finally, 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. .

  The photosensitive resin compositions obtained in each of the examples and comparative examples were evaluated by the following items.

<Processability evaluation>
Each of the photosensitive resin compositions obtained above was applied on an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120 ° C. for 3 minutes to form a coating film having a thickness of about 7.5 μm. Obtained. Using an i-line stepper (NSR-4425i, manufactured by Nikon Corporation) through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a pattern left and a blank having a width of 0.88 to 50 μm are drawn). Irradiation was performed while changing the exposure amount.
Next, using a 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution, the developing time was adjusted so that the difference between the film thickness after prebaking and the film thickness after development was 1.0 μm, and paddle was performed twice. After the exposed portion was dissolved and removed by performing development, it was rinsed with pure water for 10 seconds. The minimum exposure value at which a 100 μm square via hole pattern was formed was evaluated as sensitivity.

<Evaluation of cured residual film ratio>
Each of the photosensitive resin compositions obtained above was applied on an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120 ° C. for 3 minutes to form a coating film having a thickness of about 7.5 μm. Obtained. The coated film was heated in an oven at 150 ° C. for 30 minutes and subsequently 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 ratio between the film thickness after curing and the film thickness before curing was calculated from the following formula, and evaluated as a cured residual film ratio.
Residual film ratio = Film thickness after curing / Film thickness before curing * 100
Note that the cured residual film ratio is preferably higher in order to maintain a sufficient film thickness for protecting the semiconductor element.

<Adhesion evaluation>
Each of the photosensitive resin compositions obtained above was applied on an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120 ° C. for 3 minutes to form a coating film having a thickness of about 7.5 μm. Obtained. Using a mask in which a line-and-space pattern and a via pattern having a width of 1 to 20 μm are drawn on the coating film and using an i-line stepper (NSR-4425i, manufactured by Nikon Corporation), the exposure amount is changed and the i-line Irradiation was performed and paddle development was performed twice using a 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution to dissolve and remove the exposed portion. The pattern thus obtained was confirmed, and the exposure amount at which a 10 μm via hole pattern was formed was defined as a reference exposure amount. In the case where the development pattern formed by the 1 μm line-and-space pattern is formed on the wafer in which the exposed portion is dissolved and removed by irradiating with the reference exposure amount thus determined, the development pattern is The evaluation of adhesion after development was evaluated as x when the disappearance occurred.

<Heat resistance evaluation>
With respect to the cured film obtained by the evaluation of the cured residual film ratio, the temperature was raised by differential scanning calorimetry (DSC6000 manufactured by Seiko Instruments Inc.) at a temperature rise of 5 ° C./min, and the glass transition temperature (Tg) was calculated from the extrapolated point. Calculated. The temperature was raised at a rate of 10 ° C./min using a Tg-DTA apparatus (TG / DTA6200 manufactured by Seiko Instruments Inc.), and the 5% weight loss temperature (Td5) was measured.

<Evaluation of elongation and elastic modulus>
A tensile test (stretching speed: 5 mm / min) on a test piece (10 mm × 60 mm × 10 μm thickness) obtained by curing the photosensitive resin material obtained above under a nitrogen atmosphere at 300 ° C. for 30 minutes. ) Was performed in a 23 ° C. atmosphere. The tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. Five test pieces were measured, the tensile elongation was calculated from the distance at which the test piece was broken, and the initial distance, and the average was taken as the elongation. The tensile elastic modulus was calculated from the initial gradient of the obtained stress-strain curve, and the average was taken as the elastic modulus.

<Measurement of light transmittance>
With respect to the cured film obtained by the evaluation of the elongation and the elasticity, the light transmittance T (%) in terms of the film thickness of 10 μm with respect to the light having a wavelength of 630 nm was measured. The light transmittance T was determined by converting the light transmittance measured using a UV-160A manufactured by Shimadzu Corporation into a value of a film thickness of 10 μm according to Lambert-Beer's law.

  Hereinafter, the formulations of Examples and Comparative Examples and the evaluation results of the obtained photosensitive resin compositions are summarized and shown in Table 1.

<Production of semiconductor device>
Using a simulated element wafer having a pattern formed by an aluminum circuit on the surface, each of the photosensitive resin compositions obtained in Examples 1 to 13 was applied to a final thickness of 5 μm, and then the pattern formed on the wafer was formed. Was subjected to pattern processing and cured. Thereafter, the chip was divided for each chip size, and mounted on an organic substrate using a conductive paste using a die bonder (Bestem-D02). At this time, mounting could be performed without a decrease in visibility due to the photosensitive resin composition.

<Adhesion by high temperature and high pressure treatment>
Furthermore, the semiconductor device was produced by sealing and molding with a semiconductor sealing epoxy resin (manufactured by Sumitomo Bakelite Co., Ltd., EME-6300H). After treating these semiconductor devices (semiconductor packages) under the condition of 85 ° C./85% humidity for 168 hours, they are immersed in a solder bath at 260 ° C. for 10 seconds, and then subjected to a high-temperature, high-humidity pressure cooker treatment (125 ° C., 2.90 ° C.). (3 atm, 100% relative humidity), and the open defect of the aluminum circuit was checked. As a result, the cured film made of the photosensitive resin composition obtained in the example did not show any defect or the like, suggesting that the cured film had an adhesive property that could be used without problems as a semiconductor device.

  This application claims priority based on Japanese Patent Application No. 2014-098147 filed on May 9, 2014, the disclosure of which is incorporated herein in its entirety.

Claims (9)

An alkali-soluble resin (A),
A silane compound (B) represented by the following general formula (1),
A photoacid generator (C);
Including
The alkali-soluble resin (A) is selected from polybenzoxazole, polybenzoxazole precursor, polyimide, polyimide precursor,
The cyclic structure of A in the following general formula (1) and Si in the following general formula (1) are directly bonded ,
Shi A in the general formula (1) of the run compound (B) is an organic group selected from organic groups group represented by the following formula (3), the photosensitive resin composition.

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b each represent an integer of 0 to 3 satisfying a + b = 3; c and d each represent an integer of 0 to 3 that satisfies c + d = 3, and m and n each represent an integer of 0 to 2 and m + n ≠ 0.)

(Wherein X2 represents a single bond, C (-Y3) (-Y4), a divalent organic group containing a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, and Y3 and Y4 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group.) The photosensitive resin composition according to claim 1,
A photosensitive resin composition further comprising a phenol resin (D) obtained by reacting a phenol compound with an aromatic aldehyde compound. The photosensitive resin composition according to claim 2,
A photosensitive resin composition wherein the aromatic aldehyde compound contains an aromatic aldehyde compound represented by the following formula (4).

(In the formula, R ₁ represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxy group, and t is an integer of 0 to 3 inclusive.) The photosensitive resin composition according to claim 2 or 3,
A photosensitive resin composition wherein the phenol compound contains a phenol compound represented by the following formula (5).

(Wherein X3 represents a single bond, C (-Y7) (-Y8), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing an amide group, and Y7 and Y8 are each independently A hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted Or an unsubstituted cyclohexyl group; Y5 and Y6 each independently represent a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 20 carbon atoms, Represents an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group. Independently an integer of 1 to 3 is, r and s, each independently represent an integer of 0-3.) The photosensitive resin composition according to any one of claims 1 to 4,
A photosensitive resin composition further containing a thermal crosslinking agent (E).   A cured film comprising a cured product of the photosensitive resin composition according to claim 1.   A protective film comprising the cured film according to claim 6.   An insulating film comprising the cured film according to claim 6.   An electronic device comprising the cured film according to claim 6.

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