JP6747546B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition.

Conventionally, a polyamide resin having a specific structure has been preferably used as a surface protective film or an interlayer insulating film of a semiconductor element because of its high heat resistance, electrical characteristics, and mechanical characteristics. Here, when such a polyamide resin is used as a protective film or an interlayer insulating film of a semiconductor element, it is generally used by dissolving the polyamide resin in an organic solvent to form a varnish from the viewpoint of process efficiency. It was target.

In this regard, the technique disclosed in Patent Document 1 is known. This document discloses a photosensitive resin composition in which a polyimide precursor or a polybenzoxazole precursor is combined with a polar solvent having a specific structure, and N-methyl-in the photosensitive resin composition is also disclosed. It is disclosed that by adjusting the content of 2-pyrrolidone (NMP) to 0.1% by mass or less, a resin composition which does not gel with time and satisfies the sensitivity and mechanical properties can be obtained. ..

International publication 2014/115233 pamphlet

Here, as a result of examination by the present inventors, in the case of using the solvent disclosed in Examples 5 and 6 of Patent Document 1, as compared with N-methyl-2-pyrrolidone (NMP) which is generally used, the resin It has been found that the development adhesion decreases when the composition is developed.

Based on such knowledge, as a result of diligent study, as a result of using together an organic solvent containing a compound having an ether bond and an amide bond in the molecule and an adhesion promoter, a photosensitive resin containing a polyamide resin and a photo-acid generator was prepared. It has been found that the resin composition can suppress the increase in viscosity and improve the development adhesion while obtaining good patterning properties. It was also found that when the photosensitive resin composition was used for forming a permanent film, the occurrence of cracks during rewiring could be suppressed. With such a composition, it was found that in the photosensitive resin composition, the patterning property and the development adhesiveness are improved, and at the same time, the increase in viscosity and the suppression of crack generation during rewiring are improved, and the present invention has been completed. It was

According to the invention,
A photosensitive resin composition used for forming a permanent film,
(A) Polyamide resin having a structure selected from the group consisting of a polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, and a polyimide precursor structure (B) a photoacid generator (C) an adhesion aid (D) organic includes a solvent, the (D) organic solvent, seen containing a compound having an ether bond and an amide bond in the molecule,
The adhesion promoter (C) is a compound having at least one carboxyl group in the molecule,
The (B) photoacid generator is contained in an amount of 5 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the (A) polyamide resin,
The (C) adhesion aid is contained in an amount of 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (A) polyamide resin.
A photosensitive resin composition is provided.

According to the present invention, it is possible to provide a photosensitive resin composition used for forming a permanent film, which is excellent in patterning property and development adhesion, and can suppress increase in viscosity and generation of cracks during rewiring. ..

The above-mentioned object, other objects, features and advantages will be further clarified by the preferred embodiments described below and the accompanying drawings.

It is sectional drawing which shows an example of the electronic device which concerns on this embodiment.

Hereinafter, embodiments will be described with reference to the drawings as appropriate. In all the drawings, the same constituents will be given the same reference numeral, and the description thereof will not be repeated. Moreover, "-" represents the following from the above unless otherwise specified.

[Photosensitive resin composition]
The photosensitive resin composition according to this embodiment is a photosensitive resin composition used for forming a permanent film, and contains the following components.
(A) Polyamide resin having a structure selected from the group consisting of a polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, and a polyimide precursor structure (B) a photoacid generator (C) an adhesion aid (D) organic Solvent Here, the organic solvent (D) is characterized by containing a compound having an ether bond and an amide bond in the molecule.

First, the use of the photosensitive resin composition according to this embodiment will be described.
The photosensitive resin composition of this embodiment is used for forming a permanent film. By using the photosensitive resin composition as a cured product, a cured film forming a permanent film can be obtained. In the present embodiment, for example, a coating film made of a photosensitive resin composition is patterned into a desired shape by exposure and development, and then the coating film is cured by heat treatment or the like to form a cured film (permanent film). To be done.
In the present embodiment, the organic solvent (D) containing a compound having an ether bond and an amide bond in the molecule causes less damage to the cured film of the photosensitive resin composition and can suppress the occurrence of cracks in the cured film. There is also a side effect of being able to do it.

Examples of the cured film (permanent film) formed using the photosensitive resin composition include a protective film, an interlayer insulating film (insulating film), or a dam material. The application of the permanent film is not limited to this, but in one embodiment, the application as a film having a high light shielding property against visible light such as a color filter or a black matrix may be excluded.

The protective film refers to a film formed on the surface of the electronic component or the electronic device and protecting the surface of the electronic component or the electronic device, and the type thereof is not particularly limited. Examples of such a 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.

The interlayer insulating film refers to an insulating film provided in a multilayer structure, and the type thereof is not particularly limited. Examples of the interlayer insulating film include those used in semiconductor device applications such as an interlayer insulating film forming a multilayer wiring structure of a semiconductor element, a buildup layer or a core layer forming a circuit board. The interlayer insulating film is provided, for example, on a flattening film covering a thin film transistor (TFT) in a display device, a liquid crystal alignment film, and a color filter substrate of a MVA (Multi Domain Vertical Alignment) liquid crystal display device. Examples thereof include those used in display device applications such as projections or partition walls for forming a cathode of an organic EL element.
The dam material is a spacer used to form a hollow portion for disposing an optical element or the like on the substrate.

Next, each component constituting the photosensitive resin composition according to this embodiment will be described.

((A) Polyamide resin)
The (A) polyamide resin (hereinafter, also referred to as (A) amide resin) used in this embodiment includes a polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, and a polyimide precursor structure. A structure selected from the group is provided in the structure of the resin.
This (A) polyamide resin has, for example, a hydroxyl group, particularly a phenolic hydroxyl group and/or a carboxyl group in its main chain or side chain, and has a polybenzoxazole structure, a polybenzoxazole precursor structure, and a polyimide structure. , One of the polyimide precursor structures is included in the resin structure.
These resin components may be used alone or in combination of two or more.

More specifically, as the polyamide resin (A), a resin having a benzoxazole precursor structure and/or an imide precursor structure is preferably used.
The polyamide resin (A) may have a benzoxazole structure formed by a ring-closing reaction of a part of the benzoxazole precursor structure or an imide structure formed by a ring-closing reaction of a part of the imide precursor structure. Well, it may have an amic acid ester structure.

The specific benzoxazole precursor structure refers to the structure represented by the following general formula (6), the imide precursor structure refers to the structure represented by the following general formula (7), and the benzoxazole structure is , Refers to a structure represented by the following general formula (8), an imide structure refers to a structure represented by the following general formula (9), and an amic acid ester structure is represented by the following general formula (10). Structure.

In the formulas (6) to (10), D represents a divalent or trivalent organic group, and R′ represents a monovalent 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 heat resistance of the cured product of the photosensitive resin composition of the present embodiment.

（式（１１）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 (11), 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, and when two or more are present, they are the same. good .R ₃ also be different, a hydroxyl group, a carboxyl group, an _{-O-R 4} or _{-COO-R 4,} in the case, good .R ₂ and _{R 3} may each be the same or different plural having R ₄ 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} In the case where there is no carboxyl 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), R ₂ and R ₃ have a hydroxyl group and a carboxyl group protected by a protective group R ₄ in order to adjust the solubility of the polyamide resin in an alkaline aqueous solution. radicals can be used, specifically, can be used _{-O-R 4} and _{-COO-R 4} as _-O-R 4, R ₃ as _{R 2.} Examples of such an organic group having 1 to 15 carbon atoms as R ₄ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, Examples thereof include a tetrahydrofuranyl group and a tetrahydropyranyl group.

The organic group as X of the polyamide resin having the structure represented by the general formula (11) is not particularly limited, but is, for example, an aromatic group having a structure such as a benzene ring, a naphthalene ring and a bisphenol structure. A heterocyclic organic group having a structure such as a pyrrole ring and a furan ring; 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 if 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), * is .Z indicating that binds to the NH group in formula (11) is an alkylene group, substituted alkylene _{group, -O-C 6 H 4 -O} -, - O-, _{-S -, - SO 2 -,} - C (= O) -, - NHC (= O) - or .R ₅ is a single bond, an alkyl group, one selected from an alkyl ester group and a halogen atom R ₆ may be the same or different, and 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 addition, in the above formula (12), the substituent R ₂ of X in the above general formula (11) is omitted. )

Among the groups represented by the above formula (12), particularly preferable groups include those represented by the following formula (13) (some have 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), * represents binding to the NH group in the general formula (11). In the formula, Z represents an alkylene group, a substituted alkylene group, -O-, -S-, -SO ₂ -, -. _{C (= O) -, -} NHC (= O) -, - CH 3 -, - C (CH 3) H -, - C (CH 3) 2 -, - C (CF 3) 2 -, or a single bond R ₁₁ is one selected from an alkyl group, an alkoxy group, an acyloxy group and a cycloalkyl group, and when there are a plurality of R ₁₁ , they may be the same or different, and v is an integer of 0 or more and 3 or less. It is.)

Among the groups represented by the above formula (13), particularly preferred are groups represented by the following formula (14) (some have 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), * represents binding to the NH group in the general formula (11). R ₁₂ represents an alkylene group, a substituted alkylene group, —O—, —S—, —SO ₂ —, —C( = O) -, - NHC ( = O) -, - C (CF 3) 2 -, an organic group selected from a single bond).

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 CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 CH 2 _{CH 3) -, - CH (} CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) - and _{-C (CH 3) (CH 2} CH 2 CH 2 CH 2 CH 2 CH 3) - , and the like. Among _{these, -CH 2 -, - CH (} CH 3) -, - C (CH 3) 2 - 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, Y in the polyamide resin having the structure represented by the general formula (11) is an organic group. Examples of such an organic group include those similar to the above X. For example, examples of the organic group 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; and a siloxane group. More specifically, the one represented by the following formula (15) can be used. You may use these 1 type or in combination of 2 or more types.

（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 _{.R 13} is a single bond, an alkyl group, an alkyl ester group, alkyl ether Group, a benzyl ether group, and a halogen atom, which may be the same or different, and R ₁₄ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. w is an integer from 0 to 2. R _{15 to} R ₁₈ are each a monovalent or divalent organic group.
In the formula (15), the substituent R ₃ of Y in the general formula (11) is omitted. )

Among these groups represented by the formula (15), particularly preferable groups include those represented by the following formula (16) (some have R ₃ in the general formula (11)).
Regarding the structure derived from tetracarboxylic acid dianhydride in the following formula (16), mention may be made of those in which the positions bonded to the C═O group in the general formula (11) are both in the meta position and both are in the para position. However, the structure may include a meta position and a para position, respectively.

(In the formula (16), * represents binding to the C═O group in the general formula (11). R ₁₉ represents 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 to the extent that it does not affect the mechanical properties and heat resistance of the cured product cured at low temperature. It is also possible to use 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 to end-cap the amide.
Examples of the acid anhydride or monocarboxylic acid containing an aliphatic group or cyclic compound group having at least one organic group selected from the above alkenyl group, alkynyl group and hydroxyl group include maleic anhydride and citraconic anhydride. Substance, 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 acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, itaconic acid anhydride, het acid anhydride, 5-norbornene-2-carboxylic acid, 4-ethynylphthalic acid anhydride And 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and the like. These may be used alone, or may be used in combination of two or more kinds, and a part of the end-capped 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 is an aliphatic group having at least one organic group selected from an alkenyl group, an alkynyl group and a hydroxyl group, or An amine derivative containing a cyclic compound group can also be used to endcap the amide.

Furthermore, in the case of the polyamide resin represented by the general formula (11), at least one of the terminals is end-capped with a nitrogen-containing cyclic compound to the extent that it does not affect the mechanical properties and heat resistance of the cured product cured at low temperature. It may have a terminating group. As a result, it is possible to improve the adhesion to metal wiring (for example, copper wiring) and the like.
Examples of the nitrogen-containing cyclic compound include a 1-(5-1H-triazoyl)methylamino group, a 3-(1H-pyrazoyl)amino group, a 4-(1H-pyrazoyl)amino group, and a 5-(1H-pyrazoyl)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) An amino group, a 1-(1H-tetrazol-5-yl)methyl-amino group, a 3-(1H-tetrazol-5-yl)benz-amino group and the like can be mentioned.

The polyamide resin having the structure represented by the general formula (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 selected from tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid, dicarboxylic acid dichloride, dicarboxylic acid derivative, and the like containing Y can be reacted to synthesize.
When a dicarboxylic acid is used, an active ester type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like with dicarboxylic acid in order to increase the reaction yield of the polyamide resin and the like. 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 for dehydration ring closure may be 280°C to 380°C for heating at a high temperature, and 150°C to 280°C for heating at a low temperature.

Regarding the (A) polyamide resin contained in the photosensitive resin composition of the present embodiment, when the photosensitive resin composition is used for a certain purpose, the halogen atom content in the structure of the (A) polyamide resin is It is preferred that the amount is limited.
More specifically, the fluorine content of the polyamide resin (A) measured by elemental analysis is preferably 8 wt% or less, and more preferably 5 wt% or less.
The halogen content of the (A) polyamide resin measured by elemental analysis is preferably 8 wt% or less, more preferably 5 wt% or less.
The halogen content herein means the total content of fluorine, chlorine, bromine and iodine in the polyamide resin (A).
It is known that the solubility of the halogen atom in the polyamide resin (A) as described above usually increases the solubility in an organic solvent. However, since the organic solvent (D) used in this embodiment has a high solubility in such a polyamide resin, it can be sufficiently dissolved without containing a halogen atom as the component (A) polyamide resin. be able to.

((B) Photo-acid generator)
The photosensitive resin composition of this embodiment contains (B) a photo-acid generator.
Examples of the photoacid generator (B) include photosensitive diazoquinone compounds, diaryliodonium salts, onium salts such as triarylsulfonium salts or sulfonium borate salts, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imidosulfonates. A compound, a 2,6-bis(trichloromethyl)-1,3,5-triazine compound, or a dihydropyridine compound can be used. Among these, it is particularly preferable to use a photosensitive diazoquinone compound which is excellent in sensitivity and solvent solubility. As the photosensitive diazoquinone compound, for example, the following compounds can be used.

（ｎ２は、１以上、５以下の整数である）

(N2 is an integer of 1 or more and 5 or less)

In each of the above compounds, Q is any of the structures shown in (a) to (c) below, or a hydrogen atom. However, at least one of Q of each compound has any of the structures shown in (a) to (c) below.

In the present embodiment, as the photosensitive diazoquinone compound, 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. Is more preferably used. When the photosensitive resin composition is a positive type, it is considered that the photosensitizer remaining in the relief pattern of the unexposed portion is decomposed by heat during curing to generate an acid. The acid generator plays an important role. As the photosensitive diazoquinone compound having such a role, it is particularly preferable to use an ester of 1,2-naphthoquinone-2-diazide-4-sulfonic acid, which is more easily decomposed by heat.

The content of the photoacid generator (B) in the photosensitive resin composition of the present embodiment is not particularly limited, but is 5 parts by mass or more based on 100 parts by mass of the (A) polyamide resin. Is preferable, and more preferably 8 parts by mass or more. Further, the content of the (B) photoacid generator in the photosensitive resin composition is preferably 40 parts by mass or less, and preferably 30 parts by mass or less, relative to 100 parts by mass of the (A) polyamide resin. More preferable. When the content of the photoacid generator (B) is within the above range, good patterning performance can be exhibited.

((C) Adhesion aid)
The (C) adhesion aid is contained in the photosensitive resin composition of the present embodiment.
The (C) adhesion aid used here is a component having a function of improving the bonding strength between the coating film obtained by curing the photosensitive resin composition and the substrate on which the coating film is formed.
Examples of the adhesion promoter (C) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and p-styryltrimethoxysilane. 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 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxypropyl)tetra Examples thereof include, but are not limited to, sulfides, 3-isocyanatopropyltriethoxysilane, and silicon compounds obtained by reacting a silicon compound having an amino group with an acid dianhydride or an acid anhydride.
Among these compounds, a silicon compound obtained by reacting a silicon compound having an amino group with an acid dianhydride or an acid anhydride has an intramolecular structure when the acid dianhydride or the acid anhydride is ring-opened. A carboxyl group is generated.
Thus, by including at least one carboxyl group in the molecule as the adhesion promoter (C), while exhibiting an appropriate affinity with a compound having an ether bond and an amide bond in the molecule described later. The adhesion of the cured product of the photosensitive resin composition to the substrate can be improved. That is, in the photosensitive resin composition of the present embodiment, by using (C) the adhesion aid and (D) an organic solvent containing a compound having an ether bond and an amide bond in the molecule in combination, the viscosity increase rate is also increased. It is low, excellent in patterning and development adhesion, and can suppress the occurrence of cracks in the cured film.

The type of the silicon compound having an amino group is not particularly limited as long as it can improve the adhesion, and examples thereof include 3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3. -Aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane.
The acid dianhydride or acid anhydride is not particularly limited in type as long as it can improve the adhesiveness, but for example, 3,3′,4,4′-benzophenonetetracarboxylic acid anhydride , Cyclohexene dicarboxylic acid anhydride, maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, phthalic anhydride and the like. In addition, they can be used alone or in combination of two or more.

The content of the (C) adhesion aid in the photosensitive resin composition of the present embodiment is not particularly limited, but is 0.01 part by mass or more with respect to 100 parts by mass of the (A) polyamide resin. It is preferable that the amount is 0.1 parts by mass or more.
Further, the content of the (C) adhesion aid in the photosensitive resin composition is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the (A) polyamide resin. preferable. When the content of the (C) adhesion aid is within the above range, the adhesion to the substrate and the storability of the photosensitive resin composition can be improved in a well-balanced manner.

((D) Organic solvent)
The photosensitive resin composition of the present embodiment is usually used by dissolving the above components in the organic solvent (D) to form a varnish.
The photosensitive resin composition of the present embodiment is characterized in that the organic solvent (D) contains a compound having an ether bond and an amide bond in the molecule.

In this way, by containing a compound having an ether bond and an amide bond in the molecule as the organic solvent (D), it is possible to suppress an increase in the viscosity of the photosensitive resin composition and suppress the occurrence of cracks in the cured film. You can
The reason for this is not clear, but the polarity provided by the above-mentioned two kinds of bonds in the molecule exerts an appropriate affinity for the (B) photoacid generator, and (B) the photoacid generator due to heat or the like. It is thought to suppress the decomposition of.
Further, as compared with an organic solvent having only an amide bond, such as N-methyl-2-pyrrolidone, the load of damage to the amide resin (A) is reduced, so that cracking of the cured film can be suppressed. it can.

More specifically, as the compound having an ether bond and an amide bond in the molecule, a compound represented by the following general formula (1) can be preferably used.

（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれ炭素数１から１０のアルキル基である。）

(In the formula (1), R ₁ , R ₂ and R ₃ are each an alkyl group having 1 to 10 carbon atoms.)

Here, as the alkyl group represented by R ₁ , R ₂ and R ₃ in the formula (1), a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a pentyl group, A hexyl group, a heptyl group, an octyl group or the like can be adopted.

In the photosensitive resin composition of the present embodiment, as the (D) organic solvent, a compound usually used as a solvent can be used in combination with the above-mentioned compound having an ether bond and an amide bond in the molecule. ..
Examples of such a compound 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, and ethyl pyruvate and methyl-3. -Methoxy propionate and the like.
From the viewpoint of significantly suppressing the occurrence of cracks in the cured film, among these compounds, γ-butyrolacurone, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether. In a preferred embodiment, a compound selected from the group consisting of propylene glycol monomethyl ether acetate is used in combination.
In the present embodiment, the compound having an ether bond and an amide bond in the molecule as the organic solvent (D) can be used in combination with other solvent as described above. This can increase the usable solvent species. Therefore, it is possible to improve the solubility of the organic solvent (D) in various dissolved components while achieving the effect of the photosensitive resin composition of the present embodiment.

Further, the content of the compound having an ether bond and an amide bond in the molecule in the organic solvent (D) is preferably 25% by mass or more, and more preferably 40% by mass or more.
By setting the content of the compound having an ether bond and an amide bond in the molecule in this manner, it is possible to more significantly contribute to the suppression of the viscosity increase of the photosensitive resin composition and the suppression of the occurrence of cracks in the cured film. it can.
Further, the upper limit of the content of the compound having an ether bond and an amide bond in the molecule in the organic solvent (D) is not particularly limited, and all of the organic solvent (D) has the ether bond and the amide bond. It may be a compound having
Alternatively, in consideration of the solubility of the amide resin (A), for example, the content of the compound having an ether bond and an amide bond in the organic solvent (D) may be set to 95% by mass or less.

The content of the (D) organic solvent in the photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 100 parts by mass or more based on 100 parts by mass of the (A) polyamide resin. More preferably 150 parts by mass or more.
The content of the (D) organic solvent in the photosensitive resin composition is preferably 1000 parts by mass or less, and more preferably 800 parts by mass or less with respect to 100 parts by mass of the (A) polyamide resin. .. When the content of the (D) organic solvent is within the above range, appropriate handling properties can be provided.

(Other ingredients)
The photosensitive resin composition of the present embodiment may contain various components used as the photosensitive resin composition, in addition to the components described above. For example, as the alkali-soluble resin, a component other than the above-mentioned (A) polyamide resin can be used in combination.
Examples of such alkali-soluble resins include acrylic resins such as phenol resins, phenol aralkyl resins, hydroxystyrene resins, methacrylic acid resins, and methacrylic acid ester resins, and cyclic olefin resins.
In addition, if necessary, additives such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a terminal blocking agent and a sensitizer may be added.
In addition, the amount which can add these is arbitrary.

As described above, the resin film (cured film) obtained by curing the photosensitive resin composition of the present embodiment can form, for example, a protective film, an interlayer film, or a permanent film such as a dam material. This makes it possible to improve the durability and the like of an electronic device including the cured film as a permanent film.

Next, an example of the electronic device 100 to which the photosensitive resin composition of this embodiment is applied will be described.
The electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip. In this case, a semiconductor package is obtained, for example, by mounting electronic device 100 on a wiring board via bumps 52. The electronic device 100 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). An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided on the uppermost layer of the multilayer wiring layers. The uppermost layer wiring 34 is made of, for example, Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost wiring 34. An opening exposing the uppermost layer wiring 34 is provided in a part of the passivation film 32.

A redistribution layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 42 and an insulating layer 44 provided on the rewiring 46. Have. The insulating layer 42 has an opening connected to the uppermost layer wiring 34. The rewiring 46 is formed on the insulating layer 42 and in the opening provided in the insulating layer 42, and is connected to the uppermost wiring 34. The insulating layer 44 is provided with an opening that connects to the rewiring 46.
In the present embodiment, one or more of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be configured by a cured film formed by curing the above-mentioned photosensitive resin composition, for example. In this case, the passivation film 32, the insulating layer 42, or the insulating layer 44 is formed by exposing the coating film formed of, for example, a photosensitive resin material to ultraviolet rays, developing it to pattern it, and then heating and curing it. It is formed.

Bumps 52 are formed in the openings provided in the insulating layer 44, for example, via a UBM (Under Bump Metallurgy) layer 50. The electronic device 100 is connected to a wiring board or the like via the bumps 52, for example.

（式（１）中、Ｒ _１ 、Ｒ _２ 、Ｒ _３ はそれぞれ炭素数１から１０のアルキル基である。）
３． 前記分子内にエーテル結合とアミド結合とを有する化合物を、前記（Ｄ）有機溶剤中に２５質量％以上含む、１．または２．に記載の感光性樹脂組成物。
４． 前記（Ａ）ポリアミド樹脂の、元素分析により測定されるフッ素含有率が８ｗｔ％以下である、１．ないし３．のいずれか一つに記載の感光性樹脂組成物。
５． 前記（Ｃ）密着助剤が、分子内に少なくとも１以上のカルボキシル基を有する化合物であることを特徴とする、１．ないし４．のいずれか一つに記載の感光性樹脂組成物。
６． 前記（Ｂ）光酸発生剤が、前記（Ａ）ポリアミド樹脂１００質量部に対して５質量部以上４０質量部以下含まれる、１．ないし５．のいずれか一つに記載の感光性樹脂組成物。
７． 前記（Ｃ）密着助剤が、前記（Ａ）ポリアミド樹脂１００質量部に対して０．０１質量部以上２０質量部以下含まれる、１．ないし６．のいずれか一つに記載の感光性樹脂組成物。
８． 前記（Ｄ）有機溶剤が、前記（Ａ）ポリアミド樹脂１００質量部に対して１００質量部以上１０００質量部以下含まれる、１．ないし７．のいずれか一つに記載の感光性樹脂組成物。
９． １．ないし８．のいずれか一つに記載の感光性樹脂組成物の硬化物で構成される硬化膜。
１０． ９．に記載の硬化膜で構成される保護膜。
１１． ９．に記載の硬化膜で構成される絶縁膜。
１２． ９．に記載の硬化膜を備える電子装置。
It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.
Hereinafter, an example of the reference mode will be additionally described.
1. A photosensitive resin composition used for forming a permanent film,
(A) Polyamide resin having a structure selected from the group consisting of polybenzoxazole structure, polybenzoxazole precursor structure, polyimide structure, and polyimide precursor structure
(B) Photoacid generator
(C) Adhesion aid
(D) Organic solvent
And (D) the organic solvent contains a compound having an ether bond and an amide bond in the molecule.
2. The compound having an ether bond and an amide bond in the molecule is a compound represented by the following general formula (1):1. The photosensitive resin composition according to item 1.

(In the formula (1), R ₁ , R ₂ and R ₃ are each an alkyl group having 1 to 10 carbon atoms.)
3. 1. 25% by mass or more of the compound having an ether bond and an amide bond in the molecule is contained in the organic solvent (D). Or 2. The photosensitive resin composition according to item 1.
4. The (A) polyamide resin has a fluorine content of 8 wt% or less as measured by elemental analysis. Through 3. The photosensitive resin composition according to any one of 1.
5. 1. The adhesion promoter (C) is a compound having at least one carboxyl group in the molecule, Through 4. The photosensitive resin composition according to any one of 1.
6. The (B) photoacid generator is contained in an amount of 5 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the (A) polyamide resin. Through 5. The photosensitive resin composition according to any one of 1.
7. The (C) adhesion aid is contained in an amount of 0.01 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the (A) polyamide resin. Through 6. The photosensitive resin composition according to any one of 1.
8. 1. The organic solvent (D) is contained in an amount of 100 parts by mass or more and 1000 parts by mass or less based on 100 parts by mass of the (A) polyamide resin. Through 7. The photosensitive resin composition according to any one of 1.
9. 1. Through 8. A cured film comprising a cured product of the photosensitive resin composition according to any one of 1.
10. 9. A protective film composed of the cured film according to 1.
11. 9. An insulating film composed of the cured film according to.
12. 9. An electronic device provided with the cured film according to.

Next, examples of the present invention will be described.
First, each material used in the examples was prepared as shown below.

(Synthesis of amide resin (A-1))
Diphenyl ether-4,4'-dicarboxylic acid (1 mol) and 1-hydroxybenzotriazole (2 mol) were reacted to obtain a dicarboxylic acid derivative (40.87 g, 0.083 mol) and 2,2-bis(3-amino-). 25.82 g (0.1 mol) of 4-hydroxyphenyl)propane was placed in a 4-neck separable flask equipped with a thermometer, a stirrer, a raw material charging port, and a dry nitrogen gas introducing tube, and N-methyl-2- Pyrrolidone (3000 g) was added and dissolved. Then, the reaction was carried out at 75° C. for 12 hours using an oil bath. Next, 6.98 g (0.0425 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added, and further. The reaction was completed by stirring for 3 hours.
Then, after filtering the reaction mixture, the reaction mixture was poured into a solution of water/isopropyl alcohol=3/1, the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum, and repeated as shown below. An amide resin which is an alkali-soluble resin having a unit (a resin which becomes a polybenzoxazole by dehydration ring closure when heated at 300 to 400° C.) was obtained.

The obtained amide resin (A-1) had a repeating unit shown below, and had a weight average molecular weight (Mw) of 14,300, a number average molecular weight (Mn) of 9730, and Mw/Mn of 1.47. .. Further, the fluorine content measured by elemental analysis was 0 wt %.

(Synthesis of amide resin (A-2))
In a four-neck glass separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 21.2 g (0.2%) of 2,2-bis(3-amino-4-hydroxyphenyl)propane was added. (082 mol) was added and 400 ml of acetone was added and dissolved. Next, 33.4 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 dropping, the temperature of the mixture was heated to 40° C., and the mixture was 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. Then, the sodium hydroxide aqueous solution was gradually added while vigorously stirring the mixture, and after the addition, the mixture was heated to 55° C. and further stirred for 30 minutes. After the completion of stirring, the mixture was cooled to room temperature, 37% by weight aqueous hydrochloric acid solution and 500 ml of water were added, and the pH of the solution was adjusted to be in the range of 6.0 to 7.0. Then, the obtained precipitate is filtered off, the filtrate is washed with water, and then dried at 60 to 70° C. to obtain bis-N,N′-(para-nitrobenzoyl)-2,2-bis. A solid of (4-hydroxyphenyl)propane was obtained.
To 41.9 g of the obtained solid, 316 g of acetone and 158 g of methanol were added and heated to 50° C. to completely dissolve it. To this, 300 mL of pure water at 50° C. was added over 30 minutes and heated to 65° C. After that, the mixture was slowly cooled to room temperature, the precipitated crystal was filtered, and the crystal was purified by drying at 70° C. to obtain bis-N,N′-(para-nitrobenzoyl)-2,2-bis(4 -Hydroxyphenyl)propane was obtained.
20 g of bis-N,N'-(para-nitrobenzoyl)-2,2-bis(4-hydroxyphenyl)propane obtained above was placed in a 1 L flask, and 1.0 g of 5% palladium-carbon catalyst and acetic acid were added. 180.4 g of ethyl was added to make a suspension. Hydrogen gas was purged therein, and the mixture was shaken for 35 minutes while heating at 50 to 55° C. to carry out a reduction reaction. After the reaction was completed, the suspension was cooled to 35° C., and the suspension was purged with nitrogen. After removing the catalyst by filtration, the filtrate was evaporated to evaporate the solvent. The obtained product was dried at 90° C. to obtain bis-N,N′-(para-aminobenzoyl)-2,2-bis(4-hydroxyphenyl)propane.
To a 300 mL flask, 11.91 g (0.024 mol) of bis-N,N'-(para-aminobenzoyl)-2,2-bis(4-hydroxyphenyl)propane and 40 g of γ-butyrolactone were added, and the mixture was stirred at 15 Cooled to °C. Thereto, 6.82 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, 5.24 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 mixture was cooled to room temperature to obtain an amide resin (a resin which becomes a polyimidebenzoxazole by heating and dehydration ring closure when heated at 300 to 400° C.) which is an alkali-soluble resin having a repeating unit shown below.

The obtained amide resin (A-2) had a repeating unit shown below, and had a weight average molecular weight (Mw) of 15420, a number average molecular weight (Mn) of 10550, and Mw/Mn of 1.46. .. Further, the fluorine content measured by elemental analysis was 0 wt %.

Ｒ_２１は、水素原子または−ＣＨ_３を示す。

R ₂₁ represents a hydrogen atom or —CH ₃ .

(Synthesis of photoacid generator (B-1))
In a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 11.04 g (0.026 mol) of phenol represented by the formula (P-1) and 1, 18.81 g (0.070 mol) of 2-naphthoquinone-2-diazide-4-sulfonyl chloride and 170 g of acetone were put under a dry nitrogen stream condition, stirred and dissolved.
Next, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35°C. After reacting as it was at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added and further reacted 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). Then, the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum. Thereby, the photo-acid generator (B-1) represented by the structure of formula (Q-1) was obtained.

(Adhesion aid (C-1))
The adhesion aid (C-1) shown below was prepared.

(Adhesion aid (C-2))
The adhesion aid (C-2) shown below was prepared.

(Organic solvent (D-1))
Examide (registered trademark) B-100 manufactured by Idemitsu Kosan Co., Ltd. shown below was prepared as an organic solvent (D-1).

(Organic solvent (D-2, D-3))
Γ-butyrolactone was prepared as the organic solvent (D-2), and N-methyl-2-pyrrolidone was prepared as the organic solvent (D-3).

[Examples 1 to 6, Comparative Examples 1 to 3]
Various materials were blended in the mass proportions shown in Table 1. Then, it was filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition.
The photosensitive resin composition in each of Examples and Comparative Examples was evaluated as follows. The results are shown in Table 1.

(Rate of viscosity increase)
With respect to the photosensitive resin compositions described in each example and each comparative example, the viscosity before standing (E0) was measured using an E-type viscometer (TVE-22H manufactured by Toki Sangyo Co., Ltd.). Then, the photosensitive resin composition was allowed to stand for 1 week in a thermostatic chamber maintained at 23 degrees, and the viscosity (E1) after standing was measured. Using the viscosity E0 before standing and the viscosity E1 after standing, the rate of increase in viscosity at room temperature was derived from the following formula.
Viscosity increase rate (%)=(E1-E0)/E0*100
A gel having a viscosity increase rate of more than 100% was defined as gelation. The unit in Table 1 is%.

(Patterning)
The photosensitive resin composition produced in each Example and each Comparative Example was applied on a silicon wafer using a spin coater, and then prebaked at 120° C. for 4 minutes on a hot plate to apply a film having a thickness of about 9.4 μm. A film was obtained. An i-line stepper (manufactured by Nikon Corp., 4425i) is passed through this coating film through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a residual pattern and a blank pattern having a width of 0.88 to 50 μm are drawn). ) Was used to change the amount of exposure and to irradiate ultraviolet rays.
Next, paddle development was performed using a 2.38% tetramethylammonium hydroxide aqueous solution and adjusting the development time so that the film thickness difference between the pre-baked and unexposed areas was 1.5 μm. Then, it was rinsed with pure water for 10 seconds and then dried. After that, the 10 μm via pattern was observed with a microscope, and when the pattern was formed, it was evaluated as ◯, and when the pattern was not formed, as ×, the patterning property was evaluated.

(Development contact)
With respect to the photosensitive resin compositions prepared in each of the examples and each of the comparative examples, the adhesiveness at the time of development was evaluated as follows. First, an 8-inch silicon wafer (Si substrate) is prepared, the obtained varnish-shaped photosensitive resin composition is applied using a spin coater, and then heated at 120° C. for 240 seconds to remove the solvent. I went. Through the mask in which a line-and-space pattern with a width of 1 to 20 μm and a via hole are drawn on this coating film, the exposure amount is changed by using an i-line stepper (NSR-4425i manufactured by Nikon Corporation) to change the i-line. Then, using a 2.38% tetramethylammonium hydroxide aqueous solution as a developing solution, the developing time is adjusted so that the film thickness difference between the pre-baked and unexposed areas after development is 1.5 μm. The exposed portion was dissolved and removed by performing the paddle development twice. Then, it was rinsed with pure water for 10 seconds and then dried. The pattern thus obtained is confirmed by a microscope, and a 10 μm line-and-space pattern is formed on the wafer at an exposure dose for forming a 50 μm via hole pattern. When the and-space pattern disappeared due to peeling, the adhesion was evaluated at the time of development by setting x.

(Cracks during rewiring)
With respect to the photosensitive resin compositions produced in each of the examples and each of the comparative examples, cracks at the time of rewiring (at the time of applying two layers) were evaluated as follows. First, an 8-inch silicon wafer (Si substrate) is prepared, the obtained varnish-shaped photosensitive resin composition is applied using a spin coater, and then heated at 120° C. for 240 seconds to remove the solvent. I went. Through the mask in which a line-and-space pattern and a via pattern having a width of 1 to 20 μm are drawn on this coating film, the exposure amount is changed by using an i-line stepper (NSR-4425i manufactured by Nikon Corporation) to change the i-line. Then, using a 2.38% tetramethylammonium hydroxide aqueous solution as a developing solution, the developing time is adjusted so that the film thickness difference between the pre-baked and unexposed areas after development is 1.5 μm. The exposed portion was dissolved and removed by performing the paddle development twice. After performing the above-mentioned treatment, a high-temperature clean oven (Koyo Thermo System CLH-21CDH) was used to perform heat treatment at 230°C for 90 minutes under conditions of an oxygen concentration of 100 ppm or less. The patterned photosensitive resin composition thus prepared was coated with a second coating film using a spin coater so that the coating thickness was 12 μm, and the coating film was removed by heating at 120° C. for 240 seconds. The solvent was removed to obtain a two-layer coated wafer. The obtained two-layer coated wafer was observed using a microscope, and when the pattern of the first layer was not cracked, it was evaluated as ○, and when cracked, it was evaluated as × when rewiring (when coated with two layers). The cracking property was evaluated.

As shown in Table 1, in each of the examples, the rate of increase in viscosity was low, the patterning and development adhesion were excellent, and the occurrence of cracks in the cured film could be suppressed. From this, in the present invention, by providing each of the components (A) to (D) in combination, a photosensitive resin composition that suppresses an increase in viscosity as a resin composition and is also excellent in development adhesion is provided. You can see that you can.

This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2015-147160 for which it applied on July 24, 2015, and takes in those the indications of all here.

Claims (4)

A photosensitive resin composition used for forming a permanent film,
(A) Polyamide resin having a structure selected from the group consisting of a polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, and a polyimide precursor structure (B) a photoacid generator (C) an adhesion aid (D) organic includes a solvent, the (D) organic solvent, seen containing a compound having an ether bond and an amide bond in the molecule,
The adhesion promoter (C) is a compound having at least one carboxyl group in the molecule,
The (B) photoacid generator is contained in an amount of 5 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the (A) polyamide resin,
The (C) adhesion aid is contained in an amount of 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (A) polyamide resin.
Photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the compound having an ether bond and an amide bond in the molecule is a compound represented by the following general formula (1).

(In the formula (1), R ₁ , R ₂ and R ₃ are each an alkyl group having 1 to 10 carbon atoms.) The photosensitive resin composition according to claim 1 or 2 , wherein the (A) polyamide resin has a fluorine content of 8 wt% or less measured by elemental analysis. The photosensitive resin composition according to any one of claims 1 to 3 , wherein the organic solvent (D) is contained in an amount of 100 parts by mass or more and 1000 parts by mass or less based on 100 parts by mass of the (A) polyamide resin.

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