JP2012181273A - Photosensitive resin composition, cured film, protective film, insulator film, semiconductor device, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition leaving no scum after a portion to be exposed is exposed to light, causing little film thinning to achieve an excellent pattern shape, and having high sensitivity, a semiconductor device, and a display element.SOLUTION: A positive photosensitive resin composition contains a hydroxystyrene-styrene copolymer having a specific polyhydroxystyrene-styrene ratio and a specific weight-average molecular weight. A cured film, a protective film, and an insulator film are composed of a cured product made from the positive photosensitive resin composition. A semiconductor device and a display device comprise the cured film.

Description

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

Conventionally, polybenzoxazole resins, polyimide resins, and the like that are excellent in heat resistance and have excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protection films and interlayer insulating films of semiconductor elements. On the other hand, in order to simplify the process, a positive photosensitive resin composition in which a polyazoxazole resin, a polyimide resin, or the like is combined with a diazoquinone compound as a photosensitive agent is also used.
This photosensitive resin composition becomes hardly soluble in an alkaline aqueous solution in an unexposed portion due to the effect of inhibiting the dissolution of a diazoquinone compound in a resin such as polybenzoxazole resin or polyimide resin. On the other hand, in the exposed area, the diazoquinone compound undergoes a chemical change, and the photosensitive resin composition becomes soluble in an alkaline aqueous solution. By utilizing the difference in solubility between the exposed portion and the unexposed portion and dissolving and removing the exposed portion with an alkaline aqueous solution, it becomes possible to create a coating film pattern of only the unexposed portion.
The polybenzoxazole resin precursor in the positive photosensitive resin composition in which the coating film pattern is formed is finally dehydrated and closed by curing at a high temperature close to 300 ° C., and becomes a polybenzoxazole resin rich in heat resistance.

On the other hand, when these positive photosensitive resin compositions are actually used, the sensitivity of the photosensitive resin composition is particularly important. If the sensitivity is low, the exposure time becomes long, the throughput is lowered, and the productivity is significantly adversely affected. When the above-mentioned resins such as polybenzoxazole resin and polyimide resin are used, it is difficult to adjust the dissolution rate in the developing solution, so that the intended sensitivity cannot be reached, and development residue (scum on the exposed part after development) ) Occurred. Further, when the above resin is used, the dissolution inhibiting effect by the photosensitizer is not sufficiently exhibited, and the unexposed portion is also dissolved, so that there is a problem that the shape of the dense pattern portion is deteriorated.
For this reason, recently, various proposals have been made on high-sensitivity photosensitive resin compositions that can be developed with an alkali-soluble aqueous solution, as in the case of photoresists. (For example, see Patent Documents 1 to 7.)

JP 2001-255654 A JP 2002-241611 A JP-A-2005-352004 JP 2005-062764 A JP-A-2005-250160 JP 2006-285037 A JP 2008-225457 A

The present invention is a photosensitive resin composition that is free from generation of post-exposure residue in the exposed area, has a good pattern shape without film loss, and can be highly sensitive, and curing using the photosensitive resin composition An object is to provide a film, a protective film composed of the cured film, an insulating film, and a semiconductor device and a display device having the cured film.

Such an object is achieved by the present inventions [1] to [12] below.
[1] A photosensitive resin composition containing a hydroxystyrene / styrene copolymer and a polyamide resin, the styrene compounding amount [s] of the hydroxystyrene / styrene copolymer, the hydroxystyrene compounding amount [HS] ] The photosensitive resin composition whose product of ratio [S] / ([S] + [HS]) and weight average molecular weight (Mw) is 1000 or more and 3500 or less.
[2] The photosensitive resin composition according to [1], wherein the polyhydroxystyrene / styrene copolymer has a weight average molecular weight (Mw) of 1000 or more and 10,000 or less.
[3] The photosensitive resin composition according to [1] or [2], wherein the ratio [S] / ([S] + [HS]) is 0.2 or more and 0.7 or less.
[4] The photosensitive resin composition according to any one of [1] to [3], including a photosensitive agent.
[5] The photosensitive resin composition according to any one of [1] to [4], comprising 1 part by weight or more and 99 parts by weight or less of hydroxystyrene / styrene copolymer with respect to 100 parts by weight of the polyamide resin.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the polyamide resin has a weight average molecular weight (Mw) of 5000 or more and 20000 or less.
[7] The photosensitive resin composition according to any one of claims 1 to 6, wherein the polyamide resin is a resin having a structure represented by the general formula (1).

（式中、Ｘ、Ｙは有機基である。Ｒ^１は水酸基、カルボキシル基、−Ｏ−Ｒ^３、−ＣＯＯ−Ｒ^３のいずれかであり、Ｒ^１が複数ある場合は、同一でも異なっていてもよい。Ｒ^２は、水素原子、炭素数１〜１５の有機基である。ｌは０〜８の整数である。また、Ｒ^３は、炭素数１〜１５の有機基である。また、ａは重合度を示し、２〜５００である。）

(In the formula, X and Y are organic groups. R ¹ is a hydroxyl group, a carboxyl group, —O—R ³ , or —COO—R ³ , and when there are a plurality of R ¹ , they are the same or different. R ² is a hydrogen atom or an organic group having 1 to 15 carbon atoms, l is an integer of 0 to 8. R ³ is an organic group having 1 to 15 carbon atoms. A represents the degree of polymerization, and is 2 to 500.)

[8] A cured film composed of a cured product of the photosensitive resin composition according to any one of [1] to [7].
[9] A protective film composed of the cured film according to [8].
[10] An insulating film composed of the cured film according to [8].
[11] A semiconductor device having the cured film according to [8].
[12] A display device having the cured film according to [8].

  The photosensitive resin composition of the present invention has an excellent characteristic that there is no residue of the photosensitive resin composition in the exposed area, there is a good pattern shape with little film loss, and high sensitivity.

<Photosensitive resin composition>
First, the photosensitive resin composition of the present invention will be described.
The photosensitive resin composition of the present invention is a photosensitive resin composition containing a hydroxystyrene / styrene copolymer and a polyamide resin, wherein the amount of styrene in the hydroxystyrene / styrene copolymer [s], Hydroxystyrene / styrene copolymer having a product of the ratio [S] / ([S] + [HS]) and the weight average molecular weight (Mw) when the blending amount [HS] of hydroxystyrene is 1000 to 3500 It includes a coalescence and a polyamide resin.
By using the photosensitive resin composition having such a configuration, the coating film formed is compared with the coating film formed from a conventionally used photosensitive resin composition, after exposure of the exposed portion. There is no residue, a good pattern shape without film loss, and high sensitivity and high resolution. As a result, a cured film (protective film, insulating film) with a fine pattern can be formed, and further integration of semiconductor elements can be achieved.

Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated in detail.
[Hydroxystyrene / styrene copolymer]
In the present invention, the hydroxystyrene / styrene copolymer is a copolymer that may be composed of a hydroxystyrene derivative or a styrene derivative.
The above derivatives are those in which an alkyl group, an alkoxyl group, a hydroxyl group or the like is substituted at the ortho, meta, and para positions of the aromatic ring of hydroxystyrene and styrene.
The hydroxystyrene of the hydroxystyrene / styrene copolymer may be any of orthohydroxystyrene, metahydroxystyrene, and parahydroxystyrene. A plurality of the above hydroxystyrenes may be mixed.
The hydroxystyrene / styrene copolymer has a ratio [S] / ([S] + [HS]) based on the blending amount [s] of styrene and the blending amount [HS] of hydroxystyrene, and the hydroxystyrene / styrene. It is a copolymer having a product of 1000 or more and 3500 or less with the weight average molecular weight (Mw) of the copolymer.
The weight average molecular weight (Mw) of the hydroxystyrene / styrene copolymer is preferably 1000 or more and 10,000 or less, more preferably 2000 or more and 8000 or less, and particularly preferably 2500 or more and 7000 or less. By setting it as the said range, it has the effect excellent in compatibility with a polyamide resin and coexistence of high sensitivity.
Further, the ratio [S] / ([S] + [HS]) is preferably 0.2 or more and 0.7 or less, and more preferably 0.3 or more and 0.6 or less. By setting it as the said range, it has the effect excellent in coexistence of reduction of the post-exposure residue of an exposure part, and high sensitivity.

In the present invention, the polyamide resin refers to a resin having a benzoxazole precursor structure and / or an imide precursor structure. In addition, the polyamide resin is produced by a ring-closing reaction of a part of a benzoxazole structure, an imide precursor structure, a part of a benzoxazole precursor structure, a part of a benzoxazole structure or an imide precursor structure. It may have an imide structure or may have an amic acid ester structure.
The benzoxazole precursor structure refers to a structure represented by the following formula (2), the imide precursor structure refers to a structure represented by the following formula (3), and the benzoxazole structure refers to the following The structure represented by Formula (4) is pointed out, the imide structure refers to the structure represented by the following Formula (5), and the amido ester structure refers to the structure represented by the following Formula (6). In addition, D and R 'in following formula (2)-(6) show an organic group.

The weight average molecular weight (Mw) of the polyamide resin is preferably 5000 or more and 20000 or less, more preferably 6000 or more and 18000 or less. If the weight average molecular weight is less than the above lower limit, the film loss after development becomes large, and if the weight average molecular weight exceeds the above upper limit, there will be a problem in that the post-exposure residue in the exposed area increases.

The polyamide resin can be sealed at the end of the resin after the polymerization reaction in order to complete the synthesis reaction more stably. When the resin terminal is an amine residue, it can be sealed with a carboxylic acid anhydride or an active ester.
When sealed with an acid anhydride, the terminal structure may form an amide bond or an imide bond, but the terminal structure may be any bond.
As the acid anhydride, an aliphatic or cyclic compound having an alkenyl group or an alkynyl group is preferable. Examples of the active ester include compounds obtained by reacting an aliphatic or cyclic carboxylic acid compound having an alkenyl group or an alkynyl group with 1-hydroxy-1,2,3-benzotriazole. It is possible to improve storage stability by sealing the amine terminal.
When the resin terminal is a carboxylic acid, it can be sealed with an amine-containing compound. As the amine-containing compound, an aniline compound having a unsaturated group or a nitrogen-containing heterocyclic acid compound is preferable, and thereby adhesion can be improved.
Among these polyamide resins, a polyamide resin having a structure represented by the following general formula (1) is preferable.

（式中、Ｘ、Ｙは有機基である。Ｒ^１は水酸基、カルボキシル基、−Ｏ−Ｒ^３、−ＣＯＯ−Ｒ^３のいずれかであり、Ｒ^１が複数ある場合は、同一でも異なっていてもよい。Ｒ^２は、水素原子、炭素数１〜１５の有機基である。ｌは０〜８の整数である。また、Ｒ^３は、炭素数１〜１５の有機基である。また、ａは重合度を示し、２〜５００である。）

(In the formula, X and Y are organic groups. R ¹ is a hydroxyl group, a carboxyl group, —O—R ³ , or —COO—R ³ , and when there are a plurality of R ¹ , they are the same or different. R ² is a hydrogen atom or an organic group having 1 to 15 carbon atoms, l is an integer of 0 to 8. R ³ is an organic group having 1 to 15 carbon atoms. A represents the degree of polymerization, and is 2 to 500.)

Since the imide ring or the oxazole ring is formed by heating and curing the photosensitive resin composition using the polyamide resin having the structure represented by the general formula (1), the heat resistance of the cured film and the protection having the cured film The reliability of the film, the insulating film, and the semiconductor device can be improved.
The polyamide resin having the structure represented by the general formula (1) includes, for example, a compound selected from a bis (aminophenol) derivative containing X, a diaminophenol derivative and the like, a tetracarboxylic anhydride containing Y, and trimellitic acid. It is a polyamide resin obtained by reacting a compound selected from an anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative and the like.
In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

R ² is a hydrogen atom in the general formula (1), as long as it is an organic group having 1 to 15 carbon atoms, is not particularly limited, R ² is for adjusting the solubility in an alkali aqueous solution of the polyamide resin Examples thereof include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like.
In general formula (1) ^-O-R 3 is a substituent Y in, ^{R 3} of ^{-COO-R 3} is also a one who has the same function as that of the ^{R 2,} the same as ^{R 2} Is given as an example.

When the polyamide resin having the structure represented by the general formula (1) is heated, it is dehydrated and closed, and a heat-resistant resin is obtained in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both.
X of the polyamide resin having the structure represented by the general formula (1) is not particularly limited, and examples thereof include aromatic compounds such as a benzene ring and a naphthalene ring, bisphenols, pyrroles, and furans. A heterocyclic compound is mentioned, More specifically, what is shown by following (7) Formula can be mentioned preferably. These may be used alone or in combination of two or more.

（ここで＊はＮＨ基に結合することを示す。Ｅは、−ＣＨ_２−、ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、―Ｃ（ＣＦ_３）_２―または単結合である。Ｒ⁴は、アルキル基、アルキルエステル基、ハロゲン原子か
ら選ばれた１つを示し、Ｒ⁴が複数ある場合は、それぞれ同じでも異なっていても良い。
Ｒ⁵は、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであ
る。Ｒ⁵が複数ある場合は、同じでも異なっていても良い。Ｒ⁶は、水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを示す。ｙは０〜２の整数、ｚは０〜３の整数である。Ｒ^７〜Ｒ^１０は、有機基である。）

(Here, * indicates bonding to an NH group. E represents —CH ₂ —, CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —). , —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ⁴ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and there are a plurality of R ^4. The cases may be the same or different.
R ⁵ is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group. When there are a plurality of R ^{5 s} , they may be the same or different. R ⁶ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. y is an integer of 0 to 2, and z is an integer of 0 to 3. R ^{7 to} R ¹⁰ are organic groups. )

  Among X represented by the above formula (7), X represented by the following formula (8) is preferable from the viewpoint of excellent mechanical properties after dehydration and ring closure of the polyamide resin.

（ここで、＊はＮＨ基に、※は−ＯＲ^２基に結合することを示す。式中Ｆ、Ｇは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、 −ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。aは０〜３の整数であり、Ｒ¹¹はアルキル基、 アルコキシル基、アシルオキシ基、シクロアルキル基の内から選ば
れた１つを表す。 Ｒ^１1が複数ある場合は、それぞれ同じでも異なっていてもよい。）

(Here, * represents an NH group, and * represents an —OR ² group. In the formula, F and G are —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ ). _{-, - O -, - S} -, - SO 2 -, - CO-, -NHCO -, - C (CF 3) 2 -, or a single bond .a is an integer of 0 to 3, R ¹¹ Represents one selected from an alkyl group, an alkoxyl group, an acyloxy group, and a cycloalkyl group, and when there are a plurality of R ^{11 's} , they may be the same or different.

  Moreover, Y of the polyamide resin having the structure represented by the general formula (1) is an organic group and is not particularly limited. For example, aromatic compounds such as benzene ring and naphthalene ring, bisphenols, pyrroles And heterocyclic compounds such as pyridines and furans, siloxane compounds, and the like, and more specifically, those represented by the following formula (9) can be preferably exemplified. These may be used alone or in combination of two or more.

（ここで、＊はＣ＝Ｏ基に結合することを示し、式中J、Ｋは、−ＣＨ_２−、ＣＨ（ＣＨ
_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、 −ＮＨＣＯ−
、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ^１2 はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、Ｒ^１2が複数ある場合は、それぞれ同じでも
異なっていてもよい。また、Ｒ^１3は水素原子、アルキル基、アルキルエステル基、ハロ
ゲン原子から選ばれた１つを表す。ｂ＝０〜４の整数である。Ｒ^１4 〜Ｒ^１7は有機基で
ある。）

(Here, * indicates bonding to a C═O group, wherein J and K are —CH ₂ —, CH (CH
_{3) -, - C (CH} 3) 2 -, - O -, - S -, - SO 2 -, - CO-, -NHCO-
_{, -C (CF 3) 2 -} , or a single bond. R ¹² represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and when there are a plurality of R ^{12 s} , they may be the same or different. R ¹³ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. b is an integer of 0 to 4. R ^{14 to} R ¹⁷ are organic groups. )

The amount of the hydroxystyrene / styrene copolymer is preferably 1 part by weight or more and 99 parts by weight or less, more preferably 100 parts by weight of the total amount of the polyamide resin. 5 parts by weight or more and 80 parts by weight or less. By setting it as the above range, the cured film has excellent mechanical properties with high sensitivity.

[Photosensitive agent]
The photosensitive agent used in the present invention is a compound that generates an acid by light.
Examples of the compound that generates an acid by light include onium salts such as diphenyliodonium salt and triphenylsulfonium salt, 2-nitrobenzyl esters, N-iminosulfonates, arylsulfonate esters, and halogens such as chlorine. Examples include heterocyclic compounds and photosensitive diazoquinone compounds.
Among these compounds, a photosensitive diazoquinone compound is preferred because it has the highest sensitivity and resolution in the wavelength range of actinic radiation mainly used for exposure. Examples of the photosensitive diazoquinone compound include esters of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid.
Specific examples include ester compounds represented by the formulas (10) to (14). These may be used alone or in combination of two or more.

In the formulas (10) to (14), Q is selected from a hydrogen atom or any one of the following formulas (15) and (16). Here, at least one of Q of each compound is the formula (15) or the formula (16).

  Among these, the photosensitive agents of formulas (12), (13), and (14) that can further improve the sensitivity and resolution of the photosensitive resin composition are particularly preferable.

  The content of the photosensitizer is not particularly limited, but is preferably 1 part by weight or more and 50 parts by weight or less, and more preferably 10 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the polyamide resin. Thereby, the photosensitive resin composition provided with favorable sensitivity and resolution without scum can be obtained.

[solvent]
The photosensitive resin composition of the present invention contains a solvent.
Examples of such solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether. , Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3- A methoxy propionate etc. are mentioned, Among these, it can use 1 type or in combination of 2 or more types.

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

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

(Dissolution promoter)
In addition, a dissolution accelerator may be included in the photosensitive resin composition of the present invention.
The dissolution accelerator is a component capable of improving the solubility of the exposed portion of the coating film formed using the photosensitive resin composition in the developer and improving scum during patterning.
Examples of such a dissolution accelerator include compounds having a phenolic hydroxyl group, and specific examples include those represented by the following formulas (17) to (23).

  Among these compounds having a phenolic hydroxyl group, those selected from the formula (24) are preferable. Two or more of these may be used. Thereby, especially sensitivity can be improved.

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

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

<Method for forming cured film>
Next, a method for forming a cured film (protective film, insulating film) using the photosensitive resin composition of the present invention will be described.
(1) First, the photosensitive resin composition of the present invention is applied to an appropriate support (substrate), for example, a silicon wafer, a ceramic substrate, an aluminum substrate or the like. When applied on a silicon wafer (semiconductor element), the coating amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is below the lower limit value, it will be difficult to fully function as a protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. Takes a long time to reduce throughput. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like.
(2) Next, after prebaking at 60 to 130 ° C. and drying the coating film, actinic radiation is irradiated to a desired pattern shape (exposure process). As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

(3) Next, a pattern is obtained by dissolving and removing the irradiated portion with a developer (development step).
Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.
(4) Next, the relief pattern formed by development is rinsed (cleaned) (cleaning step). Distilled water is used as the rinse liquid.
(5) Next, by performing a heat treatment, the benzoxazole precursor structure and the imide precursor structure are subjected to a ring-closing reaction to form a benzoxazole ring and an imide ring, and a final pattern (cured film, protective film, (Insulating film) is obtained (heat treatment step).
The heat treatment temperature is preferably 180 ° C to 380 ° C, more preferably 200 ° C to 350 ° C.

  The cured film formed using the photosensitive resin composition of the present invention is used not only for semiconductor devices such as semiconductor elements, but also for display device devices such as TFT-type liquid crystals and organic EL, interlayer insulating films for flexible circuits and flexible films. It is also useful as a copper clad cover coat, solder resist film or liquid crystal alignment film.

Examples of semiconductor device applications include a passivation film formed by forming a cured film of the above-described positive photosensitive resin composition on a semiconductor element, and a cured film of the above-described photosensitive resin composition formed on the passivation film. A protective film such as a buffer coat film, an insulating film such as an interlayer insulating film formed by forming a cured film of the above-mentioned positive photosensitive resin composition on a circuit formed on a semiconductor element, and an α ray Examples thereof include a blocking film, a planarizing film, a protrusion (resin post), and a partition wall.
Examples of display device applications include a protective film formed by forming a cured film of the photosensitive resin composition of the present invention on a display element, an insulating film or a flattening film for TFT elements, color filters, etc., MVA type Examples thereof include protrusions for liquid crystal display devices, partition walls for organic EL element cathodes, and the like.
The use method is based on forming the photosensitive resin composition layer patterned on the substrate on which the display element and the color filter are formed according to the semiconductor device application by the above method. High transparency is required for display device applications, especially for insulating films and flattening films, but by introducing a post-exposure step before curing the coating film of the photosensitive resin composition of the present invention, it is transparent. A resin layer having excellent properties can be obtained, which is more preferable in practical use.

The photosensitive resin composition, cured film, protective film, insulating film, semiconductor device, and display device of the present invention have been described above, but the present invention is not limited to these.
The semiconductor device and display device to which the photosensitive resin composition of the present invention is applied are not limited to those having the above-described configuration.
The photosensitive resin composition of the present invention can be used not only for forming a protective film or insulating film of a semiconductor element as described above, but also for forming a spacer of a semiconductor element, for example.

[1] Production of photosensitive resin composition A photosensitive resin composition was produced as follows.
Example 1
[Synthesis of Polyamide Resin (A-1)]
Diphenyl ether-4,4′-dicarboxylic acid: 0.082 mol and 1-hydroxy-1,2,3-benzotriazole: 0.164 mol were reacted with a dicarboxylic acid derivative (active ester) obtained by reacting with hexa Fluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane: 36.63 g (0.1 mol) of 4 necks equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet pipe In a separable flask, 275 g of N-methyl-2-pyrrolidone was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath.
Next, N-methyl-2-pyrrolidone: 5-norbornene-2,3-dicarboxylic acid anhydride: 14.77 g (0.09 mol) dissolved in 30 g was added, and the mixture was further stirred for 3 hours to complete the reaction. .
After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the formula (2) A polyamide resin (A-1) having a structure was obtained. The weight average molecular weight was 11,200.

[Synthesis of photosensitizer]
A thermometer comprising 11.22 g (0.026 mol) of phenol represented by the formula (B-1), 18.78 g (0.070 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 170 g of acetone. The mixture was stirred and dissolved in a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C., a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting for 3 hours at room temperature, 1.05 g (0.017 mol) of acetic acid was added, and the mixture was further reacted for 30 minutes. After filtration of the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and of formula (Q-1). A photosensitizer represented by the structure was obtained.

[Preparation of photosensitive resin composition]
Hydroxystyrene / styrene copolymer (Maruka Linker, Maruzen Petrochemical Co., Ltd., styrene [S]: hydroxystyrene [PS] = 40: 60, Mw = 5000, [S] / ([S] + [HS]) × Mw = 2000): 25 g, synthesized polyamide resin (A-1): 75 g, photosensitive diazoquinone compound having the structure of the above formula (Q-1) (photosensitive agent): 15 g, KBM-503P (γ-methacrylic) as an adhesion assistant. Roxypropyltrimethoxysilane): 2 g, γ-butyrolactone (boiling point: 203 ° C.): 150 g, dissolved in a mixed solvent, and then filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a photosensitive resin composition. Obtained.

(Example 2)
[Synthesis of Polyamide Resin (A-2)]
A dicarboxylic acid derivative (active ester) obtained by reacting 0.088 mol of diphenyl ether-4,4′-dicarboxylic acid with 0.176 mol of 1-hydroxy-1,2,3-benzotriazole, hexa Fluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane: 36.63 g (0.1 mol) of 4 necks equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet pipe In a separable flask, 275 g of N-methyl-2-pyrrolidone was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath.
Next, N-methyl-2-pyrrolidone: 5-norbornene-2,3-dicarboxylic acid anhydride: 7.9 g (0.048 mol) dissolved in 20 g was added, and the reaction was terminated by further stirring for 3 hours. .
After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the formula (2) A polyamide resin (A-2) having a structure was obtained. The weight average molecular weight was 14800.

[Preparation of photosensitive resin composition]
The same procedure as in Example 1 was performed except that the polyamide resin in Example 1 was changed from (A-1) to (A-2).

(Example 3)
[Synthesis of Polyamide Resin (A-3)]
Diphenyl ether-4,4′-dicarboxylic acid: 0.076 mol and 1-hydroxy-1,2,3-benzotriazole: 0.152 mol obtained by reacting dicarboxylic acid derivative (active ester) with hexa Fluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane: 36.63 g (0.1 mol) of 4 necks equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet pipe In a separable flask, 275 g of N-methyl-2-pyrrolidone was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath.
Next, N-methyl-2-pyrrolidone: 5-norbornene-2,3-dicarboxylic acid anhydride: 15.76 g (0.096 mol) dissolved in 35 g was added, and the reaction was terminated by stirring for another 3 hours. .
After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the formula (2) A polyamide resin (A-3) having a structure was obtained. The weight average molecular weight was 6800.

[Preparation of photosensitive resin composition]
The same procedure as in Example 1 was performed except that the polyamide resin in Example 1 was changed from (A-1) to (A-3).

Example 4
Hydroxystyrene / styrene copolymer of Example 1 (Maruka Linker, Maruzen Petrochemical Co., Ltd., styrene [S]: hydroxystyrene [HS] = 40: 60, Mw = 5000, [S] / ([S] + [HS] ) × Mw = 2000): hydroxystyrene / styrene copolymer (styrene: hydroxystyrene = 30: 70, Mw = 6000, [S] / ([S] + [HS]) × Mw = 1800) instead of 25 g : A photosensitive resin composition was prepared in the same manner as in Example 1 except that 25 g was used.
(Example 5)
Hydroxystyrene / styrene copolymer of Example 2 (Maruka Linker, Maruzen Petrochemical Co., Ltd., styrene [S]: hydroxystyrene [HS] = 40: 60, Mw = 5000, [S] / ([S] + [HS] ) × Mw = 2000): hydroxystyrene / styrene copolymer instead of 25 g (styrene: hydroxystyrene = 50: 50, Mw = 3000, [S] / ([S] + [HS]) × Mw = 1500) : A photosensitive resin composition was prepared in the same manner as in Example 2 except that 25 g was used.

(Example 6)
Hydroxystyrene / styrene copolymer of Example 1 (Maruka Linker, Maruzen Petrochemical Co., Ltd., styrene [S]: hydroxystyrene [HS] = 40: 60, Mw = 5000, [S] / ([S] + [HS] ) × Mw = 2000): Hydroxystyrene / styrene copolymer instead of 25 g (styrene: hydroxystyrene = 60: 40, Mw = 5200, [S] / ([S] + [HS]) × Mw = 3120) : A photosensitive resin composition was prepared in the same manner as in Example 2 except that 25 g was used.
(Example 7)
Hydroxystyrene / styrene copolymer of Example 1 (Maruka Linker, Maruzen Petrochemical Co., Ltd., styrene [S]: hydroxystyrene [HS] = 40: 60, Mw = 5000, [S] / ([S] + [HS] ) × Mw = 2000): Hydroxystyrene / styrene copolymer (styrene [S]: hydroxystyrene [HS] = 45: 55, Mw = 3000, [S] / ([S] + [HS]) instead of 25 g ) × Mw = 1350): A photosensitive resin composition was prepared in the same manner as in Example 2 except that 25 g was used.
(Example 8)
[Synthesis of photosensitizer]
A thermometer comprising 18.8 g (0.03 mol) of phenol represented by the formula (B-2), 23.6 g (0.088 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 170 g of acetone. The mixture was stirred and dissolved in a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, a mixed solution of 9.8 g (0.097 mol) of triethylamine and 6.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 1.1 g (0.018 mol) of acetic acid was added, and the mixture was further reacted for 30 minutes. After filtration of the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and dried according to formula (Q-2). A photosensitizer represented by the structure was obtained.
(B-1) A photosensitive resin composition was prepared in the same manner as in Example 1 except that 18.8 g of the following (B-2) was used instead of 11.22 g to synthesize the photosensitive agent (Q-2). did.

Example 9
Hydroxystyrene / styrene copolymer of Example 1 (Maruka Linker, Maruzen Petrochemical Co., Ltd., styrene [S]: hydroxystyrene [HS] = 40: 60, Mw = 5000, [S] / ([S] + [HS] ) × Mw = 2000): 25 g, Synthesized polyamide resin (A-1): Same as Example 1 except that 75 g was used in an amount of 40 g of hydroxystyrene / styrene copolymer and 60 g of polyamide resin (A-1). A photosensitive resin composition was prepared.

(Example 10)
[Synthesis of Polyamide Resin (A-4)]
Dicarboxylic acid derivative obtained by reacting 0.01 mol of isophthalic acid with 0.078 mol of diphenyl ether-4,4′-dicarboxylic acid and 1-hydroxy-1,2,3-benzotriazole: 0.176 mol (Active ester) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane: 36.63 g (0.1 mol) thermometer, stirrer, raw material inlet, dry nitrogen gas inlet tube Was added to a four-necked separable flask, and 275 g of N-methyl-2-pyrrolidone was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath.
Next, N-methyl-2-pyrrolidone: 5-norbornene-2,3-dicarboxylic acid anhydride: 7.9 g (0.048 mol) dissolved in 20 g was added, and the reaction was terminated by further stirring for 3 hours. .
After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the formula (2) A polyamide resin (A-4) having a structure was obtained. The weight average molecular weight was 13800.

[Preparation of photosensitive resin composition]
The same procedure as in Example 1 was performed except that the polyamide resin in Example 1 was changed from (A-1) to (A-4).
(Example 11)
[Synthesis of Polymiad Resin (A-5)]
4,2-separator equipped with 30.0 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet pipe The solution was placed in a bull flask and dissolved by adding 400 ml of acetone. 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 to a temperature of less than 20 ° C. to obtain a mixture. After the dropwise addition, the temperature of the mixture was heated to 40 ° C. and stirred for 2 hours, and then 30.0 g (0.218 mol) of potassium carbonate was gradually added and further stirred for 2 hours. Heating was stopped and the mixture was further stirred at room temperature for 18 hours. Thereafter, an aqueous sodium hydroxide solution was gradually added while the mixture was vigorously stirred. After the addition, the mixture was heated to 55 ° C. and further stirred for 30 minutes. After completion of the stirring, the mixture was cooled to room temperature, 37% by weight aqueous hydrochloric acid solution and 500 ml of water were added, and the pH was adjusted to be in the range of 6.0 to 7.0. The obtained precipitate was filtered off, washed with water and dried at 60 to 70 ° C., and bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl). ) A propane solid was obtained. To 51.0 g of the obtained solid, 316 g of acetone and 158 g of methanol were added and heated to 50 ° C. for complete dissolution. 300 mL of 50 ° C. pure water was added thereto over 30 minutes and heated to 65 ° C. Thereafter, the crystals which have been slowly cooled to room temperature are filtered, and the crystals are purified by drying at 70 ° C., and bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis ( 4-Hydroxyphenyl) propane was obtained.
20 g of the obtained bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane was placed in a 1 L flask and 1.0 g of 5% palladium-carbon and ethyl acetate 180 were added. .4 g was added to make a suspension. Hydrogen gas was purged there, and the mixture was shaken for 35 minutes while being heated to 50 to 55 ° C. to carry out a reduction reaction. After completion of the reaction, it was cooled to 35 ° C. and the suspension was purged with nitrogen. After removing the catalyst by filtration, the filtrate was subjected to an evaporator to evaporate the solvent. The obtained product was dried at 90 ° C. to obtain bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.
14.27 g (0.024 mol) of bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane was introduced into a thermometer, a stirrer, a raw material inlet, and dry nitrogen gas. In a four-necked separable flask equipped with a tube, 40 g of γ-butyrolactone was added and dissolved, and the mixture was cooled to 15 ° C. with stirring. Thereto were added 6.86 parts by weight (0.022 mol) of 4,4′-oxydiphthalic anhydride and 12.0 parts by weight of γ-butyrolactone, and the mixture was stirred at 20 ° C. for 1.5 hours. Thereafter, the mixture was heated to 50 ° C. and stirred for 3 hours. Then, N, N-dimethylformamide dimethylacetal 5.27 g (0.044 mol) and 10.0 g of γ-butyrolactone were added, and the mixture was further stirred at 50 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a polyamide resin (A-5) having a structure of the formula (2 ′). The weight average molecular weight was 13200.

[Preparation of photosensitive resin composition]
The same procedure as in Example 1 was performed except that the polyamide resin in Example 1 was changed from (A-1) to (A-5).

(Comparative Example 1)
Hydroxystyrene / styrene copolymer of Example 1 (Maruka Linker, Maruzen Petrochemical Co., Ltd., styrene [S]: hydroxystyrene [HS] = 40: 60, Mw = 5000, styrene blending ratio × Mw = 2500): instead of 25 g Hydroxystyrene / styrene copolymer (styrene [S]: hydroxystyrene [HS] = 30: 70, Mw = 3200, [S] / ([S] + [HS]) × Mw = 960): 25 g A photosensitive resin composition was prepared in the same manner as in Example 2 except that.
(Comparative Example 2)
Hydroxystyrene / styrene copolymer of Example 1 (Maruka Linker, Maruzen Petrochemical Co., Ltd., styrene [S]: hydroxystyrene [HS] = 40: 60, Mw = 5000, [S] / ([S] + [HS] ) × Mw = 2000): hydroxystyrene / styrene copolymer instead of 25 g (styrene: hydroxystyrene = 50: 50, Mw = 8200, [S] / ([S] + [HS]) × Mw = 4100) : A photosensitive resin composition was prepared in the same manner as in Example 2 except that 25 g was used.
(Comparative Example 3)
Hydroxystyrene / styrene copolymer of Example 1 (Maruka Linker, Maruzen Petrochemical Co., Ltd., styrene [S]: hydroxystyrene [HS] = 40: 60, Mw = 5000, [S] / ([S] + [HS] ) × Mw == 2000): 25 g, synthetic resin (A-1): A photosensitive resin composition was prepared in the same manner as in Example 2 except that 100 g of polyamide resin (A-1) was used instead of 75 g. did

[2] Evaluation [Evaluation of photosensitive properties]
The photosensitive resin composition of each example and each comparative example was applied on an 8-inch silicon wafer using a spin coater, and then pre-baked at 120 ° C. for 4 minutes on a hot plate to obtain a film thickness of about 8.0 μm. A coating film was obtained.
Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern having a width of 0.88 to 50 μm are drawn), and an i-line stepper (manufactured by Nikon Corporation, 4425i). ) was used to exposure is conducted by changing the exposure dose by 10 mJ / cm ² increments from 100 mJ / cm ² to 780mJ / cm ^2.
Next, using a 2.38% TMAH aqueous solution, paddle development was performed by adjusting the development time so that the difference in film thickness between the pre-baked and the unexposed areas after development was 0.5 μm. Then, it rinsed with the pure water for 10 seconds.
Thereafter, each coating film having a different exposure amount was observed, and the exposure amount of the coating film on which a pattern was confirmed was defined as sensitivity.

[Post-exposure residue evaluation]
The silicon wafer used in the photosensitive property evaluation was observed with a microscope, and the occurrence of a residue at the boundary portion between the exposed portion and the unexposed portion was compared and evaluated.
[Pattern shape evaluation]
From the cross section of the silicon wafer used in the photosensitivity evaluation, the remaining film (C) having a circuit width / circuit interval of 5 μm and the remaining film (D) having a circuit width / circuit interval of 50 μm were measured and evaluated according to the following criteria. .
A: (C / D)> 0.95
○: 0.95 ≧ (C / D)> 0.9
Δ: 0.9 ≧ (C / D)> 0.85
×: 0.85 ≧ (C / D)
[Preparation of cured film]
The photosensitive resin composition of each example and each comparative example was applied on an 8-inch silicon wafer using a spin coater, and then pre-baked at 120 ° C. for 4 minutes on a hot plate to apply a film having a thickness of about 12.5 μm. A membrane was obtained. Next, curing was performed in a clean oven at 150 ° C./30 minutes, 320 ° C./60 minutes, and an oxygen concentration atmosphere of 10 ppm or less. Next, the obtained cured film was immersed in 2% hydrogen fluoride water, and the cured film was peeled off from the silicon wafer. The obtained cured film was sufficiently washed with pure water and then dried at 50 ° C. for 24 hours, and the desired cured film could be obtained without any problem. However, the cured film of the comparative example has problems in sensitivity, post-exposure residue, and shape.

Claims (12)

A photosensitive resin composition comprising a hydroxystyrene / styrene copolymer and a polyamide resin, wherein the blending amount of styrene [s] and the blending amount of hydroxystyrene [HS] of the hydroxystyrene / styrene copolymer are defined as The photosensitive resin composition whose product of the ratio [S] / ([S] + [HS]) of time and the weight average molecular weight (Mw) of the said hydroxystyrene / styrene copolymer is 1000-3500.   The photosensitive resin composition according to claim 1, wherein the polyhydroxystyrene / styrene copolymer has a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less. The photosensitive resin composition according to claim 1, wherein the ratio [S] / ([S] + [HS]) is 0.2 or more and 0.7 or less.   The photosensitive resin composition of any one of Claims 1 thru | or 3 containing a photosensitive agent.   The photosensitive resin composition of any one of Claims 1 thru | or 4 which contains 1 to 99 weight part of hydroxy styrene / styrene copolymers with respect to 100 weight part of polyamide resins. The photosensitive resin composition according to claim 1, wherein the polyamide resin has a weight average molecular weight (Mw) of 5,000 or more and 20,000 or less. The photosensitive resin composition according to claim 1, wherein the polyamide resin is a resin having a structure represented by the general formula (1).

(In the formula, X and Y are organic groups. R ¹ is a hydroxyl group, a carboxyl group, —O—R ³ , or —COO—R ³ , and when there are a plurality of R ¹ , they are the same or different. R ² is a hydrogen atom or an organic group having 1 to 15 carbon atoms, l is an integer of 0 to 8. R ³ is an organic group having 1 to 15 carbon atoms. A represents the degree of polymerization, and is 2 to 500.) The cured film comprised with the hardened | cured material of the photosensitive resin composition of any one of Claims 1 thru | or 7. A protective film comprising the cured film according to claim 8. The insulating film comprised with the cured film of Claim 8. A semiconductor device comprising the cured film according to claim 8. The display body apparatus which has the cured film of Claim 8.