JP2013205801A - Photosensitive resin composition, cured film of the same, protective film, insulting film, semiconductor device, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured film having excellent adhesiveness and little abnormality during coating and giving a little load on the environment, and a photosensitive resin composition from which the cured film can be formed.SOLUTION: The photosensitive resin composition comprises: an alkali-soluble resin; a photoacid generator; a fluorine-containing copolymer obtained by copolymerizing at least a compound expressed by a formula (C1):CH=C(R)-COO-(CH)-N(R)-SO-CFand a compound expressed by a formula (C2):CH=C(R)-COO-(CRR-CRR-O-)-(CRR-CRR-O-)-R; a silicon compound; and a solvent. In the formula (C1), Rrepresents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; Rrepresents a hydrocarbon group having 1 to 6 carbon atoms; P represents an integer of 1 to 10; and Q represents an integer of 1 to 7. In the formula (C2), Rto Reach represent a hydrocarbon group having 1 to 6 carbon atoms; Rrepresents a hydrocarbon group having 1 to 6 carbon atoms; J represents an integer of 0 to 30; and K represents an integer of 0 to 30.

Description

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

  Conventionally, a polyimide resin having excellent adhesion and excellent electrical and mechanical properties for a protective film and an insulating film of a semiconductor element, or a polybenzoxazole resin that has good moisture resistance reliability in addition to the above characteristics Etc. were used. In addition, by imparting photosensitivity to the polyimide resin, polybenzoxazole resin, and their resin precursors themselves, it is possible to simplify part of the relief pattern preparation process, while having high sensitivity and fine processability. In particular, photosensitive resin compositions have been developed that have excellent mechanical properties, heat resistance and electrical properties, and are effective in shortening processes and improving productivity (yield). These are protective films for semiconductor devices. It has the potential as an insulating resin composition not only for use but also for other purposes.

  Under such circumstances, a positive photosensitive resin composition that can be developed with an alkaline aqueous solution has recently been developed. For example, Patent Document 1 discloses a positive photosensitive resin composition composed of a polybenzoxazole precursor as an alkali-soluble resin and a diazoquinone compound as a photosensitive agent.

On the other hand, in recent years, in order to improve the productivity of semiconductor devices, the size of wafers used for production has been increased, and 12-inch wafers have been used. It has occurred.
For example, it is generally known that when a wafer is rotated, turbulence is generated around the wafer. However, since a 12-inch wafer is large, the turbulence itself tends to increase. Since the turbulent air may break a 12-inch wafer, it has become difficult to rotate at a high speed, and there is a need for production by low-speed rotation. In the case of small wafers that can be rotated at high speed, even if small bubbles were contained in the varnish of the photosensitive resin composition that was dripped, it was possible to defoam by rotating at high speed. Defoaming cannot be performed, and the influence of bubbles tends to remain on the wafer after coating. As a result, coating unevenness occurs and the frequency of rework is increasing.

In the case of a 12-inch wafer, the amount of varnish dripped is large. Therefore, even if the varnish contains small bubbles, when dripping onto a small wafer, the amount of varnish is small and the number of wafers on which coating unevenness occurs is small, but in the case of a 12-inch wafer, it is dripped. Since the amount of varnish is large, the probability that bubbles will enter increases. As a result, for example, in Patent Document 2, in the case of a large substrate, a wafer having uneven coating tends to occur, and the number of 12-inch wafers to be reworked tends to increase.
In other words, since 12 inch wafers are susceptible to bubbles in the varnish, it is becoming increasingly important to provide a varnish with fewer bubbles.

  Further, unlike a small wafer such as a 6-inch wafer, a 12-inch wafer is known to be warped by its own weight, and the amount of warpage is larger than that of a small wafer. In addition, the stress applied when a 12-inch wafer is rotated in the semiconductor manufacturing process also increases. For example, Patent Document 3 mentions the influence of stress on a large wafer of 8 inches or more due to a coating film. However, in recent years, the wafer has been further thinned, and in 12-inch wafers, there is a concern that the sealing resin may be peeled off from the protective film on the wafer due to stress concentration. Sex has become important.

  Furthermore, as represented by lead-free solder and perfluorooctane sulfonic acid (PFOS) regulations, even if chemical substances are dissolved into the environment after the semiconductor device is disposed of, the burden on the environment There is an increasing demand for semiconductor devices with a small amount of semiconductor devices.

  As described above, a photosensitive resin composition having few bubbles, good adhesion, and low environmental load has been strongly desired along with the spread of 12-inch wafers. In addition, unlike a photoresist that is removed after forming a desired pattern, a small environmental load has become increasingly important in recent years when used as a permanent film remaining in an apparatus.

JP-A-2-246246 JP 2008-191636 A (paragraph number 0003) JP 2008-197181 A

  The present invention has been made in view of the above circumstances, and the object of the present invention is to provide a cured film having excellent adhesion and less abnormalities during application, and having a small environmental load, and a photosensitive film capable of forming a cured film. The resin composition is provided.

Such an object is achieved by the present invention described in [1] to [15].
[1] An alkali-soluble resin (A), a photoacid generator (B), and a compound obtained by copolymerizing at least a compound represented by the following formula (C1) and a compound represented by the following formula (C2). A photosensitive resin composition containing a fluorine copolymer (C), a silicon compound (D), and a solvent (E).
^{_{CH 2 = C (R 31)}} -COO- (CH 2) P -N (R 32) -SO 2 -C Q F 2Q + 1 (C1)
(R ³¹ in Formula (C1) is a group selected from hydrogen or a hydrocarbon group having 1 to 6 carbon atoms that may be branched, and R ³² is a group having 1 to 6 carbon atoms that may be branched. And a group selected from hydrocarbon groups, P is an integer of 1 to 10, and Q is an integer of 1 to 7.)
^{_{CH 2 = C (R 33)}} -COO- (CR 34 R 35 -CR 36 R 37 -O-) J - (CR 38 R 39 -CR 40 R 41 -O-) K -R 42 (C2)
(R ^{33 to} R ⁴¹ in Formula (C2) are groups selected from hydrogen or an optionally branched hydrocarbon group having 1 to 6 carbon atoms, and R ⁴² is an optionally branched carbon number. And a group selected from hydrocarbon groups of 1 to 6. J is an integer of 0 or more and 30 or less, K is an integer of 0 or more and 30 or less, and J and K are not 0 at the same time.)
[2] The photosensitive resin composition according to [1], wherein the photosensitive resin composition includes the fluorine-containing copolymer (C) in an amount of 500 ppm to 2500 ppm.
[3] The fluorine-containing copolymer (C) comprises a compound represented by the formula (C1) and a compound represented by the formula (C2) in a molar ratio (C1: C2) of 10:90 or more and 90:10 or less. ), The photosensitive resin composition according to the above [1] or [2].
[4] The photosensitive resin according to any one of [1] to [4], wherein the fluorine-containing copolymer (C) has a weight average molecular weight of 2,000 to 60,000. Composition.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein in the compound represented by the formula (C1), Q in the formula (C1) is an integer of 1 or more and 6 or less. object.
[6] The photosensitive resin according to any one of [1] to [6], in which the compound represented by the formula (C1) is an integer of 1 to 4 in the formula (C1). Composition.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the photoacid generator (B) is a naphthoquinonediazide compound.
[8] The photosensitive resin composition according to any one of [1] to [7], further including a crosslinking agent (F).
[9] The alkali-soluble resin (A) includes a polyamide resin, a polybenzoxazole precursor resin, a polyimide precursor resin, a polybenzoxazole resin, a polyimide resin, a phenol resin, and a copolymer of styrene, hydroxystyrene, and derivatives thereof. The photosensitive resin composition according to any one of the above [1] to [8], which contains one or more kinds of resins selected from the group consisting of:
[10] The photosensitive resin composition according to [9], wherein the alkali-soluble resin (A) includes a resin having a different structure in the same type of resin.
[11] A cured film obtained by discharging and curing the photosensitive resin composition according to any one of [1] to [10] onto a 12-inch wafer.
[12] A protective film composed of the cured film according to [11].
[13] An insulating film composed of the cured film according to [11].
[14] A semiconductor device having the cured film according to [11].
[15] A display device having the cured film according to [11].

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form the cured film which has the outstanding adhesiveness, there are few abnormalities at the time of application | coating, and the load to an environment is small, and a cured film can be provided.

FIG. 1 is a cross-sectional view illustrating an example of a semiconductor device.

The present invention is obtained by copolymerizing an alkali-soluble resin (A), a photoacid generator (B), at least a compound represented by the following formula (C1) and a compound represented by the following formula (C2). A photosensitive resin composition containing a fluorine-containing copolymer (C), a silicon compound (D), and a solvent (E).
The photosensitive resin composition of the present invention is characterized by having the above-described configuration, which has few bubbles, good adhesion, and a low environmental load.

  The components used for the photosensitive resin composition of the present invention will be described in detail below. In addition, the following is an illustration and this invention is not limited to the following at all.

[Alkali-soluble resin (A)]
As the alkali-soluble resin used in the photosensitive resin composition of the present invention, any resin that is soluble in an alkaline aqueous solution can be used, and a resin having a phenolic hydroxyl group or a carboxyl group is preferably used. Specific examples include polyamide resins, polybenzoxazole resin precursors, polyimide resin precursors, polybenzoxazole resins, polyimide resins, phenol resins, and copolymers of styrene and hydroxystyrene and derivatives thereof.

  In the present invention, the polyamide resin is a resin having a benzoxazole precursor structure and / or an imide precursor structure, and a part of the benzoxazole precursor structure, the imide precursor structure, and the benzoxazole precursor structure undergoes a ring-closing reaction. The benzoxazole structure and imide precursor structure generated by the reaction may have an imide structure generated by a ring-closing reaction, or may have an amic acid ester structure. The polyimide resin precursor may be a copolymer structure of a polyimide acid structure and a polyamic acid ester structure.

  A specific benzoxazole precursor structure refers to a structure represented by the following formula (1), an imide precursor structure refers to a structure represented by the following formula (2), and a benzoxazole structure refers to the following The structure represented by Formula (3) is pointed out, the imide structure refers to the structure represented by Formula (4) below, and the amido ester structure refers to the structure represented by Formula (5) below.

なお、上記式（１）〜（５）中のＤおよびＲ^１は有機基を示す。

In the above formulas (1) to (5), D and R ¹ represent an organic group.

  Among these polyamide resins, from the viewpoint of the heat resistance of the cured product of the photosensitive resin composition of the present invention, a polyamide resin having a repeating unit represented by the following general formula (6) is preferable.

（式中、Ｘ、Ｙは、有機基である。Ｒ^２は、水酸基、−Ｏ−Ｒ^４、アルキル基、アシルオキシ基又はシクロアルキル基であり、複数有する場合、同一であっても異なっても良い。Ｒ^３は、水酸基、カルボキシル基、−Ｏ−Ｒ^４又は−ＣＯＯ−Ｒ^４であり、複数有する場合、同一であっても異なっても良い。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（６）において、Ｒ^２が、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が、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。ｍは０〜８の整数、ｎは０〜８の整数である。）

(In the formula, X and Y are organic groups. R ² is a hydroxyl group, —O—R ⁴ , an alkyl group, an acyloxy group, or a cycloalkyl group. R ³ is a hydroxyl group, a carboxyl group, —O—R ⁴ or —COO—R ⁴ , and when there are a plurality thereof, they may be the same or different, and R ⁴ in R ² and R ³ is carbon in recent 1-15 organic group. in the formula (6), ^{R 2} is, if there is no hydroxyl group, at least one of ^{R 3} is carboxyl group. Further, the ^{R 3,} a carboxyl group Otherwise, at least one of R ² is a hydroxyl group, m is an integer from 0 to 8, and n is an integer from 0 to 8.)

In the polyamide resin represented by the general formula (6), R ² and R ³ are groups in which a hydroxyl group and a carboxyl group are protected with a protecting group R ⁴ in order to adjust the solubility of the polyamide resin in an alkaline aqueous solution. , can be used ^{-O-R 4} and ^{-COO-R 4} as ^-O-R 4, R ³ as ^{R 2.} Examples of the organic group having 1 to 15 carbon atoms of R ⁴ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, and tetrahydrofuran. Nyl group, tetrahydropyranyl group, etc. are mentioned.

  X in the polyamide resin represented by the general formula (6) is not particularly limited. For example, an aromatic group having a structure such as a benzene ring, a naphthalene ring and a bisphenol structure, a pyrrole ring and a furan ring And a heterocyclic organic group having a structure of siloxane, a siloxane group, and the like. More specifically, what is represented by following formula (7) can be mentioned preferably. These may be used alone or in combination of two or more.

（ここで、＊は、一般式（６）におけるＮＨ基に結合することを示す。Ａは、アルキレン基、置換アルキレン基、−Ｏ−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良い。Ｒ^６は、水素原子、アルキル基、アルキルエステル基及びハロゲン原子から選ばれた１つを示す。ａは０〜４の整数である。Ｒ^７〜Ｒ^１０はそれぞれ有機基である。
なお、式（７）において、上記式一般式（６）におけるＸの置換基Ｒ^２は省略している。）

(Here, * indicates bonding to the NH group in the general formula (6). A represents an alkylene group, a substituted alkylene group, —O—C ₆ H ₄ —O—, —O—, —S—) , —SO ₂ —, —C (═O) —, —NHC (═O) —, or a single bond, R ⁵ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, R ⁶ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom, a is an integer of 0 to 4. R ^{7 to} R Each ¹⁰ is an organic group.
In the formula (7), the substituent R ² of X in the formula (6) is omitted. )

Specific examples of the alkylene group and substituted alkylene group of A in the above formula (7) include —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ). _{2 -, - CH (CH 2} CH 3) -, - C (CH 3) (CH 2 CH 3) -, - C (CH 2 CH 3) (CH 2 CH 3) -, - CH (CH 2 CH 2 _{CH 3) -, - C (} CH 3) (CH 2 CH 2 CH 3) -, - CH (CH (CH 3) 2) -, - C (CH 3) (CH (CH 3) 2) -, - _{CH (CH 2 CH 2 CH 2} CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 CH 3) -, - CH (CH 2 CH (CH 3) 2) -, - C (CH 3 _{) (CH 2 CH (CH 3} ) 2) -, - CH (CH 2 CH 2 CH 2 CH 2 CH 3) -, - C _{CH 3) (CH 2 CH 2} CH 2 CH 2 CH 3) -, - CH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 CH 2 CH ₂ CH ₃ ) — and the like.
Among A in the formula (7), —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—C ₆ H ₄ —O -Is preferable because a polyamide resin having sufficient solubility in not only an alkaline aqueous solution but also a solvent and having a better balance can be obtained.

Particularly preferred among the above formula (7) are those represented by the following formula (8) (some have R ² in formula (6)) and the following formula (9).

（式中、＊は一般式（６）におけるＮＨ基に結合することを示す。式中Ａは、アルキレン基、置換アルキレン基、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、又は単結合である。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つであり、それぞれ同一であっても異なっていても良い。
Ｒ^１１は、アルキル基、アルコキシ基、アシルオキシ基及びシクロアルキル基から選ばれた１つであり、同一であっても異なっても良い。ａは０〜４の整数、ｂは０〜２の整数、ｃは０〜３の整数である。）

(In the formula, * represents bonding to the NH group in the general formula (6). In the formula, A represents an alkylene group, a substituted alkylene group, —O—, —S—, —SO ₂ —, —C (= O) —, —NHC (═O) —, or a single bond, R ⁵ is one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different. good.
R ¹¹ is one selected from an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. a is an integer of 0 to 4, b is an integer of 0 to 2, and c is an integer of 0 to 3. )

Particularly preferable among the group represented by the above formula (8) and the group represented by the formula (9) are those represented by the following formula (10) (including those containing R ² in the formula (6)). Yes).

（ここで＊は一般式（６）におけるＮＨ基に結合することを示す。式中Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）Ｈ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、又は単結合から選ばれる有機基である。Ｒ^１１は、アルキル基、アルコキシ基、アシルオキシ基又はシクロアルキル基であり、それぞれ同一であっても異なっても良い。ｃは０〜３の整数である。）

(Here, * indicates binding to the NH group in the general formula (6). In the formula, A represents —CH ₂ —, —C (CH ₃ ) H—, —C (CH ₃ ) ₂ —, —C). R ¹¹ is an organic group selected from (CF ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) —, or a single bond. An alkyl group, an alkoxy group, an acyloxy group or a cycloalkyl group, which may be the same or different, and c is an integer of 0 to 3.)

  Further, Y in the polyamide resin represented by the general formula (6) is an organic group, and examples of such an organic group include the same as those described above for X. Examples include aromatic groups composed of structures such as benzene rings, naphthalene rings and bisphenol structures, heterocyclic organic groups composed of structures such as pyrrole rings, pyridine rings and furan rings, and siloxane groups. What is shown by following formula (11) can be mentioned preferably. These may be used alone or in combination of two or more.

（ここで、＊は、一般式（６）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−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−または単結合である。Ｒ^１２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、それぞれ同じであっても異なっていても良い。Ｒ^１３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。ｄは０〜４の整数である。Ｒ^１４〜Ｒ^１７は、有機基である。
なお、式（１１）において、上記式一般式（６）におけるＹの置換基Ｒ^３は省略している。）

(Here, * indicates bonding to the C═O group in the general formula (6). J represents —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) — or a single bond R ¹² represents an alkyl group, an alkyl ester group, an alkyl ether group, benzyl R ¹³ represents one selected from an ether group and a halogen atom, which may be the same or different, and R ¹³ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom. D is an integer of 0 to 4. R ^{14 to} R ¹⁷ are organic groups.
In Formula (11), Y substituent R ³ in Formula (6) is omitted. )

Among these, particularly preferred are those represented by the following formula (12) and formula (13) (some of which include R ³ in formula (6)).
Regarding the structures derived from tetracarboxylic dianhydrides in the following formulas (12) and (13), those in which the position bonded to the C═O group in the general formula (6) is both in the meta position and both in the para position. There may be a certain structure or a structure including a meta position and a para position.

（式中、＊は一般式（６）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−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−または単結合である。Ｒ^１８は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基及びハロゲン原子の内から選ばれた１つを表し、それぞれ同じであっても異なっていてもよい。Ｒ^１９は、水素原子又は炭素数１〜１５の有機基から選ばれた１つを示し、該有機基の一部が置換されていてもよい。ｅは０〜４の整数である。）

(In the formula, * indicates bonding to the C═O group in the general formula (6). J represents —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, — O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) — or a single bond, R ¹⁸ represents an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether; R ¹⁹ represents one selected from a group and a halogen atom, and may be the same or different from each other, and R ¹⁹ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms. A part of the organic group may be substituted, and e is an integer of 0 to 4.)

（式中、＊は一般式（６）におけるＣ＝Ｏ基に結合することを示す。Ｒ^２０は、水素原子又は炭素数１〜１５の有機基から選ばれた１つを示し、該有機基の一部が置換されていてもよい。）

(In the formula, * represents bonding to the C═O group in the general formula (6). R ²⁰ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms; Part of may be substituted.)

In the case of the polyamide resin represented by the above formula (6), the terminal amino group of the polyamide resin includes an aliphatic group having at least one other alkenyl group or alkynyl group or a group having a cyclic structure. An acid anhydride can be used to end-cend as an amide.
Examples of the aliphatic group having at least one alkenyl group or alkynyl group or the group having a cyclic structure include groups represented by formula (14) and formula (15). These may be used alone or in combination of two or more.

  The end-capping method is not limited to the above method, and the terminal carboxyl group contained in the polyamide resin is an aliphatic group having at least one alkenyl group or alkynyl group or a group having a cyclic structure. An amine derivative containing can be used to end-cleave as an amide.

Furthermore, in the case of the polyamide resin represented by the above formula (6), at least one of the terminals may be sealed with a nitrogen-containing cyclic compound. Thereby, adhesiveness with a metal wiring (especially copper wiring) etc. can be improved.
Examples of the nitrogen-containing cyclic compound include 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazoyl) amino group, 4- (1H-pyrazoyl) amino group, and 5- (1H-pyrazoyl). Amino group, 1- (3-1H-pyrazoyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazoyl) methylamino group, (1H-tetrazol-5-yl) ) Amino group, 1- (1H-tetrazol-5-yl) methyl-amino group, 3- (1H-tetrazol-5-yl) benz-amino group and the like.

The polyamide resin including the structure represented by the general formula (6) is, for example, a compound selected from diamine, bis (aminophenol), 2,4-diaminophenol and the like containing X in the general formula (6). And a compound selected from tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid, dicarboxylic acid dichloride or dicarboxylic acid derivative containing Y.
In addition, when using dicarboxylic acid, in order to improve the reaction yield of a polyamide resin, etc., the active ester type dicarboxylic acid which made 1-hydroxy-1,2,3-benzotriazole etc. react beforehand with dicarboxylic acid. Derivatives may be used.

  The polyamide resin represented by the general formula (6) is dehydrated and closed by heating to obtain a heat-resistant resin in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both. In addition, as temperature which performs dehydration ring closure, when heating at high temperature, it can process at 280 to 380 degreeC, and when heating at low temperature, it can process at 150 to 280 degreeC.

（式中、Ｖはジアミン残基、Ｗは酸無水物残基である。） Furthermore, you may use the polyamide resin containing the structure represented by General formula (16) as said polyamide resin.

(In the formula, V is a diamine residue, and W is an acid anhydride residue.)

  In the same manner as described above, the polyamide resin having the structure represented by the general formula (16) is obtained by reacting the diamine compound containing X in the general formula (16) with the acid anhydride containing Y. Can do.

  The diamine compound containing V in the general formula (16) is preferably a diamine containing an aromatic group from the viewpoint of not impairing heat resistance. Although not limited to this, for example, paraphenylenediamine, metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 3,4′-diamino Diphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfoxide, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2 ′ -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 1,4-bis (4-amino Phenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis 3-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 4 , 4′-bis (3-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) ether, 1,4-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) ) Anthracene, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Bis (4- (4-aminophenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-amino-4-methylphenyl) Propane, 1,4-bis (3-aminopropyl dimethylsilyl) benzene or hydrogen atom is part of methyl groups on the aromatic rings of these diamines, ethyl group, and those substituted with a halogen group.

  Moreover, as an acid dianhydride containing W in the said General formula (16), the acid dianhydride containing an aromatic group is desirable from a viewpoint which does not impair heat resistance. Although not limited to this, for example, pyromellitic dianhydride, 4,4-oxydiphthalic dianhydride, 3,3 ′, 4,4-benzophenone tetracarboxylic dianhydride, 3,3,4 , 4-diphenylsulfone tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoropropane-2,2-diphthalic dianhydride, 3,3-biphenyltetracarboxylic dianhydride, Examples include naphthalene-1,4,5,8-tetracarboxylic dianhydride and perylene-3,4,9,10-tetracarboxylic dianhydride.

  Moreover, as a phenol resin in alkali-soluble resin, resin synthesize | combined by condensation reaction of phenols and aldehydes, such as a phenol novolak resin, a cresol novolak resin, and a resole resin, can be used.

In the present invention, the alkali-soluble resin (A) is a polyamide resin, a polybenzoxazole precursor resin, a polyimide precursor resin, a polybenzoxazole resin, a polyimide resin, a phenol resin, or a copolymer of styrene, hydroxystyrene, and a derivative thereof. One or more kinds of resins selected from the group consisting of can be used. Moreover, the structure of these copolymers may be sufficient, for example, the polymer chosen from the structure of a polybenzoxazole precursor and a polyimide precursor may be sufficient. Among these, unlike the photoresist that is removed after forming the metal wiring, polyamide resin, polybenzoxazole precursor resin, polyimide precursor resin, because of the excellent mechanical properties and low environmental negatives required for the permanent film More preferably, at least one of polybenzoxazole resin and polyimide resin is contained. Moreover, in the same kind of resin, two or more resins having different structures may be included, for example, a combination of polybenzoxazole precursor resins having different structures or a polyimide precursor resin having different structures. Etc.
Furthermore, acrylic resins such as methacrylic acid resins and methacrylic acid ester resins can be used as alkali-soluble resins as long as the characteristics are not impaired.

[Photoacid generator (B)]
As a photoacid generator used in the photosensitive resin composition of the present invention, the solubility in an alkaline aqueous solution is improved by generating an acidic group by irradiation with ultraviolet rays, and the difference in solubility from an unirradiated portion such as ultraviolet rays. Added to provide. As a result, a pattern can be formed, and a cured film with a pattern can be formed on the substrate.
Examples of the photoacid generator include onium salts and quinonediazide compounds, but quinonediazide compounds are preferred from the viewpoint of reliability.

  Examples of the onium salt include iodonium salts such as diaryl iodonium salts, sulfonium salts such as triarylsulfonium salts, diazonium salts such as phosphonium salts and aryldiazonium salts. Specific examples include diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium-naphthalene-1-sulfonate, diphenyliodonium iodide, diphenyliodonium bromide, and the like.

  Examples of the quinonediazide compound include ester compounds obtained by a reaction between a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride or 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride. Can be mentioned. Specific examples include ester compounds represented by formula (17) to formula (21). Two or more of these may be used. Q in the formulas (17) to (21) represents a hydrogen atom, a 1,2-naphthoquinone-2-diazide-5-sulfonyl group, or a 1,2-naphthoquinone-2-diazide-4-sulfonyl group.

（上式（１７）中のＲ^２１は、水素、またはメチル基である）

(R ²¹ in the above formula (17) is hydrogen or a methyl group)

（上式（１９）中のＲ^２２は、水素、またはメチル基である）

(R ²² in the above formula (19) is hydrogen or a methyl group)

（上式（２０）中のＲ^２３は、水素、またはメチル基である）

(R ²³ in the above formula (20) is hydrogen or a methyl group)

（上式（２１）中のＲ^２４は、水素、またはメチル基である）

(R ²⁴ in the above formula (21) is hydrogen or a methyl group)

  The content of the photoacid generator is preferably 2 to 30 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A).

[Fluorine-containing copolymer (C)]
The fluorine-containing copolymer used in the photosensitive resin composition of the present invention reduces the dissolved amount of nitrogen in the varnish, and at the same time, the epoxy resin composition for semiconductor encapsulation used for semiconductor elements after the photosensitive resin composition is cured. It is added for the purpose of improving the adhesion to the object. In the synthesis of the fluorinated copolymer, a fluorinated acrylate monomer is used. As such an acrylate monomer, at least a compound represented by the following formula (C1) and a compound represented by the following general formula (C2) are used. It is necessary to be.

^{_{CH 2 = C (R 31)}} -COO- (CH 2) P -N (R 32) -SO 2 -C Q F 2Q + 1 (C1)
R ³¹ in the formula (C1) is a group selected from hydrogen and an optionally branched hydrocarbon group having 1 to 6 carbon atoms, and R ³² is an optionally branched hydrocarbon group having 1 to 6 carbon atoms. P is an integer of 1 or more and 10 or less, and Q is an integer of 1 or more and 7 or less. In addition, Q is preferably an integer of 1 or more and 6 or less, more preferably an integer of 1 or more and 4 or less, from the viewpoint of improving the solubility in the solvent used in the photosensitive resin composition.

_{^{CH 2 = C (R 33)}} -COO- (CR 34 R 35 -CR 36 R 37 -O-) J - (CR 38 R 39 -CR 40 R 41 -O-) K -R 42 (C2)
R ^{33 to} R ⁴¹ in Formula (C2) are groups selected from hydrogen or an optionally branched hydrocarbon group having 1 to 6 carbon atoms, and R ⁴² is an optionally branched group having 1 to 1 carbon atoms. 6 is a group selected from 6 hydrocarbon groups, J is an integer of 0 or more and 30 or less, K is an integer of 0 or more and 30 or less, and J and K are not 0 simultaneously.

  The compound represented by the formula (C1) is presumed to have an effect of reducing the dissolved amount of nitrogen in the varnish because the interaction with nitrogen is lowered by having fluorine.

  The compound represented by the formula (C2) is less soluble in the solvent to be used only by the compound represented by the formula (C1), and the fluorine-containing copolymer may be separated in the varnish. This separation can be prevented by introducing a high structure. Moreover, since polarity is high, it is guessed that interaction with the epoxy resin composition for semiconductor sealing used for a semiconductor element becomes high, and has contributed to the improvement of adhesiveness.

  In the fluorine-containing copolymer, in order to achieve both coatability, adhesion to the sealing resin, and solvent solubility, the mole of the compound represented by the formula (C1) and the compound represented by the formula (C2) during the polymerization reaction The ratio is preferably from 10:90 to 90:10, more preferably from 20:80 to 80:20.

  The fluorine-containing copolymer (C) used in the photosensitive resin composition of the present invention has a compound represented by the formula (C1) and the formula (C2) as long as they do not adversely affect the amount of dissolved nitrogen and adhesion. In addition to the compound represented by), a reactive unsaturated group-containing monomer may be copolymerized. Such a reactive unsaturated group-containing monomer is not particularly limited, and examples thereof include vinyl esters such as vinyl propionate, vinyl acetate and vinyl butyrate, acrylic acid, methacrylic acid, dimethylmaleic acid and maleic acid. , Reactive unsaturated group-containing carboxylic acids such as fumaric acid and itaconic acid, the reactive unsaturated group-containing carboxylic acids and aliphatic alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, octyl alcohol and decyl alcohol Of reactive unsaturated group-containing carboxylic acids obtained by reaction with NK ester 4G (manufactured by Shin-Nakamura Chemical), NK ester 9G (manufactured by Shin-Nakamura Chemical), triallyl-1,2,4-benzenetricarboxylate, etc. Having two or more reactive unsaturated groups Things and the like. Furthermore, for example, styrene, acrylonitrile, glycidyl methacrylate and the like can be mentioned.

  The weight average molecular weight of the fluorine-containing copolymer (C) is preferably 2,000 or more and 60,000 or less in view of solubility and reliability of metal wiring.

  The content of the fluorinated copolymer (C) in the photosensitive resin composition of the present invention is preferably 100 ppm or more and 2500 ppm or less for reducing the amount of dissolved nitrogen without causing abnormalities on the coating film surface. .

[Silicon compound (D)]
The silicon compound used in the photosensitive resin composition of the present invention is added with a silicon compound as an adhesion aid in improving the adhesion of the film during development and after curing. This is because addition of the fluorine-containing copolymer (C) is considered to inhibit the adhesion expressed by the polar group of the resin, and the adhesion may be lowered. .

  Specific examples of the silicon compound include silicon compounds having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, p. -Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxy Silicon compounds having reactive unsaturated bonds such as silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (triethoxypropyl) tetrasulfide, and 3-I Such as cyanate propyl triethoxy silane.

  Further, a silicon compound having an amino group can be used, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, and the like can be mentioned, but when added as they are, it acts with a photoacid generator in the photosensitive resin composition, and deterioration of storage stability is observed. In some cases, the silicon compound having an amino group may be used in advance as an acid dianhydride or acid anhydride. And it is desirable to use a silicon compound obtained by reacting the like dicarbonate compound or Isoshinereto compound.

  Examples of the acid dianhydride include benzophenone tetracarboxylic acid anhydride and bis (3,4-dicarboxyphenyl) ether dianhydride. Examples of the acid anhydride include maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, phthalic anhydride, and the like. Examples of the dicarbonate compound include diethyl dicarbonate and di-t-butyl dicarbonate. Examples of the isocyanate compound include methyl isocyanate and phenyl isocyanate. Moreover, in using these, it can use individually or in combination of 2 or more types.

  As content of the silicon compound in the photosensitive resin composition of this invention, when making adhesiveness and viscosity stability compatible, 0.1 mass part or more and 20 masses with respect to 100 mass parts of said alkali-soluble resin (A). Parts by weight or less, preferably 0.5 parts by weight or more and 15 parts by weight or less.

[Solvent (E)]
The solvent used in the photosensitive resin composition of the present invention is prepared by dissolving the alkali-soluble resin (A), the photoacid generator (B), the fluorinated copolymer (C), and the like into a varnish. It is used for the purpose of enabling coating on the top.
For example, N-methyl-2-pyrrolidone (hereinafter referred to as NMP), γ-butyrolactone, N, N′-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether , Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3- Examples thereof include methoxypropionate and may be used alone or in combination of two or more.

  As content of the solvent in the photosensitive resin composition of this invention, when ensuring the film thickness at the time of application | coating, 50 mass parts or more and 2500 mass parts or less are preferable with respect to 100 mass parts of said alkali-soluble resin (A). 100 parts by mass or more and 1500 parts by mass or less is more preferable.

[Crosslinking agent (F)]
A crosslinking agent can be further used in the photosensitive resin composition of the present invention. Unlike the photoresist that is removed after forming the metal wiring, such a crosslinking agent acts as a crosslinking agent for the alkali-soluble resin (A), thereby improving the mechanical properties required for the permanent film. It is added for the purpose. In addition, it is considered that the resin is cross-linked and strengthened in the film, but the adhesion with the sealing resin is improved. An alkylol compound, a methylol compound, an acrylate compound, or the like having two or more functions is preferable in terms of the action of a highly crosslinking agent.

  Specific examples of the alkylol compound include Nicarak MW390 (manufactured by Sanwa Chemical), Nicarak MX270 (manufactured by Sanwa Chemical), Nicarak MX280 (manufactured by Sanwa Chemical), Nicarak MX290 (manufactured by Sanwa Chemical), HMOM-BP ( Honshu Chemical), DMOM-PTBP (Honshu Chemical), and DMOM-PC (Honshu Chemical). Examples of the methylol compound include p-xylene glycol and m-xylene glycol. Examples of the acrylate compound include NK ester 4G (manufactured by Shin-Nakamura Chemical), NK ester 9G (manufactured by Shin-Nakamura Chemical), triallyl-1,2,4-benzenetricarboxylate, and the like.

  The content of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.5 to 30 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the alkali-soluble. .

  Further, in the photosensitive resin composition of the present invention, if necessary, an antioxidant such as hindered phenol, a filler, a photopolymerization initiator, a sensitizer, and a dissolution accelerator typified by a low molecular weight phenol. A compound such as an ester plasticizer may be added.

A cured film and a method for producing the cured film will be described.
As an example of the manufacturing method of the cured film in this invention, generally, the discharge process which dripped the photosensitive resin composition to a board | substrate, the coating process which forms a coating film in substrates, such as a wafer, The drying process which dries a coating film , The exposure process for forming the pattern on the dried coating film, the development process for forming the pattern after exposure, the rinsing process for rinsing the pattern, and the curing process in which the pattern is formed through the curing process for curing the pattern A membrane can be obtained.
Hereinafter, steps will be described in order.

<Discharge process>
First, the photosensitive resin composition of the present invention is discharged onto a suitable support or substrate, for example, a silicon wafer, a ceramic substrate, an aluminum substrate or the like.
The amount of discharge is adjusted so that the final film thickness after curing is 0.1 to 30 μm when applied onto a silicon wafer or semiconductor element. 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.

  In discharging the photosensitive resin composition, an apparatus having a mechanism for extruding varnish by nitrogen pressurization is used. Here, it is important to install a filter in the coating apparatus so that bubbles are not mixed in the discharged photosensitive resin composition, or to produce such that bubbles are not mixed into the photosensitive resin composition. When bubbles are mixed, uniform coating cannot be performed, and the yield decreases due to the occurrence of variations in film thickness. In particular, in the case of a 12-inch wafer, since the area is large, abnormalities are likely to occur in the wafer, and the frequency of rework increases, so the influence is great.

<Application process>
Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, immersion, printing, roll coating, and the like. In consideration of throughput and yield, spin coating using a spinner is preferable.

<Drying process>
Next, in order to facilitate handling, the solvent in the coating film is removed by drying. Drying may be performed at 60 to 130 ° C. for 60 to 300 seconds so as not to decompose the compound in the photosensitive resin composition.

<Exposure process>
Next, a mask having a desired pattern shape is placed on the dried coating film, and exposure is performed by irradiating with actinic radiation. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

<Development process>
Next, a pattern is obtained by dissolving and removing the actinic radiation irradiated portion with a developer.
Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine and di- Secondary amines such as n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a quaternary ammonium salt and an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added thereto can be suitably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

<Rinse process>
Next, the relief pattern formed by development is rinsed (cleaned). Distilled water can be used as the rinse liquid.

<Curing process>
Next, when the alkali-soluble resin has a benzoxazole precursor structure or an imide precursor structure by performing a heat treatment at a temperature higher than that in the drying step, the benzoxazole ring imide ring is respectively formed by a ring closure reaction. When the alkali-soluble resin is a phenol resin, or a copolymer of styrene and hydroxystyrene and derivatives thereof, by using a cross-linking agent, the resin and the cross-linking agent can react. Thus, a final pattern (cured film, protective film, insulating film) rich in heat resistance can be obtained. The heat treatment temperature is preferably 180 ° C to 380 ° C, more preferably 200 ° C to 350 ° C.

In such a manufacturing process, particularly when a 12-inch wafer is used, the pressure is released when discharged by an apparatus having a mechanism for extruding the varnish by nitrogen pressurization. Nitrogen is bubbled and mixed into the discharge varnish, and rotating the coating as it is, the surface film thickness uniformity may be lowered and an abnormality may occur. However, it is considered that the photosensitive resin composition of the present invention can suppress the interaction with nitrogen by using the fluorine-containing copolymer (C), and thus, when the varnish is pressurized with nitrogen. The amount of nitrogen dissolved can be reduced.
That is, the photosensitive resin composition of the present invention is useful in that it can be used with a high yield, particularly for large wafers such as 12-inch wafers.

  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 devices such as TFT (Thin Film Transistor) type liquid crystal and organic EL (Electro-Luminescence). It is also useful as an interlayer insulation film for multilayer circuits, a cover coat for flexible copper-clad plates, a solder resist film, and a liquid crystal alignment film.

  Examples of semiconductor device applications include a passivation film formed by forming a cured film of the above-described photosensitive resin composition on a semiconductor element, and a buffer formed by forming a cured film of the above-described photosensitive resin composition on the passivation film. A protective film such as a coating film, an insulating film such as an interlayer insulating film formed by forming a cured film of the above-described photosensitive resin composition on a circuit formed on a semiconductor element, an α-ray blocking film, a flat surface Examples thereof include a chemical film, a protrusion (resin post), and a partition wall.

  Examples of the display device application 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 planarizing film for TFT elements and color filters, MVA ( For example, protrusions for a multi-domain vertical alignment (liquid crystal display) type liquid crystal display device, partition walls for an organic EL element cathode, and the like can be given.

  The method for using the photosensitive resin composition of the present invention in a display device is the same as the method described above, except that the photosensitive resin composition layer patterned on the substrate on which the display element and the color filter are formed is applied to the above-described method. It is because it forms in. 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 semiconductor device is a semiconductor device in which the insulating film, the α-ray blocking film, the planarization film, the protrusion (resin post), the partition wall, and the like are formed.
The display device includes a TFT element, a color filter, an MVA (Multi-domain Vertical Alignment) type liquid crystal display device, an organic EL, on which the cured film, the protective film, the insulating film, the planarization film, the protrusion, and the like are formed. Such as a device cathode.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

[Alkali-soluble resin (A-1)]
Dicarboxylic acid diester consisting of 4,4′-oxybisbenzoic acid and 1-hydroxybenzotriazole in a four-neck separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. 64 g (0.18 mol), dicarboxylic acid diester composed of isophthalic acid and 1-hydroxybenzotriazole, 18.02 g (0.045 mol), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 73 .25 g (0.20 mol), 3,3′-diamino-biphenyl-4,4′-diol 10.81 g (0.05 mol), N-methyl-2-pyrrolidone (NMP) 770 ml, nitrogen atmosphere The mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was stirred at a liquid temperature of 75 ° C. for 9 hours.
Next, 12.31 g (0.075 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 65 ml of NMP 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 dried under vacuum to obtain the structure shown in Table 1. The alkali-soluble resin (A-1) containing was obtained.

[Alkali-soluble resin (A-2)]
Dicarboxylic acid diester consisting of 4,4′-oxybisbenzoic acid and 1-hydroxybenzotriazole in a four-neck separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. 64 g (0.18 mol), 18.02 g (0.045 mol) of dicarboxylic acid diester composed of isophthalic acid and 1-hydroxybenzotriazole, bis (3-amino-4-hydroxy-2,5-dimethylphenyl) methane 71 .59 g (0.25 mol) and 720 ml of N-methyl-2-pyrrolidone (NMP) were added and stirred at room temperature for 30 minutes in a nitrogen atmosphere. Then, it stirred at the liquid temperature of 75 degreeC for 10 hours. Next, 12.91 g (0.075 mol) of 5-ethynyl-isobenzofuran-1,3-dione dissolved in 65 ml of NMP 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, dried under vacuum, and as shown in Table 1. Alkali-soluble resin (A-2) containing the structure was obtained.

[Alkali-soluble resin (A-3)]
A 500 ml round bottom flask was charged with 30.0 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 400 ml of acetone, and 2,2-bis (3-amino- Stir until 4-hydroxyphenyl) hexafluoropropane is dissolved. Thereto, 12.4 g (0.18 mol) of para-nitrobenzoyl chloride dissolved in 100 ml of acetone was added dropwise over 30 minutes while cooling so that the temperature was less than 20 ° C. to obtain a mixture. After the dropwise addition, the temperature of the mixture was heated to 40 ° C. and stirred for 2 hours, and 30.0 g (0.218 mol) of potassium carbonate was gradually added thereto, and further stirred for 2 hours. Heating was stopped and the mixture was further stirred at room temperature for 18 hours. Thereafter, an aqueous sodium hydroxide solution was gradually added while 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, and a 37 mass% hydrochloric acid aqueous solution and 500 ml of water were added to adjust the pH to be in the range of 6.0 to 7.0. The obtained precipitate was filtered off, washed with water and dried at 60 to 70 ° C., and bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl). ) A propane solid was obtained. To 51.0 g of the obtained solid, 316 g of acetone and 158 g of methanol were added and heated to 50 ° C. for complete dissolution. Thereto, 300 ml of 50 ° C. pure water was added over 30 minutes and heated to 65 ° C. Thereafter, the precipitated crystals are slowly cooled to room temperature and filtered, and the crystals are purified by drying at 70 ° C. to obtain bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis. (4-Hydroxyphenyl) propane was obtained.
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. Then, hydrogen gas was purged, 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.

  Bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4- (4)) was added to a four-neck separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. Hydroxyphenyl) propane (58.72 g, 0.097 mol), 1,3-bis (aminopropyl) tetramethyldisiloxane (0.75 g, 0.003 mol) and γ-butyrolactone (158 ml) were added, and the mixture was stirred to 15 ° C. Cooled down. Thereto was added 27.92 g (0.09 mol) of 4,4′-oxydiphthalic anhydride, 2.94 g (0.01 mol) of biphenyltetracarboxylic dianhydride and 48 ml of γ-butyrolactone, and 1. Stir for 5 hours. Thereafter, the mixture was heated to 50 ° C. and stirred for 3 hours, and then 23.83 g (0.2 mol) of N, N-dimethylformamide dimethylacetal and 40.0 ml of γ-butyrolactone were added, and the mixture was further stirred at 50 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and then poured into a solution of water / isopropyl alcohol = 3/1. The precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum. A polyamide resin (A-3), which is an alkali-soluble resin containing the structure shown in Table 1, was obtained (resin that was dehydrated and ring-closed when heated at 300 to 400 ° C. to become polyimide benzoxazole).

[Alkali-soluble resin (A-4)]
In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 91.56 g of 0,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0 .25 mol) and 800 g of N-methyl-2-pyrrolidone (NMP) were added and stirred for 30 minutes at room temperature in a nitrogen atmosphere to be completely dissolved.
Next, 39.5 g (0.50 mol) of pyridine was added, and trans-3,6-endomethylene-1,2,3,6-tetrahydrophthaloyl chloride 39.43 g (maintaining 0 to 5 ° C.) 0.180 mol), 4,4′-oxydibenzoyl chloride 13.28 g (0.045 mol) in 100 g of N-methyl-2-pyrrolidone (NMP) was gradually added dropwise over 30 minutes. did. After dripping, it was made to react at the temperature of 0-5 degreeC for 1 hour, temperature was raised to normal temperature, and it was made to react for 1 hour.
To this, 14.77 g (0.09 mol) of 5-norbonene-2,3-dicarboxylic acid anhydride was added, and the temperature was raised to 75 ° C. and 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, dried under vacuum, and as shown in Table 1. Alkali-soluble resin (A-4) containing the structure was obtained.

[Alkali-soluble resin (A-5)]
Marcalinker CST-60 (Maruzen Petrochemical Co., Ltd.)

[Alkali-soluble resin (A-6)]
XPS-4958G (manufactured by Gunei Chemical Industry Co., Ltd.)

  Table 1 shows the structures of X and Y and the terminal structure in the above formula (6) and the structure of the alkali-soluble resin for the alkali-soluble resin synthesized above.

[Photoacid generator (B-1)]
11.03 g (0.026 mol) of phenol represented by the formula (P-1), 17.19 g (0.064 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and 160 g of acetone, The mixture was stirred and dissolved in a four-necked separable flask equipped with a total, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, a mixed solution of 7.07 g (0.07 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 0.96 g (0.016 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. After filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (900 ml / 9 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and expressed by the formula (B-1). The indicated photosensitizer was obtained.

[Photoacid generator (B-2)]
12.70 g (0.022 mol) of phenol of formula (P-2), 17.49 g (0.065 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 7.24 g (0.072 mol) of triethylamine and 6.1 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 0.98 g (0.016 mol) of acetic acid was added, and the mixture was further reacted for 30 minutes. After filtration of the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the formula (B-2) A photosensitizer represented by the structure was obtained.

[Fluorine-containing copolymer (C)]
The following monomers (M-1) to (M-4) used for the synthesis of the fluorine-containing copolymer were used.

[Fluorine-containing copolymer synthesis monomer (M-1)]
Stirrer, thermocouple, three-necked 1 liter flask equipped with a dropping funnel and a reflux _{condenser, C 4 F 9 -SO 2 -NCH} 3 -H (100g), sodium carbonate (3 g) and heptane (100 g) And stirred. Ethylene carbonate (35 g) was gradually added, and after completion of the addition, stirring was continued until generation of carbon dioxide gas was stopped. The temperature was lowered to 100 ° C. and reacted for 8 hours. The heating was stopped, 300 ml of pure water was gradually added, and the aqueous phase was sucked up with a tube and removed. This operation was repeated three times. 300 ml of 5 wt% aqueous sulfuric acid solution was added to remove the aqueous phase. Further, washing with pure water was repeated three times.
The solvent was removed in a reduced pressure _to obtain a _{C 4 F 9 -SO 2 -N (} CH 3) -CH 2 -CH 2 -OH (102g).
Into a 1 liter three-necked flask equipped with a stirrer, thermocouple, dropping funnel and reflux condenser, C ₄ F ₉ —SO ₂ —N (CH ₃ ) —CH ₂ —CH ₂ —OH obtained above was added. (102 g), phenothiazine (0.1 g), methoxyhydroquinone (0.1 g), heptane (100 g), acrylic acid (28 g), and triflic anhydride (2 g) were added while flowing nitrogen. The reaction was carried out at 95 ° C. for 8 hours. The temperature was lowered to 70 ° C., and the solvent and volatile components were removed by reducing the pressure. It returned to normal pressure, washed with 300 ml of pure water three times, and dried under reduced pressure. To give the object of the fluorine-containing copolymer monomer _{(M-1) CH 2 =} CH-COO-CH 2 -CH 2 -N (CH 3) -SO 2 -C 4 F 9 a (95 g).

[Fluorine-containing copolymer synthesis monomer (M-2)]
The target fluorinated copolymer monomer (M) was synthesized by the same method except that the acrylic acid (28 g) used in the fluorinated copolymer synthetic monomer (M-1) was changed to methacrylic acid (35 g). _{-2) CH 2 = C (CH} 3) -COO-CH 2 -CH 2 -N (CH 3) was obtained -SO 2 _-C 4 _{F 9.}

[Fluorine-containing copolymer synthesis monomer (M-3)]
Carbowax 750 acrylate (manufactured by Union Carbide) was used.
_{CH 2 = CH-COO- (CH} 2 -CH 2 -O-) 17 -CH 3

[Fluorine-containing copolymer synthesis monomer (M-4)]
Pluronic (manufactured by BASF) was used.
_{CH 2 = CH-COO- (CH} 2 -CH 2 -O-) 11 - (CH 2 -CH (CH3) -O-) 21 -CH 3

[Fluoropolymer (C-1)]
While flowing nitrogen, in a 500 ml four-necked flask, fluorine-containing copolymer monomer (M-1) (40 g), fluorine-containing copolymer monomer (M-3) (60 g), 2,2′-azobis Isobutyronitrile (2 g), 3-mercapto-1,2-propanediol (4 g), and toluene (150 g) were added. The mixture was heated to 78 ° C. and stirred for 8 hours under reflux. The solvent was removed under reduced pressure to obtain 91 g of a fluorinated copolymer (C-1).

[Fluorine-containing copolymer (C-2)]
The amount of the fluorine-containing copolymer monomer (M-1) (40 g) used in the fluorine-containing copolymer (C-1) was changed to (20 g), and the fluorine-containing copolymer monomer (M-3) (60 g) ) Was changed to fluorine-containing copolymer monomer (M-4) (80 g), and synthesized in the same manner as the synthesis of fluorine-containing copolymer (C-1). 87 g of a fluorine-containing copolymer (C-2) was obtained.

[Fluorine-containing copolymer (C-3)]
The fluorine-containing copolymer monomer (M-1) (40 g) used in the fluorine-containing copolymer (C-1) was changed to a fluorine-containing copolymer monomer (M-2) (35 g). The synthesis was performed in the same manner as the synthesis of the fluorine-containing copolymer (C-1) except that the amount of the combined monomer (M-3) (60 g) was changed to (75 g). 92 g of a fluorine-containing copolymer (C-3) was obtained.

[Silicone structure-containing compound (C-4)]
Silicone structure-containing compound SH-193 (manufactured by Toray Dow Corning Co., Ltd.)

[Fluorine-containing compound (C-5)]
Fluorine-containing compound FC-95 (manufactured by Sumitomo 3M Limited)
^{_{C 8 F 17 -SO 3 - K}} +

[Fluorine-containing compound (C-6)]
Fluorine-containing compound FC-171 (manufactured by Sumitomo 3M)
_{CH 3 - (O-CH 2} -CH 2) 7 -N (CH 2 CH 3) -SO 2 -C 8 F 17

[Fluorine-containing compound (C-7)]
Fluorine-containing compound FC-129 (manufactured by Sumitomo 3M)
_{C 8 F 17 -SO 2 -N (} CH 2 CH 3) -CH 2 -COO - K +

[Solvent (D-1)]
γ-butyrolactone

[Solvent (D-2)]
N-methylpyrrolidone

[Silicon compound (E-1)]
2-Methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

[Silicon compound (E-2)]
A silicon compound obtained by the following chemical formula obtained by reaction of maleic anhydride and 3-aminopropyltriethoxysilane in a molar ratio of 1: 1.
_{HOOC-CH = CH-CO-} NH- (CH 2) 3 -Si (OCH 2 CH 3) 3

[Silicon compound (E-3)]
A silicon compound obtained by the following chemical formula obtained by reaction of di-t-butyl dicarbonate and 3-aminopropyltrimethoxysilane in a molar ratio of 1: 1.
(CH ₃ ) ₃ C—O—CO—NH— (CH ₂ ) ₃ —Si (OCH ₃ ) ₃

[Silicon compound (E-4)]
A silicon compound obtained by the following chemical formula obtained by a reaction of oxydiphthalic anhydride and 3-aminopropyltriethoxysilane in a molar ratio of 1: 2.
_{O- [C 6 H 4 (-COOH} ) {- CO-NH- (CH 2) 3-Si (OCH 2 CH 3) 3

[Silicon compound (E-5)]
A silicon compound obtained by the following chemical formula obtained by a reaction of phenyl isocyanate and 3-aminopropyltrimethoxysilane in a molar ratio of 1: 1.
_{C 6 H 5 -NH-CO-} NH- (CH 2) 3 -Si (OCH 3) 3

[Silicon compound (E-6)]
3-Glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

[Crosslinking agent (F-1)]
Nicarak MW390 (manufactured by Sanwa Chemical Co., Ltd.)

[Crosslinking agent (F-2)]
p-xylene glycol

[Crosslinking agent (F-3)]
NK ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.)

Example 1
[Preparation of photosensitive resin composition]
100 g of the alkali-soluble resin (A-1), 15 g of the photoacid generator (B-1), 1000 ppm of the fluorinated copolymer (C-1) (added so that the photosensitive resin composition including the solvent is 1000 ppm) ), 3 g of the silicon compound (E-1) was dissolved in 180 g of a solvent (γ-butyrolactone), and then filtered through a polyethylene (registered trademark) filter having a pore size of 0.2 μm, and allowed to stand for 6 hours. A composition was obtained. The following evaluation was performed using the obtained resin composition.

[Evaluation of coating film surface after drying (PB)]
The photosensitive resin composition was discharged onto a 12-inch silicon wafer using a nitrogen pressure dispense pump, and spin coating was performed using a coater / developer apparatus (ACT12, manufactured by Tokyo Electron). Subsequently, the film was dried on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 6 μm. The surface state of the obtained 12-inch silicon wafer with a coating film was observed, and the results are shown in Table 2.
The evaluation of the items on the coating film surface after drying in Table 2 was based on the following evaluation.
○: There is no coating unevenness due to striation or bubbles.
(Triangle | delta): Although there is no striation, there exists a coating nonuniformity resulting from a bubble.
X: There is striation, and there is also coating unevenness due to bubbles.

[Evaluation of sensitivity]
The photosensitive resin composition was spin-coated on an 8 silicon wafer using a coater / developer apparatus (DSPIN-80A, manufactured by Dainippon Screen Mfg. Co., Ltd.), and subsequently, heated at 120 ° C. on a hot plate at 4 ° C. The film was dried for 5 minutes to obtain a coating film having a film thickness of about 6 μm. Next, an illuminometer (METER-MODEL1000, SUZU.TM.1000) is used for proximity exposure using an exposure apparatus (MA-8, manufactured by SUSS Microtech Co., Ltd.) using a glass chrome mask with 100 μm-sized via holes. Exposure was performed for 10 seconds under the conditions of illuminance 365 nm: 27.1 mW / cm ² , 405 nm: 42.2 mW / cm ² , 435 nm: 2.66 mW / cm ² (manufactured by Microtech Co., Ltd.). Next, using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, the development time was adjusted so that the difference in film thickness after drying and development was 1 μm, and paddle development was performed. Then, it rinsed with the pure water for 10 seconds. The obtained 8-inch wafer with a pattern was observed with an optical microscope, and it was confirmed whether there was any abnormality or residue in the pattern. The results are shown in Table 2.
The evaluation of the sensitivity items in Table 2 was based on the following evaluation.
○: There is no abnormality or residue in the pattern.
X: There are abnormalities and residues in the pattern.

[Evaluation of the amount of dissolved nitrogen]
5 g of the above photosensitive resin composition was put into a 10 ml glass sample tube, put into a metal pressure bottle without a lid, and pressurized with nitrogen. After 96 hours, the sample tube was carefully taken out over 60 minutes so as not to give an impact, and transferred to a glass desiccator capable of decompression. Since it can be determined that the amount of the generated foam is large, the amount of dissolved nitrogen is large. Therefore, the inside of the desiccator was decompressed with a vacuum pump, and the number of generated foam was visually counted. Table 2 shows the number of bubbles generated.

[Evaluation of shear strength with sealing resin]
The photosensitive resin composition is applied to an 8-inch silicon wafer using a spinner (D-SPIN80A, manufactured by Dainippon Screen Co., Ltd.) and heat-treated at 120 ° C. for 4 minutes to volatilize most of the solvent and be handled. I did it. This was put into an oven (CLH-21CDH, manufactured by Koyo Thermo System Co., Ltd.), and nitrogen was flowed to make the oxygen concentration 20 ppm. While maintaining the oxygen concentration at 20 ppm, the silicon substrate was cured by heat treatment in an oven at 150 ° C. for 30 minutes and 320 ° C. for 30 minutes in order, thereby obtaining a silicon wafer with a cured film having a thickness of about 5 μm. An epoxy resin composition for semiconductor encapsulation (EME-7351LS, manufactured by Sumitomo Bakelite Co., Ltd.) is cured on a silicon wafer with a cured film using a transfer molding machine, at a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and cured. An adhesion strength test piece having a size of 2 × 2 × 2 mm (width × length × height) was molded under the condition of time 120 seconds. Next, after processing by pressure cooker treatment (125 ° C., 2.3 atm, 100% RH) for 24 hours, the shear strength of the cured sealing resin molded on the cured coating film was measured using a tensile tester.

<< Examples 2 to 14 >>
The alkali-soluble resin (A-1), photoacid generator (B-1), fluorine-containing copolymer (C-1), and silicon compound (E-1) of Example 1 were replaced with those described in Table 2, When using a cross-linking agent, 2 g each was used. Other processes and evaluation were performed in the same manner as in Example 1.

  Examples 1-14 showed the favorable characteristic in each evaluation item of the coating film surface after drying, the shear strength with sealing resin, a sensitivity, and the quantity of dissolved nitrogen.

≪Comparative Examples 1-7≫
The alkali-soluble resin (A-1), photoacid generator (B-1), fluorine-containing copolymer (C-1), and silicon compound (E-1) of Example 1 were replaced with those described in Table 2, When using a cross-linking agent, 2 g each was used. Other processes and evaluation were performed in the same manner as in Example 1.

<< Comparative Examples 1 and 2 >>
Comparative Examples 1 and 2 were at a level using a silicone structure-containing compound, but there were variations in film thickness and surface unevenness on the surface after coating, and the shear strength with the sealing resin was also unfavorable. The sensitivity was inferior to that of a normal pattern, probably due to film thickness variation.

<< Comparative Examples 3 and 5 >>
Comparative Examples 3 and 5 were at a level using a fluorine-containing compound having a low molecular weight and a C8 perfluoroalkyl group, but there were problems with shear strength with the sealing resin and nitrogen penetration.

<< Comparative Example 4 >>
Comparative Example 4 is a level using a fluorine-containing compound having a low molecular weight and a C8 perfluoroalkyl group, but has a problem in shear strength with the sealing resin and nitrogen penetration.

<< Comparative Example 6 >>
In Comparative Example 6, the fluorine-containing copolymer was not added, but there was a problem in the shear strength with the sealing resin and the amount of nitrogen dissolved.

<< Comparative Example 7 >>
Comparative Example 7 is a level in which 10,000 ppm of the fluorocopolymer (C-1) was added, but the shear strength with the sealing resin was high, but the added amount was too large, so that the coating film surface after drying was applied. There was a problem.

Moreover, the semiconductor device which has the bump of FIG. 1 was produced and evaluated using the resin composition of Examples 1-14.
FIG. 1 shows an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump according to the present invention. As shown in FIG. 1, an input / output Al pad 2 is provided on a silicon substrate 1 having a semiconductor element and wiring provided on the surface, and a passivation film 3 is formed thereon, and the passivation film 3 is formed on the passivation film 3. A via hole was formed. On this, the photosensitive composition produced above was applied and dried to form a photosensitive resin film (buffer coat film) 4, and solder bumps 5 were formed in the via holes, whereby a semiconductor device 10 was obtained.
All the semiconductor devices obtained as described above operated without any problem and had a good yield.

DESCRIPTION OF SYMBOLS 1 Silicon substrate 2 Aluminum pad 3 Passivation film 4 Buffer coat film 5 Solder bump 10 Semiconductor device

Claims (15)

Fluorine-containing copolymer obtained by copolymerizing alkali-soluble resin (A), photoacid generator (B), at least a compound represented by the following formula (C1) and a compound represented by the following formula (C2) The photosensitive resin composition containing a union (C), a silicon compound (D), and a solvent (E).
^{_{CH 2 = C (R 31)}} -COO- (CH 2) P -N (R 32) -SO 2 -C Q F 2Q + 1 (C1)
(R ³¹ in Formula (C1) is a group selected from hydrogen or a hydrocarbon group having 1 to 6 carbon atoms that may be branched, and R ³² is a group having 1 to 6 carbon atoms that may be branched. And a group selected from hydrocarbon groups, P is an integer of 1 to 10, and Q is an integer of 1 to 7.)
^{_{CH 2 = C (R 33)}} -COO- (CR 34 R 35 -CR 36 R 37 -O-) J - (CR 38 R 39 -CR 40 R 41 -O-) K -R 42 (C2)
(R ^{33 to} R ⁴¹ in Formula (C2) are groups selected from hydrogen or an optionally branched hydrocarbon group having 1 to 6 carbon atoms, and R ⁴² is an optionally branched carbon number. And a group selected from hydrocarbon groups of 1 to 6. J is an integer of 0 or more and 30 or less, K is an integer of 0 or more and 30 or less, and J and K are not 0 at the same time.)   The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition contains the fluorine-containing copolymer (C) at 500 ppm or more and 2500 ppm or less.   The fluorine-containing copolymer (C) comprises a compound represented by the formula (C1) and a compound represented by the formula (C2) in a molar ratio (C1: C2) of 10:90 or more and 90:10 or less. The photosensitive resin composition according to claim 1, which is polymerized.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the fluorine-containing copolymer (C) has a weight average molecular weight of 2,000 or more and 60,000 or less.   The photosensitive resin composition according to any one of claims 1 to 4, wherein in the compound represented by the formula (C1), Q in the formula (C1) is an integer of 1 or more and 6 or less.   The photosensitive resin composition according to any one of claims 1 to 5, wherein in the compound represented by the formula (C1), Q in the formula (C1) is an integer of 1 or more and 4 or less.   The photosensitive resin composition according to claim 1, wherein the photoacid generator (B) is a naphthoquinone diazide compound.   Furthermore, the photosensitive resin composition of any one of the Claims 1 thru | or 7 containing a crosslinking agent (F).   The alkali-soluble resin (A) comprises a polyamide resin, a polybenzoxazole precursor resin, a polyimide precursor resin, a polybenzoxazole resin, a polyimide resin, a phenol resin, and a copolymer of styrene, hydroxystyrene, and a derivative thereof. The photosensitive resin composition of any one of Claims 1 thru | or 8 which contains 1 or more types of resin chosen from a group.   The photosensitive resin composition according to claim 9, wherein the alkali-soluble resin (A) contains a resin having a different structure in the same type of resin.   A cured film obtained by discharging and curing the photosensitive resin composition according to any one of claims 1 to 10 onto a 12-inch wafer.   The protective film comprised with the cured film of Claim 11.   The insulating film comprised with the cured film of Claim 11.   A semiconductor device comprising the cured film according to claim 11.   The display body apparatus which has the cured film of Claim 11.

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