JP5628104B2 - Photosensitive resin composition, pattern and method for producing the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a pattern, and a method for producing the same. The present invention also relates to an electronic device such as an organic EL display device, a liquid crystal display device, and a semiconductor element using the pattern. More specifically, a positive photosensitive resin composition suitable for forming a flattening film, a protective film, and an interlayer insulating film of electronic components such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state imaging device, and the same The present invention relates to a method of manufacturing a pattern using

  An organic EL display device, a liquid crystal display device, or the like is provided with a patterned ITO film. For this ITO film pattern formation, a method is widely known in which a photosensitive resin composition is applied on the ITO film, the solvent is removed, exposed and developed, and the ITO film is etched and processed using the formed pattern as a mask. ing.

  In recent years, high resolution of ITO processing has been demanded in order to make organic EL display devices and liquid crystal display devices have high-definition display characteristics. In order to finely process ITO, high resolution of a photosensitive resin composition that functions as a mask during etching is required.

  Further, in order to further improve the productivity of the organic EL display device and the liquid crystal display device, improvement of the process margin is an issue. From this viewpoint, further improvement in sensitivity of the photosensitive resin composition is required. Further, in recent years, during exposure of the photosensitive resin composition when forming a mask pattern, the light irradiation amount has fluctuated due to fluctuations, or has fluctuated due to a deviation in light irradiation amount according to the type of the exposure machine. However, it is also demanded that the photosensitive resin composition has a wide exposure margin and does not easily change the line width of the pattern obtained. In addition, there is a demand for a resin composition in which the resist flow by heating is small, the taper shape is good, and the line width of the pattern obtained by the flow hardly changes.

  Here, Patent Document 1, Patent Document 2 and Patent Document 3 disclose positive photosensitive resin compositions containing a resin in which a part of polyhydroxystyrene is protected with a tetrahydrofuran compound.

JP 2011-75864 A Japanese Patent Laid-Open No. 10-121029 Japanese Patent Laid-Open No. 11-190904

  When this inventor examined patent document 1 and patent document 2, it turned out that the positive type photosensitive resin composition obtained is inferior in resolution and heat resistance. The object of the present invention is to solve such problems, and an object of the present invention is to provide a positive photosensitive resin composition capable of achieving both heat resistance and resolution.

Under such circumstances, the inventors of the present application have conducted intensive studies. As a result, in Patent Document 1 and Patent Document 2, when a tetrahydrofuranyl group is used as a protecting group, a factor that cannot achieve both resolution and heat resistance is a resin. The polydispersity (weight average molecular weight / number average molecular weight, Mw / Mn) was found to be small. In the positive photosensitive resin composition, it is known that the polydispersity of a resin such as polyhydroxystyrene is preferably small, and it is extremely difficult to improve the effect by increasing the polydispersity. It's amazing.
Specifically, the problems of the present invention have been solved by the following means.

（一般式（Ｉ）中、Ｒａ¹〜Ｒａ⁶は、それぞれ、水素原子、炭素数１〜２０の置換基を有していてもよいアルキル基、または、置換基を有していてもよいアリール基であり、互いに結合して環を形成していてもよい。Ｒａ⁷は水素原子またはメチル基であり、Ｒａ⁸はハロゲン原子、水酸基または炭素数１〜３のアルキル基である。ｎ１は０〜４の整数である。）
一般式（ＩＩ）

（一般式（ＩＩ）中、Ｒａ⁹は水素原子またはメチル基であり、Ｒａ¹⁰はハロゲン原子、水酸基または炭素数１〜３のアルキル基である。ｎ２は０〜４の整数である。）
（２）前記ポリマー（Ａ）の重量平均分子量は５０００以上である、（１）に記載のポジ型感光性樹脂組成物。
（３）光酸発生剤（Ｂ）が下記一般式（ｂ１）で表されるオキシムスルホネート構造を有する、（１）または（２）に記載のポジ型感光性樹脂組成物。
一般式（ｂ１）

（一般式（ｂ１）中、Ｒ¹は、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいヘテロアリール基または置換基を有していてもよいアリール基を表す。）
（４）（Ｄ）塩基性化合物として、下記一般式（ａ）で表される化合物、下記一般式（ｂ）で表される化合物および下記一般式（ｃ）で表される化合物の少なくとも１種を含む、（１）〜（３）のいずれか１項に記載のポジ型感光性樹脂組成物。
一般式（ａ）

（一般式（ａ)中、Ｒ²は炭素数が１〜６の置換基を有していてもよいアルキル基または炭素数３〜１０の置換基を有していてもよいシクロアルキル基を表す。Ｘは酸素原子または硫黄原子を表す。Ｙ¹は酸素原子または−ＮＨ−基を表す。ｐ１は１〜３の整数を表す。）
一般式（ｂ）

（一般式（ｂ）中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰は、それぞれ、水素原子、炭素数１〜６の置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、炭素数３〜１０の置換基を有していてもよいシクロアルキル基を表す。）
一般式（ｃ）

（５）前記一般式（Ｉ）におけるＲａ¹、Ｒａ²、Ｒａ³、Ｒａ⁵が、水素原子である、（１）〜（４）のいずれか１項に記載のポジ型感光性樹脂組成物。
（６）前記一般式（Ｉ）におけるｎ１および一般式（ＩＩ）におけるｎ２が０である、（１）〜（５）のいずれか１項に記載のポジ型感光性樹脂組成物。
（７）前記一般式（Ｉ）で表される繰り返し単位が下記一般式（ＩＩＩ）で表される、（１）〜（６）のいずれか１項に記載のポジ型感光性樹脂組成物。
一般式（ＩＩＩ）

（８）前記（Ｂ）光酸発生剤が、下記一般式（ＯＳ−３）、下記一般式（ＯＳ−４）、下記一般式（ＯＳ−５）、下記一般式（ｂ２）下記一般式（Ｂ３）および一般式（ＯＳ−２）のいずれかで表される化合物である、請求項１〜７のいずれか１項に記載のポジ型感光性樹脂組成物。

（一般式（ＯＳ−３）〜一般式（ＯＳ−５）中、Ｒ²²、Ｒ²⁵およびＲ²⁸はアルキル基、アリール基またはヘテロアリール基を表し、Ｒ²³、Ｒ²⁶およびＲ²⁹はそれぞれ独立に、水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ²⁴、Ｒ²⁷およびＲ³⁰はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表し、Ｘ¹〜Ｘ³はそれぞれ独立に酸素原子または硫黄原子を表し、ｎ１〜ｎ３はそれぞれ独立に１または２を表し、ｍ１〜ｍ３はそれぞれ独立に０〜６の整数を表す。）

（一般式（ｂ２）中、Ｒ³¹はアルキル基、シクロアルキル基またはアリール基を表し、Ｘ¹¹はアルキル基、アルコキシ基またはハロゲン原子を表し、ｍ１１は０〜３の整数を表す。ｍ１１が２または３であるとき複数のＸ¹¹は同一であっても異なっていてもよい。）
式（Ｂ３）

（式（Ｂ３）中、Ｒ⁴³は置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいヘテロアリール基または置換基を有していてもよいアリール基であり、Ｘ¹は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、シアノ基またはニトロ基を表し、ｎ４は０〜５の整数を表す。）

（一般式（ＯＳ−２）中、Ｒ¹⁰¹は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基、または、ヘテロアリール基を表す。Ｒ¹⁰²は、アルキル基、または、アリール基を表す。Ｒ¹²¹〜Ｒ¹²⁴は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基、または、アリール基を表す。Ｒ¹²¹〜Ｒ¹²⁴のうち２つは、それぞれ互いに結合して環を形成してもよい。）
（９）（１）（１）〜（８）のいずれか１項に記載の感光性樹脂組成物を基板上に適用する工程、
（２）適用された感光性樹脂組成物から溶剤を除去する工程、
（３）活性放射線で露光する工程、
（４）水性現像液で現像する工程、
（５）形成されたレジストパターンをマスクとして前記基板をエッチングする工程、および、
（６）前記レジストパターンを剥離する工程、を含むことを特徴とするパターンの製造方法。
（１０）前記現像工程後、エッチング工程前に、前記レジストパターンを１００〜１６０℃でポストベークする工程を含む、（９）に記載のパターンの製造方法。
（１１）前記基板が、ＩＴＯ基板、モリブデン基板またはシリコン基板であることを特徴とする（９）または（１０）に記載のパターン製造方法。
（１２）（９）〜（１１）のいずれか１項に記載のパターン製造方法に記載のパターンの製造方法により形成されたパターン。
（１３）（９）〜（１１）のいずれか１項に記載のパターン製造方法に記載のパターンの製造方法により形成されたＩＴＯパターン。
（１４）（１３）に記載のＩＴＯパターンを具備する、有機ＥＬ表示装置または液晶表示装置。 (1) The total of the repeating unit (a1) represented by the following general formula (I) and the repeating unit (a2) represented by the following general formula (II) is 95 mol% or more of all repeating units, and A positive photosensitive resin comprising a polymer (A) having a polydispersity (weight average molecular weight / number average molecular weight) greater than 2.0, a photoacid generator (B), and a solvent (C). Composition.
Formula (I)

(In the general formula (I), Ra ^{1 to} Ra ⁶ are each a hydrogen atom, an alkyl group optionally having a substituent having 1 to 20 carbon atoms, or an aryl optionally having a substituent. Each of which may be bonded to each other to form a ring, Ra ⁷ is a hydrogen atom or a methyl group, Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and n1 is 0. It is an integer of ~ 4.)
Formula (II)

(In the general formula (II), Ra ⁹ is a hydrogen atom or a methyl group, Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. N2 is an integer of 0 to 4)
(2) The positive photosensitive resin composition according to (1), wherein the polymer (A) has a weight average molecular weight of 5000 or more.
(3) The positive photosensitive resin composition according to (1) or (2), wherein the photoacid generator (B) has an oxime sulfonate structure represented by the following general formula (b1).
Formula (b1)

(In the general formula (b1), R ¹ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heteroaryl group which may have a substituent, or Represents an aryl group which may have a substituent.)
(4) (D) As a basic compound, at least one of a compound represented by the following general formula (a), a compound represented by the following general formula (b), and a compound represented by the following general formula (c) The positive photosensitive resin composition according to any one of (1) to (3), comprising:
Formula (a)

(In general formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cycloalkyl group which may have a substituent having 3 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom, Y ¹ represents an oxygen atom or a —NH— group, and p1 represents an integer of 1 to 3.)
General formula (b)

(In the general formula (b), R ⁸ , R ⁹ and R ¹⁰ may each have a hydrogen atom, an alkyl group which may have a substituent having 1 to 6 carbon atoms, or a substituent. Represents an aryl group or an optionally substituted cycloalkyl group having 3 to 10 carbon atoms.)
Formula (c)

(5) The positive photosensitive resin composition according to any one of (1) to (4), wherein Ra ¹ , Ra ² , Ra ³ , and Ra ⁵ in the general formula (I) are hydrogen atoms. .
(6) The positive photosensitive resin composition according to any one of (1) to (5), wherein n1 in the general formula (I) and n2 in the general formula (II) are 0.
(7) The positive photosensitive resin composition according to any one of (1) to (6), wherein the repeating unit represented by the general formula (I) is represented by the following general formula (III).
Formula (III)

(8) The photoacid generator (B) has the following general formula (OS-3), the following general formula (OS-4), the following general formula (OS-5), the following general formula (b2) the following general formula ( The positive photosensitive resin composition of any one of Claims 1-7 which is a compound represented by either B3) and general formula (OS-2).

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are each independently Represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n1 to n3 each independently represents 1 or 2, and m1 to m3 each independently represents an integer of 0 to 6.)

(In the general formula (b2), R ³¹ represents an alkyl group, a cycloalkyl group, or an aryl group, X ¹¹ represents an alkyl group, an alkoxy group, or a halogen atom, and m11 represents an integer of 0 to 3. Or when it is 3, the plurality of X ¹¹ may be the same or different.)
Formula (B3)

(In the formula (B3), R ⁴³ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heteroaryl group which may have a substituent, or a substituent. X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and n4 is 0. Represents an integer of ~ 5.)

(In the general formula (OS-2), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group, R ¹⁰² represents an alkyl group or an aryl group, and R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxy group Represents a carbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group, and two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring; .)
(9) (1) A step of applying the photosensitive resin composition according to any one of (1) to (8) on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer,
(5) a step of etching the substrate using the formed resist pattern as a mask; and
(6) A method for producing a pattern comprising the step of stripping the resist pattern.
(10) The method for producing a pattern according to (9), including a step of post-baking the resist pattern at 100 to 160 ° C. after the developing step and before the etching step.
(11) The pattern manufacturing method according to (9) or (10), wherein the substrate is an ITO substrate, a molybdenum substrate, or a silicon substrate.
(12) A pattern formed by the pattern manufacturing method according to any one of (9) to (11).
(13) An ITO pattern formed by the pattern manufacturing method according to any one of (9) to (11).
(14) An organic EL display device or a liquid crystal display device comprising the ITO pattern according to (13).

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in the high resolution and high heat resistance of the photosensitive resin composition can be provided.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit and an upper limit.

（一般式（Ｉ）中、Ｒａ¹〜Ｒａ⁶は、それぞれ、水素原子、炭素数１〜２０の置換基を有していてもよいアルキル基、または、置換基を有していてもよいアリール基であり、互いに結合して環を形成していてもよい。Ｒａ⁷は水素原子またはメチル基であり、Ｒａ⁸はハロゲン原子、水酸基または炭素数１〜３のアルキル基である。ｎ１は０〜４の整数である。）
Ｒａ¹〜Ｒａ⁶におけるアルキル基としては、それぞれ、置換基を有していてもよい炭素原子数が１〜２０の直鎖状、分岐状、環状のアルキル基、置換基を有していてもよいフェニル基を挙げることができ、炭素原子数１〜１２の直鎖状、炭素原子数３〜１２の分岐状、または、炭素原子数５〜１０の環状のアルキル基が好ましくい。アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、イソプロピル基、イソブチル基、ｓ−ブチル基、ｔｅｒｔ−ブチル基、イソペンチル基、ネオペンチル基、１−メチルブチル基、イソヘキシル基、２−エチルヘキシル基、２−メチルヘキシル基、シクロヘキシル基、シクロペンチル基、２−ノルボルニル基を挙げることができる。
Ｒａ¹〜Ｒａ⁶におけるアリール基の具体例としては、フェニル基、ナフチル基を挙げることができる。
Ｒａ¹〜Ｒａ⁶は、それぞれ、水素原子、炭素原子数１〜１２の直鎖状、炭素原子数３〜１２の分岐状、または、炭素原子数５〜１０の環状のアルキル基、もしくはフェニル基が好ましく、水素原子、炭素原子数１〜１２までの直鎖状のアルキル基、または、フェニル基がより好ましく、水素原子、メチル基、フェニル基がさらに好ましい。
Ｒａ¹、Ｒａ²、Ｒａ³、Ｒａ⁵は、水素原子であることが好ましく、さらに、Ｒａ¹、Ｒａ²、Ｒａ³、Ｒａ⁵は、水素原子であって、Ｒａ⁴およびＲａ⁶が、それぞれ、上記の基であることがより好ましい。
Ｒａ⁷は水素原子またはメチル基であり、水素原子が好ましい。
Ｒａ⁸はハロゲン原子、水酸基または炭素数１〜３のアルキル基であり、塩素原子、臭素原子、水酸基またはメチル基が好ましい。
ｎ１は０〜４の整数であり、ｎ１は０が好ましい。 <Polymer (A)>
The photosensitive resin composition of the present invention (hereinafter also referred to as “the photosensitive composition of the present invention” or “the composition of the present invention”) is represented by the following general formula (I) as a polymer (A) component. The total of the repeating unit (a1) and the repeating unit (a2) represented by the following general formula (II) is 95 mol% or more of the total repeating units, and the polydispersity (weight average molecular weight / number average molecular weight) is Polymer (A) greater than 2.0 is included.
Formula (I)

(In the general formula (I), Ra ^{1 to} Ra ⁶ are each a hydrogen atom, an alkyl group optionally having a substituent having 1 to 20 carbon atoms, or an aryl optionally having a substituent. Each of which may be bonded to each other to form a ring, Ra ⁷ is a hydrogen atom or a methyl group, Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and n1 is 0. It is an integer of ~ 4.)
The alkyl group in Ra ^{1 to} Ra ⁶ may have a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a substituent. A good phenyl group can be mentioned, and a linear alkyl group having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, or a cyclic alkyl group having 5 to 10 carbon atoms is preferable. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, A cyclopentyl group and 2-norbornyl group can be mentioned.
Specific examples of the aryl group in Ra ^{1 to} Ra ⁶ include a phenyl group and a naphthyl group.
Ra ^{1 to} Ra ⁶ are each a hydrogen atom, a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, or a cyclic alkyl group having 5 to 10 carbon atoms, or a phenyl group. Are preferable, a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, or a phenyl group is more preferable, and a hydrogen atom, a methyl group, or a phenyl group is more preferable.
Ra ¹ , Ra ² , Ra ³ and Ra ⁵ are preferably hydrogen atoms, and Ra ¹ , Ra ² , Ra ³ and Ra ⁵ are hydrogen atoms, and Ra ⁴ and Ra ⁶ are each More preferably, it is the above group.
Ra ⁷ is a hydrogen atom or a methyl group, and preferably a hydrogen atom.
Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, preferably a chlorine atom, a bromine atom, a hydroxyl group or a methyl group.
n1 is an integer of 0 to 4, and n1 is preferably 0.

（一般式（ＩＩ）中、Ｒａ⁹は水素原子またはメチル基であり、Ｒａ¹⁰はハロゲン原子、水酸基または炭素数１〜３のアルキル基である。ｎ１は０〜４の整数である。）
Ｒａ⁹は水素原子またはメチル基であり、水素原子が好ましい。
Ｒａ¹⁰はハロゲン原子、水酸基または炭素数１〜３のアルキル基であり、塩素原子、臭素原子、水酸基またはメチル基が好ましい。
ｎ２は０〜４の整数であり、０が好ましい。 Formula (II)

(In the general formula (II), Ra ⁹ is a hydrogen atom or a methyl group, Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. N1 is an integer of 0 to 4)
Ra ⁹ is a hydrogen atom or a methyl group, preferably a hydrogen atom.
Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and a chlorine atom, a bromine atom, a hydroxyl group or a methyl group is preferable.
n2 is an integer of 0 to 4, and 0 is preferable.

  The component (A) is preferably insoluble or hardly soluble in alkali, and becomes alkali-soluble when the protected hydroxy group of the monomer unit (a1) is decomposed by the action of an acid. It is preferable that As a resin whose solubility in an alkaline developer is increased by the action of such an acid, it has a repeating unit corresponding to hydroxystyrene having the monomer unit (a1), and is decomposed by the action of an acid to increase the solubility in alkali. Resin is used. Here, in the present invention, “alkali-soluble” means a coating film (thickness) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. 3 μm) at 23 ° C. in a 2.38% tetramethylammonium hydroxide aqueous solution is 0.01 μm / second or more. “Alkali insoluble” means that the solution of the compound (resin) is a substrate. The dissolution rate of the coating film (thickness: 3 μm) of the compound (resin) formed by coating on the substrate and heating at 90 ° C. for 2 minutes in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. It means less than 0.01 μm / second.

  The photosensitive resin composition of the present invention is preferably a resin that is deprotected by an acid generated from a photoacid generator upon irradiation with light and increases the solubility in an alkali developer.

  The skeleton of the monomer unit of hydroxystyrene may be partially hydrogenated.

  Specific examples of the polymer (A) used in the present invention are shown below, but the present invention is not limited to the following.

  In the present invention, the content of the monomer unit (a1) in the polymer (A) is preferably from 5 to 90 mol%, more preferably from 10 to 75 mol%, still more preferably from 10 to 75 mol%, based on all repeating units. -45 mol%. Moreover, as content of a monomer unit (a2), 5-95 mol% is preferable with respect to all the repeating units, More preferably, it is 10-85 mol%. In addition, the total of the repeating unit (a1) represented by the following general formula (I) and the repeating unit (a2) represented by the following general formula (II) is more than 98 mol% of all repeating units. preferable.

  The polydispersity of the polymer (A) (sometimes referred to as weight average molecular weight / number average molecular weight, Mw / Mn, molecular weight distribution) is preferably 2.01 to 7.00, and preferably 2.01 to 5. 00 is more preferable, and 2.01 to 4.00 is particularly preferable. By setting the polydispersity to 7.00 or less, the resolution tends to be improved, and the resist pattern can be more effectively suppressed from becoming a tapered shape. On the other hand, if it is 2.00 or less, the resolution is deteriorated and a development residue is generated. Here, the weight average molecular weight and the number average molecular weight are defined by polystyrene conversion values of gel permeation chromatography.

  The weight average molecular weight (Mw) of the polymer (A) is preferably in the range of 5,000 to 300,000, more preferably 5,000 to 100,000, most preferably 5,000 to 60,000. By setting it to 5,000 or more, film loss due to development of the unexposed portion can be suppressed, and by setting it to 300,000 or less, it is more effective that the dissolution rate of the resin itself in alkali is slowed and the sensitivity is lowered. Can be suppressed. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  Moreover, you may use the polymer (A) of the photosensitive composition of this invention in mixture of 2 or more types. The amount of the polymer (A) used is preferably 40 to 99% by weight, more preferably 60 to 98% by weight, still more preferably 80%, based on the total weight of the photosensitive composition (excluding the solvent). ~ 98 wt%.

  The photosensitive resin composition of the present invention is prepared as a solution by dissolving it in a solvent that dissolves each of the above components and then filtering it with a filter having a pore size of about 0.05 μm to 0.2 μm. Examples of the solvent used here include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, 3 -Methyl methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N -Methylpyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetamide, propylene Examples include carbonate and ethylene carbonate. These solvents are used alone or in combination. The selection of the solvent is important because it affects the solubility in the positive photoresist composition of the present invention, the coating property on the substrate, the storage stability, and the like. Further, it is preferable that the amount of water contained in the solvent is small because it affects the performance of the resist.

  Furthermore, the photosensitive resin composition of the present invention preferably has metal impurities such as metal and impurity components such as halogen ions reduced to 100 ppb or less. The presence of a large amount of these impurities is not preferable because it causes malfunctions, defects, and a decrease in yield in manufacturing a semiconductor device.

  The solid content of the photosensitive resin composition is preferably dissolved in the solvent and dissolved in a solid content concentration of 3 to 40%. More preferably, it is 5 to 30%.

<< Synthesis of Polymer (A) >>
The polymer used as the polymer (A) can be synthesized using either a method using a vinyl ether or an acetal exchange method using an alcohol and an alkyl vinyl ether for acetalization. Moreover, in order to synthesize | combine efficiently and stably, the dehydration azeotropic method as shown in a following example can also be used. However, it is not limited to these synthesis methods.

<Photoacid generator (B)>
The photosensitive resin composition of the present invention contains a photoacid generator (B). The radiation-sensitive acid generator used in the present invention is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm and generates an acid, but its chemical structure is not particularly limited. Absent. Further, a radiation-sensitive acid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with the sensitizer. It can be preferably used in combination. The radiation-sensitive acid generator used in the present invention is preferably a radiation-sensitive acid generator that generates an acid having a pKa of 4 or less, and more preferably a radiation-sensitive acid generator that generates an acid having a pKa of 3 or less.

  In the present invention, an oxime sulfonate compound, that is, a compound having an oxime sulfonate residue can be preferably used as the photoacid generator, and the oxime sulfonate compound contains an oxime sulfonate residue represented by the formula (b1). Preferred examples of the compound are:

（一般式（ｂ１）中、Ｒ¹は、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいヘテロアリール基または置換基を有していてもよいアリール基を表す。） Formula (b1)

(In the general formula (b1), R ¹ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heteroaryl group which may have a substituent, or Represents an aryl group which may have a substituent.)

Any group may be substituted, and the alkyl group in R ¹ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
The aryl group for R ¹ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.
As a heteroaryl group of R < ¹ >, the preferable range is the same as the heteroaryl group of R <^22> , R <^25> and R < ²⁸ > in the general formulas (OS-3) to (OS-5) described later.
Two connectors extending from the carbon atom of the general formula (b1) are bonded to a substituent or an atom. Here, the carbon atom of the general formula (b1) is preferably a part of a cyclic structure or bonded to a substituent having a cyclic structure. Such a cyclic structure is preferably a 5-membered ring, a 6-membered ring, or two or three condensed rings thereof. The molecular weight of the compound represented by the general formula (b1) is preferably 100 to 600.

  The compound containing an oxime sulfonate structure represented by the general formula (b1) is also preferably an oxime sulfonate compound represented by the following general formula (b2).

（一般式（ｂ２）中、Ｒ³¹は、アルキル基またはアリール基を表し、Ｘ¹¹は、アルキル基、アルコキシ基、または、ハロゲン原子を表し、ｍ１１は、０〜３の整数を表し、ｍ１１が２または３であるとき、複数のＸ¹¹は同一でも異なっていてもよい。）

(In General Formula (b2), R ³¹ represents an alkyl group or an aryl group, X ¹¹ represents an alkyl group, an alkoxy group, or a halogen atom, m11 represents an integer of 0 to 3, and m11 represents When it is 2 or 3, the plurality of X ¹¹ may be the same or different.)

The alkyl group as X ¹¹ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X ¹¹ is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X ¹¹ is preferably a chlorine atom or a fluorine atom.
m11 is preferably 0 or 1.
In the general formula (b2), m11 is 1, X ¹¹ is a methyl group, the substitution position of X ¹¹ is an ortho position, R ³¹ is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  The compound containing the oxime sulfonate structure represented by the general formula (b1) is more preferably an oxime sulfonate compound represented by the following general formula (B3).

（式（Ｂ３）中、Ｒ⁴³は式（ｂ１）におけるＲ¹と同義であり、Ｘ¹は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、シアノ基またはニトロ基を表し、ｎ４は０〜５の整数を表す。）

(In formula (B3), R ⁴³ has the same meaning as R ¹ in formula (b1), and X ¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano A group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As n4, 0-2 are preferable and 0-1 are especially preferable.

  Specific examples of the compound represented by the general formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino). ) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4- Methoxyphenyl] acetonitrile, α-[(4- Toluene sulfonyl) -4-methoxyphenyl] can be mentioned acetonitrile.

  Specific examples of preferred oxime sulfonate compounds include the following compounds (i) to (viii) and the like, and these can be used alone or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

  The compound containing an oxime sulfonate structure represented by the general formula (b1) is preferably a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ^{105 to} R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.
As R ^{121 to} R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and an embodiment in which at least two of R ^{121 to} R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Among these, an embodiment in which R ^{121 to} R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  The compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).

In the general formula (OS-2), R ¹⁰¹ , R ¹⁰² , R ^{121 to} R ¹²⁴ have the same meanings as those in the formula (OS-1), and preferred examples thereof are also the same.
Among these, the embodiment in which R ¹⁰¹ in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2). And R ¹⁰¹ is most preferably a cyano group, a phenyl group, or a naphthyl group.

  In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

  Specific examples (exemplary compounds b-1 to b-34) of the compounds represented by the general formula (OS-1) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto. Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, Ts represents a tosyl group, and Ph represents a phenyl group.

  Among the above compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.

  In the present invention, as a compound containing the oxime sulfonate structure represented by the general formula (b1), the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5) It is also preferable that it is an oxime sulfonate compound represented by these.

（一般式（ＯＳ−３）〜一般式（ＯＳ−５）中、Ｒ²²、Ｒ²⁵およびＲ²⁸はそれぞれ独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ²³、Ｒ²⁶およびＲ²⁹はそれぞれ独立に水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ²⁴、Ｒ²⁷およびＲ³⁰はそれぞれ独立にハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表し、Ｘ¹〜Ｘ³はそれぞれ独立に酸素原子または硫黄原子を表し、ｎ¹〜ｎ³はそれぞれ独立に１または２を表し、ｍ¹〜ｍ³はそれぞれ独立に０〜６の整数を表す。）

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represents an integer of 0 to 6 Represents.)

In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.

Examples of the alkyl group for R ²² , R ²⁵ and R ²⁸ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, tert-butyl group, n-pentyl group, An n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group and benzyl group are preferred.
Examples of the substituent that the alkyl group in R ²² , R ²⁵ and R ²⁸ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, An aminocarbonyl group is mentioned.

Moreover, in said general formula (OS-3)-(OS-5), as an aryl group in R <^22> , R <^25> and R < ²⁸ >, the aryl group with a total carbon number of 6-30 which may have a substituent is mentioned. preferable.

As the aryl group for R ²² , R ²⁵ and R ²⁸ , a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group are preferable. .
Examples of the substituent which the aryl group in R ²² , R ²⁵ and R ²⁸ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxy group Examples include a carbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

Moreover, in said general formula (OS-3)-(OS-5), as heteroaryl group in R <^22> , R <^25> and R < ²⁸ >, C4-30 heteroaryl which may have a substituent Groups are preferred.

In the general formulas (OS-3) to (OS-5), at least one ring of the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be a heteroaromatic ring. For example, a heteroaromatic ring and benzene The ring may be condensed.
As the heteroaryl group in R ²² , R ²⁵ and R ²⁸ , which may have a substituent, a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and And a group in which one hydrogen atom is removed from a ring selected from the group consisting of benzimidazole rings.
Examples of the substituent that the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryl Examples thereof include an oxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

In the general formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. preferable.
In the general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in the compound is an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
In the general formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have a substituent. Here, the substituent which the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have may be the alkyl group or aryl group in R ²² , R ²⁵ and R ²⁸ . Examples of the same group as a good substituent can be given.

The alkyl group for R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.
As the alkyl group for R ²³ , R ²⁶ and R ²⁹ , methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group Group, chloromethyl group, bromomethyl group, methoxymethyl group and benzyl group are preferred, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n -Hexyl group is preferable, methyl group, ethyl group, n-propyl group, n-butyl group and n-hexyl group are more preferable, and methyl group is preferable.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Specifically, the aryl group in R ²³ , R ²⁶ and R ²⁹ is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.

Examples of the halogen atom for R ²³ , R ²⁶ and R ²⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Among these, a chlorine atom and a bromine atom are preferable.

In the general formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.
In the general formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n ^{1 to} n ³ each independently represent 1 or 2, and when X ^{1 to} X ³ are O, n ^{1 to} n ³ are each independently 1 is preferable, and when X ^{1 to} X ³ are S, n ^{1 to} n ³ are preferably 2 each independently.

In the general formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Represent. Among them, R ²⁴ , R ²⁷ and R ³⁰ are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.
In the general formulas (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.

Examples of the alkyl group for R ²⁴ , R ²⁷ and R ³⁰ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a tert-butyl group, an n-pentyl group, An n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group and benzyl group are preferred.
Examples of the substituent that the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, An aminocarbonyl group is mentioned.

In the general formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.

The alkyloxy group for R ²⁴ , R ²⁷ and R ³⁰ is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group.
Examples of the substituent that the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. And aminocarbonyl group.

In the general formulas (OS-3) to (OS-5), examples of the aminosulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, and a methylphenylaminosulfonyl group. Group and aminosulfonyl group.

In the general formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group. It is done.

In the general formulas (OS-3) to (OS-5), m ^{1 to} m ³ each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.

  The compound containing an oxime sulfonate structure represented by the general formula (B1) is particularly an oxime sulfonate compound represented by any one of the following general formulas (OS-6) to (OS-11). preferable.

（式（ＯＳ−６）〜（ＯＳ−１１）中、Ｒ³⁰¹〜Ｒ³⁰⁶はアルキル基、アリール基またはヘテロアリール基を表し、Ｒ³⁰⁷は、水素原子または臭素原子を表し、Ｒ³⁰⁸〜Ｒ³¹⁰、Ｒ³¹³、Ｒ³¹⁶およびＲ³¹⁸はそれぞれ独立に水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基またはクロロフェニル基を表し、Ｒ³¹¹およびＲ³¹⁴はそれぞれ独立に水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、Ｒ³¹²、Ｒ³¹⁵、Ｒ³¹⁷およびＲ³¹⁹はそれぞれ独立には水素原子またはメチル基を表す。）

(In the formulas (OS-6) to (OS-11), R ^{301 to} R ³⁰⁶ represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ^{308 to} R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; R ³¹¹ and R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.)

R ^{301 to} R ³⁰⁶ in the general formulas (OS-6) to (OS-11) have the same meanings as R ²² , R ^25, and R ^{28 in the} general formulas (OS-3) to (OS-5), The preferred embodiment is also the same.
R ³⁰⁷ in the general formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ^{308 to} R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ in the general formulas (OS-6) to (OS-11) are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, chloro Represents a methyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, and an alkyl group having 1 to 8 carbon atoms; More preferably, it is more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.
R ³¹¹ and R ³¹⁴ in the general formula (OS-8) and the general formula (OS-9) each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and preferably a hydrogen atom.
R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ in the general formulas (OS-8) to (OS-11) represent a hydrogen atom or a methyl group, and are preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.

  Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include the following exemplary compounds, but the present invention is not limited thereto. Absent.

  In the positive photosensitive resin composition of the present invention, a photoacid generator represented by formula (1) or formula (2) can also be used.

（式中、Ｒ⁵、Ｒ⁶およびＲ⁷はそれぞれ独立に、置換基を有していてもよい、アルキル基又は芳香族基を表し、アルキル基の場合、互いに連結し環を形成してもよく、Ｒ⁸およびＲ⁹はそれぞれ独立に、置換基を有していてもよい芳香族基を表し、Ｘ^-はＢＹ₄ ^-、ＰＹ₆ ^-、ＡｓＹ₆ ^-、ＳｂＹ₆ ^-、または、式（３）若しくは式（４）で表される一価のアニオンを表し、Ｙはそれぞれ独立に、ハロゲン原子を表す。）

(In the formula, R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group or an aromatic group which may have a substituent, and in the case of an alkyl group, they may be linked to each other to form a ring. R ⁸ and R ⁹ each independently represents an optionally substituted aromatic group, and X ⁻ represents BY ₄ ⁻ , PY ₆ ⁻ , AsY ₆ ⁻ , SbY ₆ ⁻ , or the formula ( 3) represents a monovalent anion represented by the formula (4), and each Y independently represents a halogen atom.)

（式中、Ｒ²¹、Ｒ²²およびＲ²³はそれぞれ独立に、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のフッ素原子を有するアルキル基、または、Ｒ²¹とＲ²²とが互いに炭素原子数２〜６のアルキレン基若しくは炭素原子数２〜６のフッ素原子を有するアルキレン基で結合した環を表す。）

(Wherein R ²¹ , R ²² and R ²³ are each independently an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or R ²¹ and R ²² are And represents a ring bonded to each other by an alkylene group having 2 to 6 carbon atoms or an alkylene group having 2 to 6 carbon atoms.

In formula (1), the alkyl group in R ⁵ , R ⁶ and R ⁷ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a tertiary butyl group (tert-butyl group). More preferred. In the formula (1), when two or more of R ⁵ , R ⁶ and R ⁷ are alkyl groups, it is preferable that the two or more alkyl groups are connected to each other to form a ring, As such a ring form, in the form containing a sulfur atom, a 5-membered ring (thiacyclopentane) and a 6-membered ring (thiacyclohexane) are more preferable, and a 5-membered ring is more preferable.
The aromatic group for R ⁵ , R ⁶ and R ⁷ is preferably an aromatic group having 6 to 30 carbon atoms and may have a substituent. Such aromatic groups include phenyl, naphthyl, 4-methoxyphenyl, 4-chlorophenyl, 4-methylphenyl, 4-tertiarybutylphenyl, 4-phenylthiophenyl, 2,4 , 6-trimethylphenyl group, 4-methoxy-1-naphthyl group, and 4- (4′-diphenylsulfoniophenylthio) phenyl group.
In the formula (2), preferred examples of the aromatic group in R ⁸ and R ⁹ are the same as the examples of R ⁵ , R ⁶ and R ⁷ .
As the substituent in R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , an aromatic group is particularly preferable. Specifically, a phenyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, 4- (4 ′ A -diphenylsulfoniophenylthio) phenyl group is particularly preferred.
Moreover, the acid generator represented by Formula (1) or Formula (2) may combine with any of R ^{5 to} R ⁹ to form a multimer such as a dimer. For example, the 4- (4′-diphenylsulfoniophenylthio) phenyl group is an example of a dimer, and the counter anion in the 4- (4′-diphenylsulfoniophenylthio) phenyl group is BY ₄ ⁻ , PY ₆ ⁻ , AsY ₆ ⁻ , SbY ₆ ⁻ , or a monovalent anion represented by formula (3) or formula (4) is preferable.

In formulas (1) and (2), Y in BY ₄ ⁻ , PY ₆ ⁻ , AsY ₆ ⁻ and SbY ₆ ⁻ in X ⁻ is preferably a fluorine atom or a chlorine atom, and fluorine in terms of anion stability. Atoms are particularly preferred.
In formula (3) and formula (4), examples of the alkyl group having 1 to 10 carbon atoms in R ²¹ , R ²² and R ²³ include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, and a cyclohexyl group. And octyl group. Examples of the alkyl group having a fluorine atom having 1 to 10 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a dodecafluoropentyl group, and a perfluorooctyl group. Can be mentioned. Among these, R ²¹ , R ²² and R ²³ are preferably alkyl groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 6 carbon atoms, and 1 carbon atom. Alkyl groups having 4 to 4 fluorine atoms are particularly preferred in terms of sensitivity.
In formulas (3) and (4), when R ²¹ and R ²² are bonded to each other to form a ring, the alkylene group having 2 to 6 carbon atoms may be ethylene, propylene, butylene, or pentylene. Group, hexylene group and the like. Examples of the alkylene group containing a fluorine atom having 2 to 6 carbon atoms include a tetrafluoroethylene group, a hexafluoropropylene group, an octafluorobutylene group, a decafluoropentylene group, and a dodecafluorohexylene group. it can. Among these, when R ²¹ and R ²² are bonded to each other to form a ring, they are preferably bonded with an alkylene group having 2 to 6 carbon atoms, and a fluorine atom having 2 to 4 carbon atoms. It is more preferable to bond with an alkylene group having a hydrogen atom, and bonding with an alkylene group having 3 fluorine atoms is particularly preferable in terms of sensitivity.
In Formula (3) and Formula (4), R ²¹ and R ²² are a ring in which they are bonded to each other by an alkylene group having 2 to 6 carbon atoms or an alkylene group having 2 to 6 carbon atoms. Preferably there is.
In Formula (1) and Formula (2), X ⁻ is preferably BY ₄ ⁻ , PY ₆ ⁻ , or a monovalent anion represented by Formula (3) or Formula (4). It is particularly preferable in terms of sensitivity that it is a monovalent anion represented by (3).

  Moreover, as an acid generator represented by Formula (1), the acid generator represented by following formula (5) can also be used.

（式中、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²およびＲ¹³はそれぞれ独立に、置換基を有していてもよい、アルキル基または芳香族基を表し、Ａｒ³およびＡｒ⁴はそれぞれ独立に、置換基を有していてもよい二価の芳香族基を表し、Ｘ^1-およびＸ^2-はそれぞれ独立に、ＢＹ₄ ^-、ＰＹ₆ ^-、ＡｓＹ₆ ^-、ＳｂＹ₆ ^-、または、前記式（３）若しくは前記式（４）で表される一価のアニオンを表し、Ｙはそれぞれ独立に、ハロゲン原子を表す。）

(In the formula, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group or an aromatic group which may have a substituent, and Ar ³ and Ar ⁴ are each independently substituted. X ¹⁻ and X ²⁻ each independently represents BY ₄ ⁻ , PY ₆ ⁻ , AsY ₆ ⁻ , SbY ₆ ⁻ , or the above formula ( 3) or a monovalent anion represented by the formula (4), and each Y independently represents a halogen atom.)

Preferred embodiments of the alkyl group and aromatic group in R ¹⁰ , R ¹¹ , R ¹² and R ¹³ of formula (5) are preferred for the alkyl group and aromatic group in R ⁵ , R ⁶ and R ⁷ of formula (1). This is the same as the embodiment.
The divalent aromatic group in Ar ³ and Ar ⁴ in the formula (5) is preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group.
Examples of the compound represented by formula (1) or formula (2) are given below. Among these, PAG-7, PAG-12, and PAG-14 are preferable, and PAG-12 is particularly preferable.

  Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl-4- (2 ′) -Hydroxy-1'-tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy) -1′-tetradecaoxy) phenyliodonium p-toluenesulfonate and the like.

As the photoacid generator used in the present invention, trichloromethyl-s-triazines and quaternary ammonium salts are also preferably used.
As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s -Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methyl) Butylphenyl) ethenyl] - bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methoxynaphthyl) - bis (4,6-trichloromethyl) -s-triazine are exemplified.

  As quaternary ammonium salts, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Examples thereof include dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, and benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate.

In the present invention, the following photoacid generators can also be suitably used.

The (B) photoacid generator used in the present invention is most preferably an oxime sulfonate system from the viewpoint of higher heat resistance and resolution, but an onium system can also be suitably used.
In the photosensitive resin composition of the present invention, (B) the photoacid generator is based on 100 parts by mass of all resin components (preferably solid content, more preferably polymer (A)) in the photosensitive resin composition. It is preferable to use 0.1-10 mass parts, and it is more preferable to use 0.5-10 mass parts.

  The photosensitive resin composition of the present invention may contain a 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. The 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is always 1 or less.

<Solvent (C)>
The photosensitive resin composition of the present invention contains a solvent (C). The photosensitive resin composition of the present invention is a solution in which components (D) to (I) as optional components are dissolved in a solvent (C) in addition to the polymer (A) and the photoacid generator (B) as essential components. It is preferable to be prepared as
As the solvent (C) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like.

As the (C) solvent used in the photosensitive resin composition of the present invention, for example,
(1) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;
(3) Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate;
(4) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(5) Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;

(6) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
(7) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
(8) Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate;
(9) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
(10) Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether;

(11) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate;
(12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
(13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, propionate Aliphatic carboxylic acid esters such as isobutyl acid, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl Other esters such as butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(15) Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;

(16) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(17) Examples include lactones such as γ-butyrolactone.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.

The component (C) is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof. A solvent having a boiling point of 200 ° C. or lower or a mixture thereof is more preferable, and a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. and a solvent having a boiling point of 160 ° C. or higher and 200 ° C. or lower is more preferable.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

  Content of the solvent (C) in the photosensitive resin composition of this invention is 50- per 100 mass parts of all the resin components (preferably solid content, more preferably the said polymer (A)) in the photosensitive resin composition. It is preferably 3,000 parts by mass, more preferably 100 to 2,000 parts by mass, and even more preferably 150 to 1,500 parts by mass.

<Basic compound (D)>
The photosensitive resin composition of the present invention preferably contains a basic compound (D).
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -Undecene and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

（一般式（ａ)中、Ｒ²は炭素数が１〜６の置換基を有していてもよいアルキル基または炭素数３〜１０の置換基を有していてもよいシクロアルキル基を表す。Ｘは酸素原子または硫黄原子を表す。Ｙ¹は酸素原子または−ＮＨ−基を表す。ｐ１は１〜３の整数を表す。）
一般式（ｂ）

（一般式（ｂ）中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰は、それぞれ、水素原子、炭素数１〜６の置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、炭素数３〜１０の置換基を有していてもよいシクロアルキル基を表す。）
一般式（ｃ）

In addition, the photosensitive resin composition of the present invention is particularly composed of a compound represented by the following general formula (a), a compound represented by the following general formula (b), and a compound represented by the following general formula (c). At least one kind is preferable, and a compound represented by the general formula (a) is more preferable.
Formula (a)

(In general formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cycloalkyl group which may have a substituent having 3 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom, Y ¹ represents an oxygen atom or a —NH— group, and p1 represents an integer of 1 to 3.)
General formula (b)

(In the general formula (b), R ⁸ , R ⁹ and R ¹⁰ may each have a hydrogen atom, an alkyl group which may have a substituent having 1 to 6 carbon atoms, or a substituent. Represents an aryl group or an optionally substituted cycloalkyl group having 3 to 10 carbon atoms.)
Formula (c)

（一般式（ＩＩ）中、Ｒ³は炭素数が１〜６のアルキル基または炭素数３〜１０のシクロアルキル基を表す。Ｙ²は酸素原子または−ＮＨ−基を表す。ｐ２は１〜３の整数を表す。） The compound represented by the general formula (a) is a thiourea compound represented by the following general formula (II) where X is a sulfur atom from the viewpoint of exposure margin, that is, represented by a thiourea bond. It preferably has a partial structure.

(In General Formula (II), R ³ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Y ² represents an oxygen atom or an —NH— group. Represents an integer of 3.)

（一般式（ＩＩＩ）中、Ｒ⁴は炭素数が１〜６のアルキル基または炭素数３〜１０のシクロアルキル基を表す。ｐ３は１〜３の整数を表す。） The compound (D) is more preferably a thiourea compound represented by the following general formula (III), that is, it preferably contains a morpholino group.

(In general formula (III), R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. P3 represents an integer of 1 to 3)

Examples of the alkyl group having 1 to 6 carbon atoms in R ^{2 to} R ⁴ of the compounds represented by the general formulas (a), (II), and (III) include a methyl group, an ethyl group, a propyl group, and n-butyl. Group, sec-butyl group, tert-butyl group and other alkyl groups having 1 to 4 carbon atoms are preferable, linear alkyl groups having 1 to 4 carbon atoms are more preferable, and methyl group is particularly preferable.

Examples of the cycloalkyl group having 3 to 10 carbon atoms in R ^{2 to} R ⁴ of the compounds represented by the general formulas (a), (II), and (III) include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group. A cycloalkyl group having 3 to 10 carbon atoms such as cycloalkyl group having 5 to 10 carbon atoms is more preferable, and a cyclohexyl group is particularly preferable.

  Specific examples of the basic compound (D) represented by the general formula (a) include the following compounds, but the present invention is not limited thereto.

  These basic compounds (D) can be used alone or in admixture of two or more.

  In the present invention, the addition amount of the basic compound (D) is from the viewpoint of satisfying all of sensitivity, resolution and exposure margin, all resin components in the photosensitive resin composition (preferably solid content, more preferably (A) copolymer) is usually used in the range of 0.001 to 20% by weight, preferably 0.005 to 10% by weight, and most preferably 0.01 to 5% by weight. The

<Other ingredients>
In addition to the component (A), the component (B), the component (C) and the component (D), the positive photosensitive resin composition of the present invention includes (N) a sensitizer, G) an adhesion improver and (I) a surfactant can be preferably added. Further, the positive photosensitive resin composition of the present invention includes a plasticizer, a thermal radical generator, an antioxidant, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives can be added.

Sensitizer (N)
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with the photoacid generator (B). The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

Adhesion improver (G)
The photosensitive resin composition of the present invention may contain an adhesion improving agent (G). The adhesion improver (G) that can be used in the photosensitive resin composition of the present invention is an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum. It is a compound that improves adhesion to an insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improver (G) used in the present invention is for the purpose of modifying the interface, and any known one can be used without any particular limitation.
Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
The content of the adhesion improving agent (G) in the photosensitive resin composition of the present invention is based on 100 parts by mass of all resin components (preferably solid content, more preferably the polymer (A)) in the photosensitive resin composition. 0.1 to 20 parts by mass is preferable, and 0.5 to 10 parts by mass is more preferable.

Surfactant (I)
The photosensitive resin composition of the present invention may contain a surfactant (I). As the surfactant (I), any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by JEMCO), Mega Fuck (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Made by Co., Ltd.), Asahi Guard, Surflon (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), and the like.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following general formula (1), and is a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.

（式（１）中、Ｒ⁴⁰¹およびＲ⁴⁰⁴はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ⁴⁰²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴⁰⁴は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す重量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。） General formula (1)

(In the formula (1), R ⁴⁰¹ and R ⁴⁰⁴ each independently represents a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10% by mass to 80% by mass. Q represents a numerical value of 20% by mass to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

The L is preferably a branched alkylene group represented by the following general formula (2). R ⁴⁰⁵ in the general formula (2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Or the alkyl group of 3 is more preferable. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

General formula (2)

  The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of (I) surfactant in the photosensitive resin composition of the present invention is 100 mass of all resin components (preferably solid content, more preferably (A) copolymer) in the photosensitive resin composition. The amount is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass, and still more preferably 0.01 to 1 part by mass with respect to parts.

Antioxidant The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.

  As a commercial item of a phenolic antioxidant, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (made by Ciba Japan Co., Ltd.) are mentioned, for example.

The content of the antioxidant is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

[Pattern manufacturing method]
Next, the pattern manufacturing method of the present invention will be described.
The pattern manufacturing method of the present invention includes the following steps (1) to (6).
(1) The process of applying the photosensitive resin composition of this invention on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer,
(5) a step of etching the substrate using the formed resist pattern as a mask; and
(6) A step of removing the resist pattern.
Each step will be described below in order.

In the application step (1), the positive photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
In the solvent removing step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.

  In the exposure step (3), the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, (B) the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the protected hydroxy group of the monomer unit (a1) of hydroxystyrene contained in the component (A) is hydrolyzed to produce a phenolic hydroxyl group.

  In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment (post-bake): Post Exposure Bake (hereinafter also referred to as “PEB”) is performed as necessary. it can. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The pattern manufacturing method of the present invention preferably includes a step of post-baking and thermosetting the resist pattern after the development step and before the etching step.

  In the pattern production method of the present invention, it is preferable to promote hydrolysis of acid-decomposable groups without causing a crosslinking reaction by performing PEB at a relatively low temperature. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 1 to 60 minutes.

In the developing step (4), the polymer having a liberated phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
In the pattern manufacturing method of the present invention, it is preferable to include a post-baking step between the developing step (4) and the etching step described later. It is more preferable to include a step of post-baking at ° C. In the post-baking step after the developing step (4), the obtained positive image is heated, so that the effect of improving the dimensional stability of the etching is obtained.
More preferably, the post-baking step after the development step and before the etching step is 120 to 150 ° C. By performing PEB at a relatively low temperature, an effect of improving etching dimensional stability without causing heat flow of the resist pattern can be obtained.
The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 1 to 60 minutes.
Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition is prepared by mixing the essential components (A) to (C) in a predetermined ratio and by an arbitrary method, stirring and dissolving. For example, it is possible to prepare a resin composition by mixing the components (A) to (C) in advance in a solution in which the components (A) to (C) are previously dissolved in the solvent (D) and mixing them at a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<Application process and solvent removal process>
A desired dry coating film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by decompression and / or heating (pre-baking). As the substrate, for example, in the production of a liquid crystal display element, a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as required, and further a transparent conductive circuit layer can be exemplified. Although there is no restriction | limiting in particular as a method of applying the photosensitive resin composition to a board | substrate, Among these, it is preferable to apply | coat a touristic resin composition to a board | substrate in this invention. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Manufacturing with a large substrate is preferable because of high productivity. Here, the large substrate means a substrate having a side of 1 m or more on each side.

  In addition, the heating condition in the (2) solvent removal step is such that the acid-decomposable group is decomposed in the monomer unit (a1) in the component (A) in the unexposed area, and the component (A) is not soluble in the alkaline developer. Although it varies depending on the type and blending ratio of each component, it is preferably about 80 to 130 ° C. for 30 to 120 seconds.

<Exposure process and development process (pattern formation method)>
In the exposure step, the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in the development step, the exposed area is removed using an alkaline developer to form an image pattern.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

  The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, and a desired pattern can be formed.

<Etching process>
The pattern manufacturing method of the present invention includes the step (5) of etching the substrate using the formed resist pattern as a mask.
There is no restriction | limiting in particular as a method of etching the said board | substrate using the said resist pattern as a mask, A well-known method can be used.

<Step of peeling resist pattern>
The pattern manufacturing method of the present invention includes the step (6) of peeling off the resist pattern.
There is no restriction | limiting in particular as a peeling method of the said resist pattern, A well-known method can be used.

<Board>
The substrate used in the pattern manufacturing method of the present invention is not particularly limited. For example, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, an indium oxide (ITO) film doped with tin oxide, or tin oxide. Film, Ni, Cu, Fe, Al, etc. metal substrate; quartz, glass, silicon nitride film, silicone, silicone nitride, polysilicone, silicone oxide, amorphous silicone film, SOG, silicon wafer for semiconductor device manufacturing, liquid crystal device manufacturing A silicon substrate such as a glass square substrate for use; a polymer substrate such as paper, a polyester film, a polycarbonate film, a polyimide film, and other polymer substrates used in an organic EL display device; a ceramic material, or the like can be used. Among them, in the present invention, an ITO substrate, a molybdenum substrate or a silicon substrate is preferable, and an ITO substrate is more preferable.
The shape of the substrate may be a plate shape or a roll shape.

[pattern]
The pattern of the present invention is a pattern obtained by etching the substrate using a resist pattern obtained by curing the photosensitive resin composition of the present invention as a mask. The pattern of the present invention can be preferably used as an ITO pattern, a molybdenum pattern or a silicon pattern, and more preferably used as an ITO pattern.
Since the photosensitive resin composition of the present invention is excellent in sensitivity, resolution and exposure margin, a resist pattern having excellent rectangularity can be obtained. Since the pattern of the present invention is obtained by the pattern manufacturing method of the present invention using the resist pattern, it can be finely processed, and the organic EL display device and the liquid crystal display device can have high-definition display characteristics.

[Organic EL display device, Liquid crystal display device]
The organic EL display device and the liquid crystal display device of the present invention are characterized by comprising the pattern of the present invention. The organic EL display device and the liquid crystal display device of the present invention preferably have an ITO pattern.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a flattening film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, but can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

FIG. 1 is a conceptual diagram illustrating an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

  FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

Synthetic resin (R-1)
113.5 g (0.7 mol) of p-acetoxystyrene was dissolved in 500 ml of propylene glycol monomethyl ether acetate (PGMEA), and dimethyl 2,2′-azobis (2-methyl) at 65-75 ° C. under nitrogen flow and stirring. Propionate) (V-601) 6.6 g (0.025 mol) of PGMEA solution was added, and stirring was continued for 6 hours to carry out a polymerization reaction. It melt | dissolved in 200 ml of methanol, 14 g of sodium methoxide methanol solutions (SM-28) were added, and it was made to react for 3 hours. The mixture was neutralized with hydrochloric acid, diluted with 200 ml of water, diluted with 300 ml of ethyl acetate, and washed three times with water. Thereafter, a white resin was deposited. The resin was filtered off, washed with water and dried. Furthermore, it melt | dissolved in 200 ml of acetone, and it dripped and reprecipitated, stirring to a 3 liter hexane / ethyl acetate = 10/1 solution. The obtained resin was dried in a vacuum dryer at 40 ° C. for 24 hours to obtain a poly (p-hydroxystyrene) alkali-soluble resin (R-1). The obtained resin had a weight average molecular weight of 15000 and a polydispersity of 3.50.

Resin (R-2)
Poly (p-hydroxystyrene) (Marcalinker S-4P, manufactured by Maruzen Petrochemical Co., Ltd.) was used. The weight average molecular weight was 9400, and the polydispersity was 2.19.

Resin (R-3)
Poly (p-hydroxystyrene) (Marcalinker H-2P, manufactured by Maruzen Petrochemical Co., Ltd.) was used. The weight average molecular weight was 21400, and the polydispersity was 5.78.

Resin (R-4)
(R-4) was obtained by synthesis in the same manner as (R-1). However, the amount of V-601 was changed to 19.8 g (0.075 mol), and the amount of PGMEA as a solvent was changed to 820 ml. The weight average molecular weight of the resin was 4000, and the polydispersity was 3.20.

Resin (R-5)
(R-5) was obtained by synthesis in the same manner as (R-1). However, the above polymerization reaction was dissolved in 50 ml of propylene glycol monomethyl ether acetate (PGMEA), and 113.5 g (0.7 mol) of p-acetoxystyrene and dimethyl 2,2 ′ were added at 75-80 ° C. under nitrogen flow and stirring. -A solution in which 6.6 g (0.025 mol) of azobis (2-methylpropionate) (V-601) was dissolved in 200 ml of PGMEA was added dropwise over 2 hours, and the stirring was continued for another 4 hours. The weight average molecular weight of the obtained resin was 12500, and the polydispersity was 1.57.

Resin (R-6)
(R-6) was obtained by synthesis in the same manner as (R-1). However, the above polymerization reaction was dissolved in 50 ml of propylene glycol monomethyl ether acetate (PGMEA), and 113.5 g (0.7 mol) of p-acetoxystyrene and dimethyl 2,2 ′ were added at 75-80 ° C. under nitrogen flow and stirring. -A solution in which 8.0 g (0.035 mol) of azobis (2-methylpropionate) (V-601) was dissolved in 200 ml of PGMEA was added dropwise over 1 hour, and the stirring was further continued for 4 hours. The obtained resin had a weight average molecular weight of 13,000 and a polydispersity of 1.81.

Resin (R-7)
A brominated product of polyparavinylphenol (Marcalinker MB, manufactured by Maruzen Petrochemical Co., Ltd.) was used. The weight average molecular weight was 7200, and the polydispersity was 3.05.

Synthesis of polymer (A-1) 15.6 g of the alkali-soluble resin (R-2) obtained above and 100 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask, distilled under reduced pressure, and water and PGMEA were dissolved. Azeotropic distillation was performed. After confirming that the water content was sufficiently low, 3.2 g of 2,3-dihydrofuran and 0.015 g of p-toluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.090 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water. Then, ethyl acetate and water were distilled off under reduced pressure to obtain a polymer (A-1) which is a soluble resin having a protection rate of 30 mol%.

Synthesis of Polymers (A-2) to (A-5) In the synthesis example of the polymer (A-1), the addition amount of 2,3-dihydrofuran was changed and the others were performed in the same manner, and are shown in the following table. Polymers (A-2) to (A-5) having a protection rate were obtained.

Polymer (A-6), (A-7)
In the synthesis example of the polymer (A-1), 2,3-dihydro-4-methylfuran or 2,3-dihydro-4,5-diphenylbenzofuran was used instead of 2,3-dihydrofuran, respectively. A polymer having the protection ratio shown in FIG.

Polymers (A-8) to (A-10), (A-14)
In the synthesis example of the polymer (A-1), (R-1), (R-3), (R-4), and (R-7) are used instead of (R-2) as the alkali-soluble resin. Thus, a polymer having the following protection ratio was synthesized.

Polymer (A-11), (A-12)
In the synthesis example of the polymer (A-1), polymers having the following protection rates were synthesized using (R-5) and (R-6) instead of (R-2) as the alkali-soluble resin. .

Polymer (A-13)
In the synthesis example of the polymer (A-1), a polymer was synthesized using (R-1) instead of (R-2) and further using ethyl vinyl ether instead of 2,3-dihydrofuran.

(B) Photoacid generator B-1: CGI-1397 (trade name, structure shown below, manufactured by Ciba Specialty Chemicals)
B-2: Structure shown below (synthesis examples will be described later)
B-3: Structure shown below (synthesis examples will be described later)
B-4: Structure shown below (synthesis examples will be described later)
B-5: Structure shown below (synthesis examples will be described later)
B-6: Structure shown below (synthesis example will be described later)
B-7: Structure shown below (Synthesis examples will be described later)
B-8: Structure shown below (synthesized by the method described in US4329300A1)
B-9: Structure shown below (synthesized by the method described in US6965040B1)
B-10: Structure shown below (synthesized by the method described in Angew. Chem. Int. Ed., 2005, vol.44, p.6685)
B-11: Structure shown below (synthesized by the method described in Tetrahedron 1994, 50, p 3195)

<Synthesis of B-2>
Α- (p-Toluenesulfonyloxyimino) phenylacetonitrile (Compound B-2) was synthesized according to the method described in paragraph No. [0108] of JP-T-2002-528451.

<Synthesis of B-3>
1-1. Synthesis of Synthesis Intermediate B-3A 2-Aminobenzenethiol: 31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C.). . Next, 40.6 g of phenylacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour and then at 100 ° C. for 2 hours to cause a reaction. 500 mL of water was added to the resulting reaction solution to dissolve the precipitated salt, toluene oil was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B-3A.

1-2. Synthesis of B-3 2.25 g of the synthetic intermediate B-3A obtained as described above was mixed with 10 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), then placed in an ice bath and the reaction solution was placed at 5 ° C. Cooled to: Next, tetramethylammonium hydroxide: 4.37 g (25% by weight methanol solution, manufactured by Alfa Acer) was added dropwise to the reaction solution, and the mixture was stirred for 0.5 hour in an ice bath to be reacted. Furthermore, 7.03 g of isopentyl nitrite: was dropped while maintaining the internal temperature at 20 ° C. or lower, and after completion of the dropping, the reaction solution was warmed to room temperature and stirred for 1 hour.
Subsequently, after cooling the reaction liquid to 5 ° C. or lower, p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred for 1 hour while maintaining 10 ° C. or lower. Thereafter, 80 mL of water was added and stirred at 0 ° C. for 1 hour. After filtration of the resulting precipitate, 60 mL of isopropyl alcohol (IPA) was added, heated to 50 ° C., stirred for 1 hour, filtered while hot, and dried to obtain B-3 (the aforementioned structure). 8 g was obtained.
¹ H-NMR spectrum (300 MHz, deuterated DMSO ((D ₃ C) ₂ S═O)) of the obtained B-3 is δ = 8.2 to 8.17 (m, 1H), 8.03 to It was 8.00 (m, 1H), 7.95 to 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), 2.45 (s, 3H).
From the above ¹ H-NMR measurement results, it was estimated that the obtained B-3 was a single geometric isomer.

<Synthesis of B-4>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by weight hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, then reslurried with methanol (20 mL), filtered and dried to obtain 2.3 g of B-4 (the above-mentioned structure).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-4 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

<Synthesis of B-5>
2-Naphthol (20 g) is dissolved in N, N-dimethylacetamide (150 mL), potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) are added and reacted at 100 ° C. for 2 hours. It was. To the reaction solution are added water (300 mL) and ethyl acetate (200 mL), and the mixture is separated. The organic layer is concentrated, and then 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water (50 mL) are added. The reaction was performed for 2 hours. The reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid, and then 30 g of polyphosphoric acid was added and reacted at 170 ° C. for 30 minutes. The reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added for liquid separation, and the organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).
Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the resulting ketone compound (10.0 g) and methanol (100 mL) for 24 hours. Heated to reflux. After standing to cool, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and the organic layer was separated four times with 80 mL of water, concentrated and purified by silica gel column chromatography to obtain an oxime compound (5.8 g). Got.
The obtained oxime (3.1 g) was sulfonated in the same manner as B-4 to obtain 3.2 g of B-5 (the aforementioned structure).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-5 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H) , 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 1.4 to 1.2 (m, 8H), 0.8 (t, 3H) there were.

<Synthesis of B-6>
B-6 (the aforementioned structure) was synthesized in the same manner as B-5, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B-5.
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-6 is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (D, 3H).

Ｄ−３：1、5―ジアザビシクロ［4.3.0］-5-ノネン、東京化成株式会社製、Ｄ１３１３
Ｄ−５： ジシクロヘキシルメチルアミン、東京化成株式会社製、Ｄ０８２０
Ｄ−８：２，４，５−トリフェニルイミダゾール、東京化成株式会社製、Ｔ０９９９ (D) Basic compound D-2: CMTU manufactured by Toyo Kasei Kogyo

D-3: 1,5-diazabicyclo [4.3.0] -5-nonene, manufactured by Tokyo Chemical Industry Co., Ltd., D1313
D-5: Dicyclohexylmethylamine, manufactured by Tokyo Chemical Industry Co., Ltd., D0820
D-8: 2,4,5-triphenylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd., T0999

(N) Sensitizer N-1: DBA (trade name, 9,10-dibutoxyanthracene, manufactured by Kawasaki Chemical Industries)
N-2: DETX (trade name, diethylthioxanthone, manufactured by Sun Chemical Co., Ltd.)

（Ｃ） 溶剤
MEDG:ジエチレングリコールエチルメチルエーテル（東邦化学工業株式会社製）
PGMEA:プロピレングリコールモノメチルエーテルアセテート（三井化学株式会社製） (I) Surfactant I-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula

(C) Solvent
MEDG: Diethylene glycol ethyl methyl ether (Toho Chemical Co., Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (Mitsui Chemicals)

[Example 1]
Each component was dissolved and mixed so that it might become the following composition A, and it filtered with the filter made from a polytetrafluoroethylene with a diameter of 0.2 micrometer, and obtained the photosensitive resin composition of Example 1. FIG.
<Composition A>
-Polymer (A): Polyethylene glycol methyl ether acetate solution of polymer A-1 100.0 parts by solid content-Photoacid generator (B): 2.0 parts of B-1 shown below-Compound (D): D-2 0.2 parts as shown in Table 1 and surfactant (I): I-1 0.02 parts shown below

[Examples 2-29, Comparative Examples 1-3]
As in Example 1, except that each component was blended as shown in Table 2 to obtain a photosensitive resin composition of Example. However, when using the sensitizer N, it was used in the same amount as the photoacid generator (B).

[Comparative Example 4]
As a photosensitive resin composition, the composition described in Example 1 of Unexamined-Japanese-Patent No. 2011-75864 was prepared.

  About the Example and comparative example which were obtained by the above, each evaluation shown below was performed.

<Evaluation of sensitivity>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness A photosensitive resin composition layer having a thickness of 1.5 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive composition layer was developed with an alkali developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
By these operations, the optimum i-line exposure (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity. The evaluation criteria are as follows. The results are shown in the table below. When the optimum i-line exposure amount is less than 20 mJ / cm ² , that is, when the evaluation is “1”, it can be said that the sensitivity is the best.
1: 20mJ / cm ² less than ^2: 20mJ / cm 2 or more 30 mJ / cm ² less than 3: 30mJ / cm ² or more 40 mJ / cm ² less than 4: 40mJ / cm ² or more 50 mJ / cm ² less than 5: 50mJ / cm ² or more

<Evaluation of resolution>
Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), and then the solvent was removed on a hot plate at 90 ° C./120 seconds to obtain a film thickness of 1.5 μm. The photosensitive resin composition layer was formed.
Subsequently, an exposure amount (illuminance: 20 mW) that gives a line and space of 10 μm after development for 60 seconds at 23 ° C. using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer for the obtained photosensitive resin composition layer. / Cm ² , i-line), and exposure was performed through a mask having a line and space of 1 to 10 μm.
The exposed substrate was subjected to paddle development at 23 ° C. for 60 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer.
The patterned glass substrate with the photosensitive resin composition layer was cut, and the patterned line and space was observed with a field emission scanning electron microscope S-4800 (manufactured by HITACHI) to evaluate the resolution.
The evaluation criteria are as follows. The results are shown in the table below. When the contact hole of 3 μm can be resolved, that is, when the evaluation is “1” or “2”, the resolution is at a practical level.

1: 2 μm line and space can be resolved 2: 2 μm line and space cannot be resolved 3 μm line and space can be resolved 3: 3 μm line and space cannot be resolved 5 μm line and space can be resolved Resolution: 4: 5 μm line and space cannot be resolved 10 μm line and space can be resolved 5: 10 μm line and space cannot be resolved

<Evaluation of heat resistance>
The shape of the resist pattern resolved at 2 μm was observed using a scanning electron microscope, and as a heat resistance test, the resist pattern was heated on a hot plate at 130 ° C. for 5 minutes (post-baking), and before and after heating. The change in pattern shape was observed and evaluated as follows.
1: No change in pattern shape before and after heating, variation in line width compared to after development <0.1 μm
2: Slight change in pattern shape before and after heating, line width variation 0.1 to 0.2 μm compared to after development
3: Variation in pattern shape before and after heating is seen, line width variation 0.2 to 0.5 μm compared to after development
4: Large change in pattern shape before and after heating, line width variation 0.5 to 1 μm compared to after development
5: Pattern degradation due to thermal dripping after heating The evaluation results of the resist materials, examples and comparative examples are shown in the following table.

Of the following, Example 10 and Example 27 are reference examples.

  As shown in Table 3 above, the photosensitive resin composition of each example was excellent in all evaluations of sensitivity, resolution, and heat resistance in comparison with the photosensitive resin composition of each comparative example. It turned out that the result was obtained. Here, Comparative Example 4 was an additional test of the example of JP 2011-75864 A, and it was found that the evaluation of heat resistance was particularly inferior.

[Example 30 ]
In Example 30 , Example 1 was used except that the photosensitive resin composition of Example 16 was used and the substrate was changed from a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) to a 6 inch silicon wafer. The sensitivity, resolution, and heat resistance were evaluated in the same manner as the evaluation of sensitivity, resolution, and heat resistance performed on the photosensitive resin composition.
The results are shown in Table 3 below.

[Example 31 ] to [Example 32 ]
In Examples 31 and 32 , the photosensitive resin composition of Example 16 was used, and the exposure machine was changed from a Canon-made PLA-501F exposure machine to Nikon Corporation's FX-803M (gh-Line stepper). The sensitivity, resolution, and heat resistance were evaluated in the same manner as in the sensitivity, resolution, and heat resistance evaluation performed on the photosensitive resin composition of Example 1, except that the change was made.
The results are shown in Table 3 below.

[Example 33 ]
In Example 33 , the photosensitive resin composition of Example 16 was used, and the exposure machine was changed from a Canon-made PLA-501F exposure machine to a 355 nm laser exposure machine, and 355 nm laser exposure was performed. The sensitivity, resolution, and heat resistance were evaluated in the same manner as the sensitivity, resolution, and heat resistance evaluation performed on the photosensitive resin composition of Example 1.
In addition, as a 355 nm laser exposure machine, "AEGIS" by a buoy technology company was used (wavelength 355nm, pulse width 6nsec), and the exposure amount was measured using "PE10B-V2" by OPHIR. The results are shown in Table 3 below.

[Example 34 ]
In Example 34 , the photosensitive resin composition of Example 16 was used, and the exposure machine was changed from a Canon-made PLA-501F exposure machine to a UV-LED light source exposure machine. The sensitivity, resolution, and heat resistance were evaluated in the same manner as the sensitivity, resolution, and heat resistance evaluation performed on the photosensitive resin composition.
The results are shown in Table 3 below.

  As shown in Table 3 above, the photosensitive resin compositions of the examples had excellent sensitivity and exposure margin regardless of the substrate and the exposure machine. Moreover, it turned out that the photosensitive resin composition of an Example is excellent also in the resolution, ie, the shape of the formed pattern is also excellent in the rectangularity.

[Example 32]
(Organic EL display device)
An organic EL display device having an ITO pattern was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition described in Example 1 of JP-A-2009-98616 on a substrate and pre-baking (90 ° C. × 2 minutes), after irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a high-pressure mercury lamp from above the mask, developing with an alkaline aqueous solution to form a pattern at 230 ° C. A heat treatment for 60 minutes was performed.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, the photosensitive resin composition of Example 1 was spin-coated on an ITO substrate, pre-baked on a hot plate (90 ° C. × 2 minutes), and then i-line (365 nm) was 20 mJ from above the mask using a high-pressure mercury lamp. After irradiation with / cm ² (illuminance 20 mW / cm ² ), the pattern was formed by developing with an alkaline aqueous solution. Then, the post-baking heat processing for 3 minutes were performed at 140 degreeC before the etching process. Using this resist pattern as a mask, ITO was patterned by wet etching by dipping in an ITO etchant (3% aqueous oxalic acid solution) at 40 ° C./1 min. Thereafter, the resist pattern was peeled off by dipping in a resist stripping solution (MS2001, manufactured by Fuji Film Electronics Materials) at 70 ° C. for 7 min. The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition described in Example 1 of JP-A-2009-98616 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

  As described above, an organic EL display device having an active matrix type ITO pattern formed by connecting each organic EL element to TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

[Example 33]
(Liquid crystal display device)
A liquid crystal display device having an ITO pattern was produced by the following method.
In the active matrix liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 16 was obtained.
That is, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 32.

  When a drive voltage was applied to the obtained liquid crystal display device having the ITO pattern, it was found that the liquid crystal display device showed good display characteristics and high reliability.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims (11)

The total of the repeating unit (a1) represented by the following general formula (I) and the repeating unit (a2) represented by the following general formula (II) is 95 mol% or more of the total repeating units, and the polydispersity degree It contains a polymer (A) having a weight average molecular weight / number average molecular weight of greater than 2.0 and a weight average molecular weight of 11100 or more , a photoacid generator (B), and a solvent (C). A positive photosensitive resin composition.
Formula (I)

(In the general formula (I), Ra ^{1 to} Ra ⁶ are each a hydrogen atom, an alkyl group optionally having a substituent having 1 to 20 carbon atoms, or an aryl optionally having a substituent. Each of which may be bonded to each other to form a ring, Ra ⁷ is a hydrogen atom or a methyl group, Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and n1 is 0. It is an integer of ~ 4.)
Formula (II)

(In the general formula (II), Ra ⁹ is a hydrogen atom or a methyl group, Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. N2 is an integer of 0 to 4) The positive photosensitive resin composition according to claim 1, wherein the photoacid generator (B) has an oxime sulfonate structure represented by the following general formula (b1).
Formula (b1)

(In the general formula (b1), R ¹ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heteroaryl group which may have a substituent, or Represents an aryl group which may have a substituent.) (D) As a basic compound, at least one of a compound represented by the following general formula (a), a compound represented by the following general formula (b) and a compound represented by the following general formula (c) is included. The positive photosensitive resin composition according to claim 1 or 2.
Formula (a)

(In general formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cycloalkyl group which may have a substituent having 3 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom, Y ¹ represents an oxygen atom or a —NH— group, and p1 represents an integer of 1 to 3.)
General formula (b)

(In the general formula (b), R ⁸ , R ⁹ and R ¹⁰ may each have a hydrogen atom, an alkyl group which may have a substituent having 1 to 6 carbon atoms, or a substituent. Represents an aryl group or an optionally substituted cycloalkyl group having 3 to 10 carbon atoms.)
Formula (c)

Formula Ra ^1, Ra ^2, Ra ³ in (I), Ra ⁵ is hydrogen atom, the positive photosensitive resin composition according to any one of claims 1 to 3. The positive photosensitive resin composition according to claim 1, wherein n1 in the general formula (I) and n2 in the general formula (II) are 0. The positive photosensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (I) is represented by the following general formula (III).
Formula (III)

The (B) photoacid generator includes the following general formula (OS-3), the following general formula (OS-4), the following general formula (OS-5), the following general formula (b2), the following general formula (B3), and The positive photosensitive resin composition of any one of Claims 1-6 which is a compound represented by either of general formula (OS-2).

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are each independently Represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n1 to n3 each independently represents 1 or 2, and m1 to m3 each independently represents an integer of 0 to 6.)

(In the general formula (b2), R ³¹ represents an alkyl group, a cycloalkyl group, or an aryl group, X ¹¹ represents an alkyl group, an alkoxy group, or a halogen atom, and m11 represents an integer of 0 to 3. Or when it is 3, the plurality of X ¹¹ may be the same or different.)
Formula (B3)

(In the formula (B3), R ⁴³ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heteroaryl group which may have a substituent, or a substituent. X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and n4 is 0. Represents an integer of ~ 5.)

(In the general formula (OS-2), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group, R ¹⁰² represents an alkyl group or an aryl group, and R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxy group Represents a carbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group, and two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring; .) The photoacid generator (B) has an oxime sulfonate structure represented by the following general formula (b1), and as the basic compound (D), a compound represented by the following general formula (a), the following general formula: The positive photosensitive resin composition according to claim 1, comprising at least one of a compound represented by (b) and a compound represented by the following general formula (c).
Formula (b1)

(In the general formula (b1), R ¹ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heteroaryl group which may have a substituent, or Represents an aryl group which may have a substituent.)
Formula (a)

(In general formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cycloalkyl group which may have a substituent having 3 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom, Y ¹ represents an oxygen atom or a —NH— group, and p1 represents an integer of 1 to 3.)
General formula (b)

(In the general formula (b), R ⁸ , R ⁹ and R ¹⁰ may each have a hydrogen atom, an alkyl group which may have a substituent having 1 to 6 carbon atoms, or a substituent. Represents an aryl group or an optionally substituted cycloalkyl group having 3 to 10 carbon atoms.)
Formula (c)

(1) The process of applying the photosensitive resin composition of any one of Claims 1-8 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer,
(5) a step of etching the substrate using the formed resist pattern as a mask; and
(6) A method for producing a pattern comprising the step of stripping the resist pattern. The manufacturing method of the pattern of Claim 9 including the process of post-baking the said resist pattern at 100-160 degreeC after the said image development process and before an etching process. The pattern manufacturing method according to claim 9, wherein the substrate is an ITO substrate, a molybdenum substrate, or a silicon substrate.

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