JP5462904B2 - Photosensitive resin composition and method for producing pattern using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition and a method for producing a pattern using the same. Furthermore, the present invention relates to a method for manufacturing an organic EL display device or a liquid crystal display device including the pattern manufacturing method, and a pattern manufactured by the pattern manufacturing method. More specifically, the present invention relates to a positive photosensitive resin composition suitable for forming resist etching of electronic parts such as liquid crystal display devices and organic EL display devices, and a pattern manufacturing method using the same.

  An organic EL display device, a liquid crystal display device, and the like are provided with a metal wiring pattern such as a patterned ITO film. A widely known method for forming a pattern such as an ITO film is to apply a photosensitive resin composition on the ITO film, remove the solvent, expose and develop, and etch the ITO film using the formed pattern as a mask for processing. It has been.

  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 with high definition, high resolution of a photosensitive resin composition that functions as a mask during etching is required.

  For example, Patent Document 1 discloses a monomer unit of a hydroxystyrene monomer and a monomer unit of a hydroxystyrene monomer in which a hydroxyl group is protected with an acid-decomposable group, as a photosensitive resin composition capable of obtaining a high-definition and fine pattern shape. The radiation sensitive resin composition containing the copolymer which consists of is disclosed. Further, Patent Document 2 discloses a positive photoresist in which a photoacid generator and a tertiary amine compound having an ether bond are blended with a resin that becomes alkali-soluble by the action of an acid from an insoluble or hardly soluble state with respect to alkali. A composition is disclosed.

JP 9-325473 A Japanese Patent Laid-Open No. 10-326015

  Here, as a trend of development in recent years, there is a tendency to pursue a composition having an absorption region matched to an exposure wavelength of a short wave for high resolution, and a tendency to seek a material transparent to visible light. . However, such a composition requires the use of an expensive exposure apparatus with good resolving power such as an i-line stepper. The present invention has been accomplished in view of the above circumstances, and is highly sensitive and uses an i-line stepper using an inexpensive gh-line scanner or a low NA (aperture) exposure apparatus (NA = 0.1 or less). An object is to provide a photosensitive resin composition having excellent resolution and rectangularity.

  Under such circumstances, the inventors of the present invention have conducted intensive studies, and as a result, have found that the above-described problems can be solved by employing a specific sensitizer. Such a sensitizer has an absorption region in long waves (ghi line, gh line), high i-line absorption, gh absorption, and good electron transfer efficiency, so it contributes appropriately to photoacid generators. In addition, sensitivity, resolution, and rectangularity can be improved.

（一般式（０）中、Ｒ¹およびＲ²は、それぞれ、アリール基、またはエチレン結合を１つ以上有するヘテロ環構造を表す。Ｌ¹はエチレン結合を２〜４個有する２〜４価の連結基を表す。ｎおよびｍは、それぞれ、１または２を表す。）
＜２＞Ｌ¹が、−（ＣＲ＝ＣＲ）ｐ−（Ｒは水素原子またはメチル基、ｐは２以上の整数）、またはエチレン結合を１つ以上有するヘテロ環構造を少なくとも有する＜１に記載の感光性樹脂組成物。
＜３＞（Ｃ）一般式（Ｏ）で表される化合物おけるエチレン結合の数が４〜１４である、＜１＞または＜２＞に記載の感光性樹脂組成物。
＜４＞Ｒ¹およびＲ²における、アリール基、またはエチレン結合を１つ以上有するヘテロ環構造は、それぞれ、環状構造として、単環のみを含む、＜１＞〜＜３＞のいずれかに記載の感光性樹脂組成物。
＜５＞Ｒ¹およびＲ²が、それぞれ、置換基を有していてもよいフェニル基、または、下記一般式（Ｏ−１）で表される基である、＜１＞〜＜４＞のいずれかに記載の感光性樹脂組成物。
一般式（Ｏ−１）

（一般式（Ｏ−１）中、Ｒは置換基を表し、ｒは０〜２の整数である。）
＜６＞Ｌ¹が下記一般式（Ｏ−２）または（Ｏ−３）で表される基である、＜１＞〜＜４＞のいずれかに記載の感光性樹脂組成物。
一般式（Ｏ−２）

（一般式（Ｏ−２）中、Ｓ１は１〜６の整数である。）
一般式（Ｏ−３）

（一般式（Ｏ−３）中、Ｓ２は２〜４の整数である。）
＜７＞Ｒ¹およびＲ²が、それぞれ、置換基を有していてもよいフェニル基、または、下記一般式（Ｏ−１）で表される基であり、Ｌ¹が下記一般式（Ｏ−２）または（Ｏ−３）で表される基である、＜１＞〜＜４＞のいずれかに記載の感光性樹脂組成物。
一般式（Ｏ−１）

（一般式（Ｏ−１）中、Ｒはハロゲン原子または炭素数１〜３のアルキル基であり、ｒは０〜２の整数である。）
一般式（Ｏ−２）

（一般式（Ｏ−２）中、Ｓ１は１〜６の整数である。）
一般式（Ｏ−３）

（一般式（Ｏ−３）中、Ｓ２は２〜４の整数である。）
＜８＞化学増幅型感光性樹脂組成物である、＜１＞〜＜７＞のいずれかに記載の感光性樹脂組成物。
＜９＞（Ａ）酸分解性基で保護されたモノマー単位を含有する重合体が、酸分解性基で保護されたヒドロキシスチレン由来のモノマー単位または酸分解性基で保護された保護カルボキシル基を有するモノマー単位を含む、＜１＞〜＜８＞のいずれかに記載の感光性樹脂組成物。
＜１０＞（Ａ）酸分解性基で保護されたモノマー単位を含有する重合体が下記一般式（Ｉ）〜（ＩＩＩ）の少なくとも１つを含む、＜１＞〜＜９＞のいずれかに記載の感光性樹脂組成物。

（一般式（Ｉ）中、Ｒ²、Ｒ³、Ｒ⁴は、それぞれ、水素原子またはメチル基を表し、Ｒ⁵は、置換基を有していてもよい、直鎖、分岐または環状の炭素数１〜６のアルキル基を表す；
一般式（ＩＩ）中、Ｒａ¹〜Ｒａ⁶は、それぞれ、水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基、または置換基を有していてもよいアリール基を表し、Ｒａ²とＲａ³、Ｒａ⁴とＲａ⁵は、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を表し、Ｒａ⁸は、ハロゲン原子、水酸基または炭素数１〜３のアルキル基を表し、ｎ１は、０〜４の整数を表す；
一般式（ＩＩＩ）中、Ｒ¹およびＲ²は、それぞれ、水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基であり、Ｒ³は、アルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
＜１１＞（Ａ）酸分解性基で保護されたモノマー単位を含有する重合体が、さらに、ヒドロキシ基スチレン由来のモノマー単位を有する、＜１＞〜＜１０＞のいずれかに記載の感光性樹脂組成物。
＜１２＞（Ｂ）光酸発生剤が、オキシムスルホネート化合物またはオニウム塩化合物である、＜１＞〜＜１１＞のいずれかに記載の感光性樹脂組成物。
＜１３＞（１）＜１＞〜＜１２＞のいずれか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。
＜１４＞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、＜１３＞に記載のパターンの製造方法。
＜１５＞前記基板が、ＩＴＯ基板、モリブデン基板、シリコン基板、Ｃｕ基板、または、Ａｌ基板であることを特徴とする＜１３＞または＜１４＞に記載のパターンの製造方法。
＜１６＞＜１３＞〜＜１５＞のいずれかに記載のパターンの製造方法を含む、有機ＥＬ表示装置または液晶表示装置の製造方法。
＜１７＞＜１＞〜＜１２＞のいずれかに記載の感光性樹脂組成物を硬化してなる硬化膜。 Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <17>.
<1> (A) a polymer component containing a polymer containing a monomer unit protected with an acid-decomposable group,
(B) a photoacid generator,
(C) a compound represented by the following general formula (0), and
(D) solvent,
Containing a photosensitive resin composition.

(In the general formula (0), R ¹ and R ² each represent an aryl group or a heterocyclic structure having one or more ethylene bonds. L ¹ is a 2-4 valent group having 2-4 ethylene bonds. Represents a linking group, and n and m each represent 1 or 2.)
<2> L ¹ is, - (CR = CR) p- (R is a hydrogen atom or a methyl group, p is an integer of 2 or more) having at least <claimed in 1 hetero ring having, or one or more ethylenic bonds Photosensitive resin composition.
<3> (C) The photosensitive resin composition according to <1> or <2>, wherein the number of ethylene bonds in the compound represented by the general formula (O) is 4 to 14.
<4> The aryl group or the heterocyclic structure having one or more ethylene bonds in R ¹ and R ² each includes only a single ring as the cyclic structure, according to any one of <1> to <3>. Photosensitive resin composition.
<5> R < ¹ > and R < ² > are each a phenyl group which may have a substituent, or a group represented by the following general formula (O-1), <1> to <4> The photosensitive resin composition in any one.
Formula (O-1)

(In general formula (O-1), R represents a substituent, and r is an integer of 0 to 2.)
<6> The photosensitive resin composition according to any one of <1> to <4>, wherein L ¹ is a group represented by the following general formula (O-2) or (O-3).
Formula (O-2)

(In general formula (O-2), S1 is an integer of 1-6.)
General formula (O-3)

(In general formula (O-3), S2 is an integer of 2 to 4.)
<7> R ¹ and R ² are each a phenyl group which may have a substituent, or a group represented by the following general formula (O-1), and L ¹ is represented by the following general formula (O -2) or the photosensitive resin composition according to any one of <1> to <4>, which is a group represented by (O-3).
Formula (O-1)

(In general formula (O-1), R is a halogen atom or a C1-C3 alkyl group, and r is an integer of 0-2.)
Formula (O-2)

(In general formula (O-2), S1 is an integer of 1-6.)
General formula (O-3)

(In general formula (O-3), S2 is an integer of 2 to 4.)
<8> The photosensitive resin composition according to any one of <1> to <7>, which is a chemically amplified photosensitive resin composition.
<9> (A) A polymer containing a monomer unit protected with an acid-decomposable group is a hydroxystyrene-derived monomer unit protected with an acid-decomposable group or a protected carboxyl group protected with an acid-decomposable group. The photosensitive resin composition in any one of <1>-<8> containing the monomer unit which has.
<10> (A) The polymer containing a monomer unit protected with an acid-decomposable group includes at least one of the following general formulas (I) to (III), and any one of <1> to <9> The photosensitive resin composition as described.

(In the general formula (I), R ² , R ³ and R ⁴ each represent a hydrogen atom or a methyl group, and R ⁵ represents a linear, branched or cyclic carbon which may have a substituent. Represents an alkyl group of formula 1-6;
In general formula (II), Ra ^{1 to} Ra ⁶ are each a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group. And Ra ² and Ra ³ , Ra ⁴ and Ra ⁵ may be bonded to each other to form a ring. Ra ⁷ represents a hydrogen atom or a methyl group, Ra ⁸ represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and n1 represents an integer of 0 to 4;
In general formula (III), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is Represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may combine to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group Represents. )
<11> (A) The photosensitivity according to any one of <1> to <10>, wherein the polymer containing a monomer unit protected with an acid-decomposable group further has a monomer unit derived from a hydroxy group styrene. Resin composition.
<12> The photosensitive resin composition according to any one of <1> to <11>, wherein the (B) photoacid generator is an oxime sulfonate compound or an onium salt compound.
<13> (1) The process of applying the photosensitive resin composition in any one of <1>-<12> 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 peeling off the resist pattern.
<14> The method for producing a pattern according to <13>, including a step of post-baking the resist pattern at 100 to 160 ° C. after the developing step and before the etching step.
<15> The method for producing a pattern according to <13> or <14>, wherein the substrate is an ITO substrate, a molybdenum substrate, a silicon substrate, a Cu substrate, or an Al substrate.
<16> A method for producing an organic EL display device or a liquid crystal display device, comprising the method for producing a pattern according to any one of <13> to <15>.
<17> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <12>.

  According to the present invention, it is possible to provide a photosensitive resin composition having high sensitivity and excellent resolution and rectangularity. In particular, an inexpensive low NA (aperture) exposure apparatus (NA = 0.1) can be used without using an expensive exposure apparatus with good resolving power such as an i-line stepper or a short-wave exposure light source. The present invention is highly valuable in that these performances can be achieved.

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. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL display device in the present invention refers to an organic electroluminescence display device. The polydispersity in the present invention refers to the value of Mw / Mn.

The photosensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) is (A) a polymer component including a polymer containing a monomer unit protected with an acid-decomposable group, (B And (C) a photoacid generator, (C) a compound represented by the following general formula (0), and (D) a solvent. The photosensitive resin composition of the present invention is preferably used as a chemically amplified positive photosensitive resin composition.
Hereinafter, the composition of the present invention will be described in detail.

(A) Polymer component containing a polymer containing a monomer unit protected with an acid-decomposable group The composition of the present invention comprises (A) a monomer unit protected with an acid-decomposable group as a polymer component. Including the containing polymer.
(A) The polymer component is preferably insoluble or hardly soluble in alkali, and when the protected group (acid-decomposable group) of the monomer unit protected by the action of an acid is decomposed. The polymer component is preferably alkali-soluble. Here, in the present invention, “alkali-soluble” means that a polymer coating film (thickness 3 μm) formed by applying a solution of the polymer component on a substrate and heating at 90 ° C. for 2 minutes, The dissolution rate in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. is 0.01 μm / second or more. “Alkali insoluble” means that the polymer solution is applied on a substrate, 90 The dissolution rate of the polymer coating film (thickness: 3 μm) formed by heating at 2 ° C. for 2 minutes in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. is less than 0.01 μm / second. That means.

  The component (A) used in the present invention has a polymer having a monomer unit (a1) protected with an acid-decomposable group (hereinafter, simply referred to as “monomer unit (a1)”). The monomer unit (a1) protected with an acid-decomposable group is preferably a monomer unit derived from hydroxystyrene protected with an acid-decomposable group or a monomer unit having a protected carboxyl group protected with an acid-decomposable group. .

<Monomer unit derived from hydroxystyrene protected with an acid-decomposable group>
The skeleton of the monomer unit derived from hydroxystyrene may be o-, m-, or p-hydroxystyrene, but the p-hydroxystyrene skeleton is preferable from the viewpoint of the pattern shape after development. The skeleton of the monomer unit derived from hydroxystyrene may be partially hydrogenated.

  Furthermore, the skeleton of the monomer unit derived from hydroxystyrene may have a substituent other than the hydroxy group protected by a hydroxy group (hydroxyl group) and an acid-decomposable group. Examples of such a substituent include an alkyl group, an alkoxy group, an aralkyl group, and an aryl group.

  Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a t-butyl group. Are preferably those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and examples of the alkenyl group include those having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Four groups are preferable, and the aryl group is preferably a group having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group, and an anthracenyl group.

  Substituents other than hydroxy groups (hydroxyl groups) and hydroxy groups protected by acid-decomposable groups include hydroxyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), nitro groups, cyano groups, and the above alkyls. Group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, methoxycarbonyl group, ethoxycarbonyl group, etc. Aralkyl groups such as alkoxycarbonyl groups, benzyl groups, phenethyl groups, cumyl groups, aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, acyl groups such as cyanamyl groups and valeryl groups, acyloxy groups such as butyryloxy groups, Above alkenyl group, vinyloxy group, propenylo Shi group include an allyloxy group, an alkenyloxy group such as a butenyloxy group, the above-mentioned aryl group, an aryloxy group such as phenoxy group, aryloxycarbonyl group such as benzoyloxy group.

  In the present invention, in the hydroxystyrene-derived monomer unit (a1) protected with an acid-decomposable group contained in the component (A), the protective group protecting the hydroxy group is not particularly limited. The protecting group protecting the hydroxy group is preferably a silyl group, cumylcarbonyl group, acetal group, tetrahydropyranyl group, tetrahydrofuranyl group, enol group, enolcarbonyl group, tertiary alkyl group, tertiary alkyl group, A tertiary alkylcarbonyl group, a tertiary alkyloxycarbonyl group, and the like. More preferred are a tertiary alkylcarbonyl group, a tertiary alkyloxycarbonyl group, a cumylcarbonyl group, an acetal group, a tetrahydropyranyl group, and a tetrahydrofuranyl group. Most preferred is an acetal group.

  The component (A) used in the present invention is an acid in an alkali-soluble resin as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It can be obtained by reacting a precursor of a group capable of decomposing, or copolymerizing an alkali-soluble resin monomer having a group capable of decomposing with an acid with various monomers.

<Monomer unit having a protected carboxyl group protected with an acid-decomposable group>
The monomer unit having a protected carboxyl group protected by an acid-decomposable group is a monomer unit having a protected carboxyl group in which the carboxyl group of the monomer unit having a carboxyl group is protected by an acid-decomposable group. .
The monomer unit having a carboxyl group that can be used for the monomer unit having a protected carboxyl group protected with an acid-decomposable group is not particularly limited, and a known monomer unit can be used. For example, a monomer unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid, or an ethylenically unsaturated group and an acid And a monomer unit having a structure derived from an anhydride.
Examples of the acid-decomposable group include a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group) and a group that is relatively hardly decomposed by an acid (for example, t- Tertiary alkyl groups such as butyl ester groups and tertiary alkyl carbonate groups such as t-butyl carbonate groups) can be used.
In addition, details of the monomer unit in which the carboxyl group is protected with an acid-decomposable group can be referred to the descriptions in paragraph numbers 0029 to 0044 of JP-A No. 2011-215580.

（一般式（Ｉ）中、Ｒ²、Ｒ³、Ｒ⁴は、それぞれ独立に水素原子またはメチル基を表し、Ｒ⁵は、置換基を有していてもよい、直鎖、分岐または環状の炭素数１〜６のアルキル基を表す；
一般式（ＩＩ）中、Ｒａ¹〜Ｒａ⁶は、それぞれ独立に水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基、または置換基を有していてもよいアリール基を表し、Ｒａ²とＲａ³、Ｒａ⁴とＲａ⁵は、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を表し、Ｒａ⁸は、ハロゲン原子、水酸基または炭素数１〜３のアルキル基を表し、ｎ１は、０〜４の整数を表す；
一般式（ＩＩＩ）中、Ｒ¹およびＲ²は、それぞれ、水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基であり、Ｒ³は、アルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。） (A) The monomer unit (a1) protected with an acid-decomposable group is preferably at least one of the following general formulas (I) to (III), and at least one of the general formulas (I) or (II) More preferably.

(In the general formula (I), R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group, and R ⁵ is a linear, branched or cyclic group which may have a substituent. Represents an alkyl group having 1 to 6 carbon atoms;
In general formula (II), Ra ^{1 to} Ra ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group. Ra ² and Ra ³ , Ra ⁴ and Ra ⁵ may be bonded to each other to form a ring. Ra ⁷ represents a hydrogen atom or a methyl group, Ra ⁸ represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and n1 represents an integer of 0 to 4;
In general formula (III), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is Represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may combine to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group Represents. )

(General formula (I))
R ² is a hydrogen atom or a methyl group, preferably a hydrogen atom.
One of R ³ and R ⁴ is preferably a hydrogen atom and the other is a methyl group.
R ⁵ is methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, s-butyl group, t-butyl group, neopentyl group, s-pentyl group, t-pentyl group, s- Examples include hexyl group, t-hexyl group, s-heptyl group, t-heptyl group, cyclopentyl group, cyclohexyl group, and the like, and methyl group, ethyl group, propyl group, t-butyl group, and cyclohexyl group are preferable.
Examples of the substituent that R ⁵ may have include an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, Examples include aralkylthio groups, thiophenecarbonyloxy groups, thiophenemethylcarbonyloxy groups, and heterocyclic residues such as pyrrolidone residues. These substituents preferably have 12 or less carbon atoms. Further, these groups may be further substituted with these groups. R ⁵ preferably has no substituent.

(General formula (II))
Ra ^{1 to} Ra ⁷ are preferably hydrogen atoms.
Ra ⁸ is preferably a halogen atom.
n1 is preferably 0 or 1, and more preferably 0.

(General formula (III))
When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.

  The protection ratio of the component A is preferably 1 to 60%, more preferably 5 to 50%, and still more preferably 10 to 40%. By setting it as such a range, a sensitivity improves and the difference (discrimination) of the solubility of an exposed part and an unexposed part becomes favorable. The protection rate refers to the ratio of protected groups, where the total of monomer units in the polymer is 100 mol%.

<Other monomer unit (a2)>
The composition of the present invention comprises (A) a polymer component containing (A ′) a monomer unit (a1) protected with an acid-decomposable group and (A ″) another monomer unit (a2). It is preferable to include a polymer containing
The photosensitive resin composition of the present invention is a polymer in which the polymer (A ′) containing the monomer unit (a1) and the polymer (A ″) containing another monomer unit (a2) are different from each other. Even if the component is included, the polymer (A ′) containing the monomer unit (a1) and the polymer (A ″) containing the other monomer unit (a2) are the same copolymer (A). There may be. In the present specification, the term “component A” includes both the polymer (A ′), the polymer (A ″), and the copolymer (A) unless otherwise specified.
In the photosensitive resin composition of the present invention, the polymer (A ′) containing the monomer unit (a1) and the polymer (A ″) containing another monomer unit (a2) have the same copolymer weight. It is preferable that it is a coalescence (A).
That is, it is preferable that the photosensitive resin composition of the present invention contains (A) a copolymer,
(A1) a monomer unit protected with an acid-decomposable group (hereinafter also referred to as “monomer unit (a1)”);
(A2) another monomer unit (hereinafter also referred to as “monomer unit (a2”)),
Is a copolymer containing

The other monomer unit (a2) may be only one type or two or more types.
Other monomer units include, for example, styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimides Examples thereof include compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds.
Moreover, the monomer unit which has an acid group, and the monomer unit which has a crosslinkable group can also be mentioned.

In the present invention, the other monomer unit (a2) is preferably a monomer unit derived from hydroxystyrene, which may be o-,-, or p-hydroxystyrene, but p is preferred from the viewpoint of the pattern shape after development. -A hydroxystyrene skeleton is preferred. The skeleton of the monomer unit of hydroxystyrene may be partially hydrogenated. The skeleton of the monomer unit of hydroxystyrene may have a substituent other than a hydroxy group. Such substituents include hydroxyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), nitro groups, cyano groups, the above alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, aralkyl group such as benzyl group, phenethyl group, cumyl group, aralkyloxy Group, formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, alkenyl group, vinyloxy group, propenyloxy group, allyloxy group, butenyloxy group, etc. An alkenyloxy group, as described above Aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group. However, it preferably has no substituent.
That is, at least one of the other monomer units (a2) is preferably the following monomer unit.

  The ratio of the monomer unit (a1) to the monomer unit (a2) is preferably 1/99 to 60/40, more preferably 5/95 to 50/50, still more preferably 10/90 to 40. / 60.

  The weight average molecular weight (Mw) of the component A is preferably in the range of 2000 to 15000, more preferably 5000 to 12000, and still more preferably 7500 to 12000. By setting it to 2000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 15000 or less, an effect that sensitivity and PED characteristics are improved is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The polydispersity of the component A (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and 1.0 to 1 .5 is more preferred. By setting it as such a range, the difference (discrimination) of the solubility of an exposed part and an unexposed part improves, and rectangularity also becomes favorable.

Although the preferable example of the polymer component (A) used by this invention below is shown, it cannot be overemphasized that this invention is not limited to these.

  The composition of the present invention preferably contains (A) the polymer component in a proportion of 60% by weight or more, more preferably 80% by weight or more, based on the total solid content.

<(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (also referred to as “component (B)”) used in the present invention, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if 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 a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate. However, if the acid is too strong, there arises a problem that the underlying metal is corroded.

  Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, from the viewpoint of insulation, it is preferable to use an onium salt compound and an oxime sulfonate compound, and an oxime sulfonate compound is more preferable. When the oxime sulfonate compound is used, the effect of the compound represented by the general formula (O) of the present invention is more effectively exhibited. This is excellent in terms of sensitivity when the compound represented by the general formula (O) is used. This is because the compound has high light absorption efficiency and low energy level (LUMO), and the energy level of the oxime sulfonate compound. It is estimated that (HOMO) is very close and the electron transfer efficiency is high. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A. It can be illustrated.

  Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).

（一般式（Ｂ１）中、Ｒ²¹は、アルキル基またはアリール基を表す。波線は他の基との結合を表す。） General formula (B1)

(In the general formula (B1), R ²¹ represents an alkyl group or an aryl group. A wavy line represents a bond with another group.)

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
As the alkyl group for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group represented by R ²¹ 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.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

  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、Ｒ⁴²は、アルキル基またはアリール基を表し、Ｘは、アルキル基、アルコキシ基、または、ハロゲン原子を表し、ｍ４は、０〜３の整数を表し、ｍ４が２または３であるとき、複数のＸは同一でも異なっていてもよい。）

(In the general formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and m4 represents 2 Or when it is 3, the plurality of X may be the same or different.)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1.
In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

  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).

（一般式（Ｂ３）中、Ｒ⁴³は式（Ｂ１）におけるＲ⁴²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 General Formula (B3), R ⁴³ has the same meaning as R ⁴² in Formula (B1), and 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, Represents a cyano 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 also 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 are respectively synonymous with those in the formula (OS-1), and preferred examples are also the same.
Among these, an 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 of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include the compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to 1). b-34), but the present invention is not limited thereto.

  In the present invention, the compound containing the oxime sulfonate structure represented by the general formula (B1) is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is 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 above 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.

In the general formulas (OS-3) to (OS-5), as the aryl group in R ²² , R ²⁵ and R ^28, an aryl group having 6 to 30 carbon atoms which may have a substituent may be used. preferable.

Further, in the above general formula (OS-3) ~ (OS -5), as the heteroaryl group in R ^1, heteroaryl group having a total carbon number of 4-30 which may have a substituent is preferable.

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.

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, and 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 are 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.

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.

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.

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.

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.

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.
Further, with respect to each of the substituents of (OS-3) to (OS-5), the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A. The preferred range of groups is likewise preferred.

  The compound containing the 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.)

  Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.

  Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. However, the present invention is not limited to these.

  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 a solid content, more preferably a total of copolymers) in the photosensitive resin composition. 0.1 to 10 parts by mass is preferably used, and 0.5 to 10 parts by mass is more preferably used. Two or more kinds can be used in combination.

（一般式（０）中、Ｒ¹およびＲ²は、それぞれ、アリール基、またはエチレン結合を１つ以上有するヘテロ環構造を表す。Ｌ¹はエチレン結合を２〜４個有する２〜４価の連結基を表す。ｎおよびｍは、それぞれ、１または２を表す。） (C) The compound represented by general formula (0) The photosensitive resin composition of this invention contains the compound represented by general formula (O). In the present invention, the compound represented by the general formula (O) functions as a sensitizer for the photoacid generator. Conventionally, in the field of organic EL display devices, a compound having a structure similar to that of the compound represented by the general formula (O) used in the present invention has been employed. As in the present invention, a photoacid generator sensitizer is used. It was not intended for use. In addition, a compound having a structure similar to that of the compound represented by the general formula (O) has been employed in a field completely different from the present invention, but the purpose to be pursued is also different.

(In the general formula (0), R ¹ and R ² each represent an aryl group or a heterocyclic structure having one or more ethylene bonds. L ¹ is a 2-4 valent group having 2-4 ethylene bonds. Represents a linking group, and n and m each represent 1 or 2.)

R ¹ and R ² each preferably represents an aryl group or a heterocyclic structure having one or more ethylene bonds, and at least one of R ¹ and R ² preferably represents a heterocyclic structure having one or more ethylene bonds. More preferably, R ¹ and R ² both represent a heterocyclic structure having one or more ethylene bonds. The heterocycle preferably contains a sulfur atom.
The cyclic structure possessed by R ¹ and R ² may be a single ring or a condensed ring. In the present invention, each of the heterocyclic structures having one or more aryl groups or ethylene bonds in R ¹ and R ² preferably includes only a single ring as the cyclic structure. In this case, there may be only one monocycle or two or more, preferably 1 to 4, and more preferably 1.
The ring contained in R ¹ and R ² is exemplified by two or more condensed rings of a 5-membered ring, a 6-membered ring, a 5-membered ring and a 6-membered ring, and a 5-membered ring or a 6-membered ring is preferable.

（一般式（Ｏ−１）中、Ｒは置換基を表し、ｒは０〜２の整数である。） R ¹ and R ² are each preferably a phenyl group which may have a substituent, or a group represented by the following general formula (O-1).
Formula (O-1)

(In general formula (O-1), R represents a substituent, and r is an integer of 0 to 2.)

As for the substituent which the phenyl group may have and the substituent in the general formula (O-1), the mass of one substituent portion per molecule is preferably 250 or less, and 100 or less. Is more preferable. The substituent that the phenyl group may have and the substituent in the general formula (O-1) are each preferably a halogen atom, an alkoxy group, an alkyl group, or an amino group. Are more preferable, and an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 4 carbon atoms is more preferable.
The phenyl group preferably has no substituent.
r is preferably 0 or 1, more preferably 0.

R ¹ and R ² are preferably the same group.

  n and m each represent 1 or 2, each is preferably 1, and both are more preferably 1.

L ¹ may have a cyclic structure, and the cyclic structure may contain an ethylene bond. L ¹ preferably has-(CR = CR) p- (R is a hydrogen atom or a methyl group, p is an integer of 2 or more), or at least a heterocyclic structure having one or more ethylene bonds. A group represented by (O-2) or (O-3) is more preferred, and a group represented by general formula (O-2) is more preferred.
The number of ethylene bonds in L ¹ is preferably 2 or 3, and more preferably 2.

（一般式（Ｏ−２）中、Ｓ１は１〜６の整数である。）
Ｓ１は１〜４の整数が好ましく、１がより好ましい。
一般式（Ｏ−３）

（一般式（Ｏ−３）中、Ｓ２は２〜４の整数である。）
Ｓ２は、２または３が好ましい。 Formula (O-2)

(In general formula (O-2), S1 is an integer of 1-6.)
S1 is preferably an integer of 1 to 4, and more preferably 1.
General formula (O-3)

(In general formula (O-3), S2 is an integer of 2 to 4.)
S2 is preferably 2 or 3.

一般式（Ｏ−５）

一般式（Ｏ−６）

（一般式（Ｏ−４）〜（Ｏ−６）において、Ｒ¹〜Ｒ⁶は、それぞれ、水素原子または置換基である。）
一般式（Ｏ−４）〜（Ｏ−６）において、Ｒ¹〜Ｒ⁶は、それぞれ、水素原子、ハロゲン原子、アルコキシ基、アルキル基がより好ましく、それぞれ、水素原子、炭素数１〜３のアルコキシ基または炭素数１〜４のアルキル基がより好ましく、水素原子がさらに好ましい。 (C) It is preferable that the compound represented by the general formula (O) is a compound represented by any one of the following general formulas (O-4) to (O-6).
General formula (O-4)

General formula (O-5)

General formula (O-6)

(In general formulas (O-4) to (O-6), R ^{1 to} R ⁶ are each a hydrogen atom or a substituent.)
In general formulas (O-4) to (O-6), R ^{1 to} R ⁶ are each more preferably a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group. An alkoxy group or an alkyl group having 1 to 4 carbon atoms is more preferable, and a hydrogen atom is more preferable.

  In the general formula (O), the number of ethylene bonds is preferably 4 to 14, and more preferably 5 to 10.

Although the compound represented by general formula (O) preferably used for this invention below is illustrated, it cannot be overemphasized that this invention is not limited to these. In the following, Me represents a methyl group.

  (C) The compound represented by the following general formula (0) is added in an amount of 0.1 to 100 parts by mass with respect to 100 parts by mass of all resin components (preferably a solid content, more preferably a total of copolymers) in the photosensitive resin composition. It is preferable to use 1-10 mass parts, and it is more preferable to use 0.5-5.0 mass parts. By using the addition amount in this range, the effect of the present invention can be exhibited effectively, and even if there is an influence of absorption by the sensitizing dye, the light reaches the bottom of the film, so the rectangularity is good. Two or more kinds can be used in combination.

<(D) Solvent>
The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the components (A) to (C), which are essential components, and other components described later are dissolved in a solvent (D).
As the solvent (D) 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.

Specific examples of the solvent (D) used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers [0174] to [0178] of JP2011-221494A.
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 (D) is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof, a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., and a boiling point of 160 ° C. 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.

  The content of the solvent (D) in the photosensitive resin composition of the present invention is 50 per 100 parts by weight of all resin components (preferably solid content, more preferably the polymer (A)) in the photosensitive resin composition. It is preferably ˜3,000 parts by weight, more preferably 100 to 2,000 parts by weight, and even more preferably 150 to 1,500 parts by weight.

<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 a basic compound, an adhesion improver, an interface as necessary. An activator and an antioxidant 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.
In the present invention, a sensitizer other than the compound represented by the general formula (O) may be used in combination, but it is preferable that such a sensitizer is not substantially contained. “Substantially not contained” is intended to include, for example, a case where it is blended within a range not exhibiting the effects of the present invention.

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

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.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. It is preferable to use two kinds of heterocyclic amines in combination.

（一般式（Ｑ−ａ）中、Ｒ²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。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。）
本発明で用いられる塩基性化合物は、分子内に少なくとも１つの尿素、もしくはチオ尿素結合で表わされる部分構造を有し、しかもモルフォリノ基、またはピペラジノ基を含有するという構造上の特徴を有する化合物である。 In the present invention, the basic compound is preferably at least one of compounds represented by the following general formulas (Qa), (Qb), and (Qc).

(In the general formula (Qa), R ² represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom. Or -NH- group, p1 represents an integer of 1 to 3)
The basic compound used in the present invention is a compound having a structural feature of having a partial structure represented by at least one urea or thiourea bond in the molecule and containing a morpholino group or a piperazino group. is there.

（一般式（Ｑ−ａ２）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 basic compound is preferably a thiourea compound represented by the following general formula (Q-a2), in which X is a sulfur atom, that is, a partial structure represented by a thiourea bond.

(In the general formula (Q-a2), 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 1 to 3)

（一般式（Ｑ−ａ３）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。） More preferably, the basic compound is a thiourea compound represented by the following general formula (Q-a3), that is, it contains a morpholino group.

(In the general formula (Q-a3), 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 (Qa) to (Qa3) include a methyl group, an ethyl group, a propyl group, and n-butyl. C1-C4 alkyl groups, such as a group, a sec-butyl group, and a t-butyl group, are preferable, a linear C1-C4 alkyl group is more preferable, and a methyl group is especially 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 (Qa) to (Qa3) 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 represented by the general formula (Qa) include the following compounds (C-1) to (C-7), but the present invention is limited to these. It is not something.

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

一般式（Ｑ−ｂ）中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰は、それぞれ独立に水素原子、置換基を有していてもよい炭素数１〜６のアルキル基、置換基を有していてもよいアリール基、または置換基を有していてもよい炭素数３〜１０のシクロアルキル基を表す。

In general formula (Qb), R < ⁸ >, R <^9> , R < ¹⁰ > has a hydrogen atom and the C1-C6 alkyl group which may have a substituent, and a substituent each independently. Or an aryl group which may be substituted or a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent.

Examples of the alkyl group or aryl group having 1 to 6 carbon atoms in R ^{8 to} R ¹⁰ of the compound represented by the general formula (Qb) include a methyl group, an ethyl group, a propyl group, an n-butyl group, sec -A butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group and the like are preferable, a linear alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is particularly preferable.

Examples of the cycloalkyl group having 3 to ¹⁰ carbon atoms in R ^{8 to} R ¹⁰ of the compound represented by the general formula (Qb) include 3 to 3 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group. A cycloalkyl group having 10 carbon atoms is preferable, a cycloalkyl group having 5 to 10 carbon atoms is more preferable, and a cyclohexyl group is particularly preferable.

Examples of the substituent that the alkyl group and aryl group in R ^{8 to} R ¹⁰ of the compound represented by the general formula (Qb) may have include an alkyl group of R ^{3 in} the general formula (I). It is the same as the preferable substituent which can be made.

  In the present invention, the addition amount of the basic compound is all resin components (preferably solid content, more preferably the (A) polymer in the photosensitive resin composition) from the viewpoint of satisfying all of sensitivity and resolution. ) 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.

Adhesion improving agent The photosensitive resin composition of the present invention may contain an adhesion improving agent. The adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic material 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, and an insulating film. It is a compound that improves the adhesion. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as an adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As a preferable silane coupling agent, for example, the description of paragraph number 0175 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification. 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 in the photosensitive resin composition of the present invention is based on 100 parts by weight of all resin components (preferably solid content, more preferably (A) copolymer) in the photosensitive resin composition. 0.1 to 20 parts by weight is preferable, and 0.5 to 10 parts by weight is more preferable.

Surfactant The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
As preferable examples of the surfactant, for example, the description of paragraph numbers 0184 to 0196 in JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The amount of (I) surfactant added in the photosensitive resin composition of the present invention is 100 weights of all resin components (preferably solid content, more preferably (A) copolymer) in the photosensitive resin composition. The amount is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 1 part by weight 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.
As such an antioxidant, for example, the description of paragraph numbers 0194 to 0196 in JP 2012-042837 A can be referred to, and the contents thereof are incorporated in the present specification.

The content of the antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by weight. 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) 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 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 step (2), the solvent is removed from the applied film by decompression (vacuum) and / or heating to form a dry coating film on the substrate.

  (3) In the exposing step, the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm to 450 nm. In this step, (C) the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the hydroxy group protected by the acid-decomposable 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 Exposure Bake (hereinafter also referred to as “PEB”) can be performed as necessary. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. In the pattern manufacturing method of the present invention, it is also effective to include a step of post-baking and thermosetting the resist pattern after the development step and before the etching step.

The hydroxy group protected with the acid-decomposable group of the monomer unit (a1) of hydroxystyrene contained in the component (A) in the present invention has a low activation energy for acid decomposition, and is an acid derived from a photoacid generator by exposure. Can be easily decomposed to produce a phenolic hydroxyl group, so that a positive image can be formed by development without necessarily carrying out PEB, but it is not essential in the pattern production method of the present invention.
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 to 130 ° C, more preferably 40 ° C to 110 ° C, and particularly preferably 50 ° C to 100 ° C. 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.

(4) In the developing step, the copolymer having a liberated carboxyl group or 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 carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
By performing PEB at a relatively low temperature, it is preferable to promote hydrolysis of the acid-decomposable group without causing a crosslinking reaction. The temperature for performing PEB is preferably 30 ° C to 130 ° C, more preferably 40 ° C to 110 ° C, and particularly preferably 50 ° C to 80 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.
In the pattern manufacturing method of the present invention, it is preferable that a post-baking step is included between (4) the developing step and an etching step described later, and (4) the resist pattern after the developing step and before the etching step. It is more preferable to include a step of post-baking at 100 to 160 ° C. (4) By heating the obtained positive image in the post-baking step after the developing step, the effect of improving etching dimensional stability can be obtained.
The post-baking step after the step (4) developing and before the step (5) etching is more preferably 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 (D) at a predetermined ratio and by any method, and 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.

<(1) Step of applying photosensitive resin composition on substrate and (2) Step of removing solvent>
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). Examples of the substrate include, for example, a glass plate in which a polarizing plate, a black matrix layer and a color filter layer are provided as necessary, and a transparent conductive circuit layer is further provided in the production of a liquid crystal display element. 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.

  Further, the heating condition in the step (2) is a range in which 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 alkali 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.

<(3) Step of exposing and (4) Step of developing (pattern forming method)>
In the step (3), 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 step (4), an 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 ultra-high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used, and g-line (436 nm), i-line (365 nm), h-line (405 nm). Actinic rays having a wavelength of 300 nm to 450 nm such as) 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.
As the mask used in the step (3), it is preferable to use a halftone phase mask capable of obtaining a pattern having a plurality of thicknesses at a time.

  The developer used in the step (4) 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.

<(5) Step of etching>
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.

<(6) Step of peeling resist pattern>
The pattern production method of the present invention includes the step (6) of peeling 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 Silicon substrates such as glass square substrates for use; paper, polyester film, polycarbonate film, polyimide film, polymer substrates such as other polymer substrates used in organic EL display devices; ceramic materials, Ti substrates, Al substrates, etc. may be used it can. Among these, in the present invention, it is preferably an ITO substrate, a molybdenum substrate, a silicon substrate, a Cu substrate, or an Al substrate, more preferably an ITO substrate, a molybdenum substrate, or a silicon substrate, and an ITO substrate. Is more preferable.
The shape of the substrate may be a plate shape or a roll shape.

[Curing film]
In the present invention, (4) after the developing step, the pattern corresponding to the unexposed area obtained by development is predetermined at a predetermined temperature, for example, 180 to 250 ° C., using a heating device such as a hot plate or an oven. For example, 5 to 60 minutes on a hot plate and 30 to 90 minutes on an oven to form a cured film such as a protective film or an interlayer insulating film having excellent heat resistance and hardness. Can do.
Moreover, when performing heat processing, transparency of a cured film can also be improved by performing in nitrogen atmosphere.
Prior to the heat treatment, it is preferable that the substrate having the cured film formed in a pattern is re-exposed with actinic rays and then heated.

That is, in order to form the cured film of the present invention, it is preferable to include a step of re-exposing with actinic rays between the developing step and the thermosetting step.
The exposure in the re-exposure step may be performed by the same means as in the exposure step. However, in the re-exposure step, the entire surface of the substrate on the side where the film is formed by the photosensitive resin composition of the present invention is used. It is preferable to perform exposure. A preferable exposure amount for the re-exposure step is 100 to 1,000 mJ / cm ² .

[pattern]
The pattern of this invention is a pattern obtained by etching the said board | substrate using the resist pattern obtained by hardening | curing the photosensitive resin composition of this 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 method for producing a pattern of the present invention using the resist pattern, it can be finely processed, and an organic EL display device or a liquid crystal display device can have high definition display characteristics.

[Organic EL display device, Liquid crystal display device]
The photosensitive resin composition of the present invention can also be used as an interlayer insulating film, and an organic EL display device and a liquid crystal display device can be manufactured by the pattern manufacturing method 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 planarizing 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, It 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 weight.

(Synthesis Example 1: Synthesis of polymer PHS-EVE)
20 g of alkali-soluble resin (Marcalinker MS-4P manufactured by Maruzen Petrochemical Co., Ltd.) and 320 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 4.48 g of ethyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added and stirred at room temperature for 1 hour. Thereto, 0.28 g of triethylamine was added to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water, and then ethyl acetate, water, and azeotropic PGMEA were distilled off by distillation under reduced pressure to obtain a polymer PHS-EVE. The weight average molecular weight of the obtained resin was 11,000. The polydispersity was 2.6.
The structure of PHS-EVE is a 1-ethoxyethyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).
PHS-EVE

(Synthesis Example 2: Synthesis of polymer PHS-THF)
15.6 g of alkali-soluble resin (Marcalinker MS-4P: manufactured by Maruzen Chemical Industry Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) are dissolved in a flask and distilled under reduced pressure to azeotropically distill water and PGMEA. Left. After confirming that the water content was sufficiently low, 2.7 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, and then ethyl acetate and water were distilled off under reduced pressure to obtain a polymer PHS-THF, which is a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 2.6.
The structure of PHS-THF is a 2-tetrahydrofuranyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (25 mol% / 75 mol%).
PHS-THF

(Synthesis Example 3: Synthesis of Polymer PHS-THP)
15.6 g of alkali-soluble resin (Marcalinker MS-4P, manufactured by Maruzen Petrochemical Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) are dissolved in a flask and distilled under reduced pressure to azeotropically distill water and PGMEA. did. After confirming that the water content was sufficiently low, 3.4 g of 2,3-dihydropyran and 0.015 g of p-toluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.10 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution and the mixture was further washed with water, and then ethyl acetate and water were distilled off under reduced pressure to obtain PHS-THP which is a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 2.6.
The structure of PHS-THP is a 2-tetrahydropyranyl protector / p-hydroxystyrene copolymer (25 mol% / 75 mol%) of p-hydroxystyrene.

(Synthesis Example 4: THF / MAA / MMA = 60/15/25)
<Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.
<Synthesis of MATHF / MAA / MMA = 60/15/25>
PGMEA (29.6 g) was placed in a three-necked flask and heated to 80 ° C. in a nitrogen atmosphere. MATHF (28.1 g), MMA (7.51 g), MAA (3.87 g), V-601 (1.93 g, 2.8 mol% based on monomer) were dissolved in PGMEA (29.6 g) in the solution. And added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, a polymer was obtained. The weight average molecular weight was 11,000.

(Synthesis Example 5: Polymer A)
15.6 g of alkali-soluble resin (Marcalinker MS-4P, manufactured by Maruzen Petrochemical Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) are dissolved in a flask and distilled under reduced pressure to azeotropically distill water and PGMEA. did. After confirming that the water content was sufficiently low, 3.4 g of 2,3-dihydropyran and 0.015 g of p-toluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.10 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution and the mixture was further washed with water, and then ethyl acetate and water were distilled off under reduced pressure to obtain a polymer A which is a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 2.6.
The structure of the polymer A is 2-tetrahydropyranyl protected body of p-hydroxystyrene / p-hydroxystyrene copolymer (25 mol% / 75 mol%).

(Synthesis Example 6: Polymer B)
The synthesis was performed according to a known synthesis method (functional material, 17 (12), 16 (1997)).
The structure of the polymer B is p-hydroxystyrene-protected t-butylcarboxylic acid / p-hydroxystyrene copolymer (25 mol% / 75 mol%).

(Synthesis Example 7: Polymer C)
The synthesis was performed according to a known synthesis method (functional material, 17 (12), 16 (1997)).
The structure of polymer A is a t-Boc protector / p-hydroxystyrene copolymer (25 mol% / 75 mol%) of MMA.

(Synthesis Example 8: EVE / MMA / HEMA = 60/15/25)
<Synthesis of MAEVE>
After adding phenothiazine (0.5 part) to ethyl vinyl ether (144.2 parts, 2 molar equivalents) and adding dropwise methacrylic acid (86.1 parts, 1 molar equivalent) while cooling the reaction system to 10 ° C or lower. And stirred at room temperature (25 ° C.) for 4 hours. After adding pyridinium p-toluenesulfonate (5.0 parts), the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. Sodium bicarbonate (5 parts) and sodium sulfate (5 parts) were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower. (Bp.) 1-ethoxyethyl methacrylate (MAEVE) (134.0 parts) of a 43-45 ° C./7 mmHg fraction was obtained as a colorless oil.
MMA (methyl methacrylate) was manufactured by Wako Pure Chemical Industries. HEMA (2-hydroxyethyl methacrylate) was manufactured by Wako Pure Chemical Industries.
<Synthesis of MAEVE / MMA / HEMA = 60/15/25>
A polymer was obtained in the same manner as in Synthesis Example 4 except that the material and molar ratio were changed as described above.

(Synthesis Example 9: MATHF / MMA / MAA / HEMA = 60/10/5/25)
MAA (methacrylic acid) manufactured by Wako Pure Chemical Industries, Ltd. was used.
A polymer was obtained in the same manner as in Synthesis Example 4 except that the material and molar ratio were changed as described above.

（Ｂ−２）ＣＧＩ−１３９７（ＢＡＳＦ社製）

(B) Photoacid generator (B-1) The following compound α- (p-toluenesulfonyloxyimino) phenylacetonitrile was synthesized according to the method described in paragraph No. [0108] of JP-T-2002-528451.

(B-2) CGI-1397 (manufactured by BASF)

（Ｔｓは、トシル基（ｐ−トルエンスルホニル基）を表す。）
以下の方法に従って合成した。
２−ナフトール（１０ｇ）、クロロベンゼン（３０ｍＬ）の懸濁溶液に塩化アルミニウム（１０．６ｇ）、２−クロロプロピオニルクロリド（１０．１ｇ）を添加し、混合液を４０℃に加熱して２時間反応させた。氷冷下、反応液に４ＮＨＣｌ水溶液（６０ｍＬ）を滴下し、酢酸エチル（５０ｍＬ）を添加して分液した。有機層に炭酸カリウム（１９．２ｇ）を加え、４０℃で１時間反応させた後、２ＮＨＣｌ水溶液（６０ｍＬ）を添加して分液し、有機層を濃縮後、結晶をジイソプロピルエーテル（１０ｍＬ）でリスラリーし、ろ過、乾燥してケトン化合物（６．５ｇ）を得た。
得られたケトン化合物（３．０ｇ）、メタノール（３０ｍＬ）の懸濁溶液に酢酸（７．３ｇ）、５０重量％ヒドロキシルアミン水溶液（８．０ｇ）を添加し、加熱還流した。放冷後、水（５０ｍＬ）を加え、析出した結晶をろ過、冷メタノール洗浄後、乾燥してオキシム化合物（２．４ｇ）を得た。
得られたオキシム化合物（１．８ｇ）をアセトン（２０ｍＬ）に溶解させ、氷冷下トリエチルアミン（１．５ｇ）、ｐ−トルエンスルホニルクロリド（２．４ｇ）を添加し、室温に昇温して１時間反応させた。反応液に水（５０ｍＬ）を添加し、析出した結晶をろ過後、メタノール（２０ｍＬ）でリスラリーし、ろ過、乾燥してＢ−３を２．３ｇ得た。
なお、Ｂ−３の¹Ｈ−ＮＭＲスペクトル（３００ＭＨｚ、ＣＤＣｌ₃）は、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）であった。 (B-3) The following compound

(Ts represents a tosyl group (p-toluenesulfonyl group).)
Synthesis was performed according to the following method.
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. 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, reslurried with methanol (20 mL), filtered, and dried to obtain 2.3 g of B-3.
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-3 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).

(B-4) The following compound

以下の方法に従って合成した。
２−ナフトール（２０ｇ）をＮ，Ｎ−ジメチルアセトアミド（１５０ｍＬ）に溶解させ、炭酸カリウム（２８．７ｇ）、２−ブロモオクタン酸エチル（５２．２ｇ）を添加して１００℃で２時間反応させた。反応液に水（３００ｍＬ）、酢酸エチル（２００ｍＬ）を添加して分液し、有機層を濃縮後、４８重量％水酸化ナトリウム水溶液（２３ｇ）、エタノール（５０ｍＬ）、水（５０ｍＬ）を添加し、２時間反応させた。反応液を１Ｎ ＨＣｌ水溶液（５００ｍＬ）にあけ、析出した結晶をろ過、水洗してカルボン酸粗体を得た後、ポリリン酸３０ｇを添加して１７０℃で３０分反応させた。反応液を水（３００ｍＬ）にあけ、酢酸エチル（３００ｍＬ）を添加して分液し、有機層を濃縮した後シリカゲルカラムクロマトグラフィーで精製し、ケトン化合物（１０ｇ）を得た。
得られたケトン化合物（１０．０ｇ）、メタノール（１００ｍＬ）の懸濁溶液に酢酸ナトリウム（３０．６ｇ）、塩酸ヒドロキシルアミン（２５．９ｇ）、硫酸マグネシウム（４．５ｇ）を添加し、２４時間加熱還流した。放冷後、水（１５０ｍＬ）、酢酸エチル（１５０ｍL）添加して分液し、有機層を水８０ｍＬで４回分液し、濃縮した後シリカゲルカラムクロマトグラフィーで精製してオキシム化合物（５．８ｇ）を得た。
得られたオキシム化合物（１．８ｇ）をアセトン（２０ｍＬ）に溶解させ、氷冷下トリエチルアミン（１．５ｇ）、ｐ−トルエンスルホニルクロリド（２．４ｇ）を添加し、室温に昇温して１時間反応させた。反応液に水（５０ｍＬ）を添加し、析出した結晶をろ過後、メタノール（２０ｍＬ）でリスラリーし、ろ過、乾燥してＢ−５を３．２ｇを得た。
なお、Ｂ−５の¹Ｈ−ＮＭＲスペクトル（３００ＭＨｚ、ＣＤＣｌ₃）は、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），１．４〜１．２（ｍ，８Ｈ），０．８（ｔ，３Ｈ）であった。

Synthesis was performed according to the following method.
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 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, reslurried with methanol (20 mL), filtered and dried to obtain 3.2 g of B-5.
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.

(B-6) The following compound

(B-7) The following compound

(B-8) The following compound

(B-9) The following compound

(C-1) The following compound (Tokyo Chemical Industry Co., Ltd., D2077)

(C-2) The following compound (Tokyo Chemical Industry, T1196)

(C-3) The following compound

It was synthesized by the following method.
2,4-Dimethoxybenzyl chloride (0.19 mol, 1 eq), triphenylphosphine (PPh3) (0.19 mol, 1 eq), N-methylpyrrolidone (NMP) (100 ml) was added to a 300 ml three-necked flask at 140 ° C. for 4 hours. Stir with heating. Thereafter, the solution was poured into water, KPF6 (0.23 mol, 1.2 eq) was added, and the mixture was stirred at room temperature for 1 hour. As a result, a solid was precipitated, which was filtered, washed with water, and dried to obtain phosphonium salt A. Obtained.
Phosphonium salt A (37.8 mmol, 1 eq) and THF (100 ml) were added to a 500 ml three-necked flask and stirred on an ice bath. NaH (56.7 mmol, 1.5 eq) / THF (20 ml) was slowly added thereto, and after the addition was completed, the mixture was stirred for 15 minutes on an ice bath, and then returned to room temperature. Then, trans-cinnamic aldehyde (37.8 mmol, 1 eq) was added and heated to reflux for 4 hours. Then, when it put into ice water, solid precipitated, it filtered, and also wash | cleaned with methanol, and the compound (C-3) was obtained.

(C-4) The following compound

(C-5) The following compound

Compound (C-5) was obtained in the same manner as in the synthesis example of (C-3) except that 2,4-dimethoxybenzyl chloride was changed to 4-methoxybenzyl chloride.

(C-6) The following compound (manufactured by Kyosei Kogyo Co., D0879)

以下の方法で合成した。
５００ｍｌ三口フラスコにＮａＨ（水酸化ナトリウム、７８．６ｍｍｏｌ，１．５ｅｑ）、ホスホニウム塩Ｂ（５２．４ｍｍｏｌ，１ｅｑ）、ＴＨＦ（テトラヒドロフラン、１００ｍｌ）を加え氷浴上で撹拌した。そこへスルホニウム塩（５２．４ｍｍｏｌ，１ｅｑ）をゆっくりと加え、添加終了後氷浴上で１５分間撹拌し、その後室温に戻した。そこへｔｒａｎｓ−シンナムアルデヒド（５２．４ｍｍｏｌ，１ｅｑ）を加え、３時間加熱還流させた。その後、氷水に投入したところ固体が析出し、ろ過を行い、さらにメタノールリスラリーを行うことで化合物（Ｃ−７）を得た。
ホスホニウム塩Ｂ

(C-7) The following compound

It was synthesized by the following method.
NaH (sodium hydroxide, 78.6 mmol, 1.5 eq), phosphonium salt B (52.4 mmol, 1 eq) and THF (tetrahydrofuran, 100 ml) were added to a 500 ml three-necked flask, and the mixture was stirred on an ice bath. A sulfonium salt (52.4 mmol, 1 eq) was slowly added thereto, and after completion of the addition, the mixture was stirred for 15 minutes on an ice bath and then returned to room temperature. To this, trans-cinnamaldehyde (52.4 mmol, 1 eq) was added and heated to reflux for 3 hours. Then, when it put into ice water, solid precipitated, and it filtered, and also compounded (C-7) by performing methanol reslurry.
Phosphonium salt B

(C-8) The following compound (Tokyo Chemical Industry, T0168)

(C-9) The following compound

(C-10) The following compound DBA (trade name, 9,10-dibutoxyanthracene, manufactured by Kawasaki Chemical Industries)

(D) Solvent propylene glycol monomethyl ether acetate (PGMA) (Mitsui Chemicals)

Basic compound The following compound (Toyo Kasei Kogyo, CMTU)

(Adjustment of photosensitive resin composition)
Each component was dissolved and mixed so that it might become a composition shown in the following table | surface, and it filtered with the filter made from a polytetrafluoroethylene with a diameter of 0.2 micrometer, and obtained the photosensitive resin composition of an Example and a comparative example.
(A) Polymer (B) Photoacid generator (A) 2.7 parts by weight with respect to 100 parts by weight of polymer (C) Compound represented by formula (O) (A) Polymer 100 1.3 parts by weight with respect to parts by weight / basic compound (A) 0.2 parts by weight with respect to 100 parts by weight of polymer Megasurf F-554 (manufactured by DIC Corporation) 0.10 parts by weight・ Solvent PGMEA Non-volatile content was adjusted to 10% by weight of the composition.

  Each evaluation shown below was performed about the photosensitive resin composition of each Example obtained by the above and each comparative example.

<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.
Evaluation was made according to the following criteria.
1: 100mJ / cm ² or more ^2: 45mJ / cm 2 or more 100 mJ / cm ² less than 3: 2.0mJ / cm ² or more 45 mJ / cm ² less than 4: 1.0mJ / cm ² or more 2.0 mJ / cm ² less than 5 : 0.01mJ / cm ² or more 1.0mJ / cm less than ²

<Evaluation of resolution>
A photosensitive resin composition having a film thickness of 1.3 μm was applied to a glass substrate that had been cleaned and treated with HMDS, exposed and developed through a mask, and the smallest pattern that could be resolved in the line and space pattern was defined as the resolution.
1 point: resolution 5 μm or more 2 points: 3.0 μm resolves but 2.5 μm does not resolve 3 points: 2.5 μm resolves but 2.0 μm does not resolve 4 points: 2.0 μm Resolved but 1.5 μm not resolved 5 points: 1.5 μm resolved.

<Evaluation of rectangularity>
A photosensitive resin composition is applied to a cleaned and HMDS-treated glass substrate with a film thickness of 1.3 μm, exposed and developed through a mask, then post-baked at 140 ° C., and 2.5 μm line and space after post-baking. The rectangularity of the shape of the pattern part was evaluated.
1 point: Dome-shaped cross section with no corners and taper angle of less than 45 ° 2 points: Dome shape with cross-sections with no corners and taper angle of 45 ° to less than 60 ° 3 points: Dome shape with cross-sections and corners Tapering angle of 60 ° or more and less than 75 ° 4 points: Cross section has an angle and taper angle of 60 ° or more but less than 75 ° 5 points: Section shape has an angle and taper angle of 75 ° or more

<Overall performance>
The numerical values of the sensitivity, resolution, and rectangularity were summed up, and the total performance was evaluated according to the following criteria.
5: Level that can be used without any problems.
4: Level that can be used without problems.
3: Level that can be used by process handling.
2: Level that cannot be used.
1: Level that cannot be used at all.

  As shown in the above table, the photosensitive resin composition of each example is excellent in any evaluation of sensitivity, resolution, and rectangularity in comparison with the photosensitive resin composition of each comparative example. It was found that the results were obtained. In particular, when the polymer has a monomer unit protected with an acid-decomposable group represented by any one of the general formulas (I) to (III), it can be seen that the effects of the present invention are more effectively exhibited. It was.

(Example 100)
<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 subjected to i-line (365 nm) using a high-pressure mercury lamp from the mask at 20 mJ. 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 being immersed in a resist stripping solution (MS2001, manufactured by Fuji Film Electronics Materials Co., Ltd.) at 70 ° C. for 7 minutes. 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 JP2009-98616A 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 101)
<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 described 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 200 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 100.

  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.

  Recent development trends have tended to pursue compositions having an absorption region in the shortwave, and also sought transparent materials. There has been a tendency to use an expensive exposure apparatus such as an i-line stepper with a good resolving power, a short-wave exposure light source, and a photoacid generator with little absorption in the exposure region. However, in the present invention, by using a sensitizer having an absorption region in a long wave (ghi line, Gh line), an inexpensive low NA (aperture) exposure apparatus can be used (NA = 0.1 or less). Thus, it has become possible to provide a photosensitive resin composition having high sensitivity and excellent resolution and rectangularity. Such a photosensitive resin composition also has an advantage that an improved version of an existing apparatus can be adopted. The sensitizer used in the present invention is colored in the visible range, but there is no problem as long as it is used as an etching material.

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 (17)

(A) a polymer component containing a polymer containing a monomer unit protected with an acid-decomposable group,
(B) a photoacid generator,
(C) a compound represented by the following general formula (0), and
(D) solvent,
Containing a photosensitive resin composition.

(In the general formula (0), R ¹ and R ² each represent an aryl group or a heterocyclic structure having one or more ethylene bonds. L ¹ is a 2-4 valent group having 2-4 ethylene bonds. Represents a linking group, and n and m each represent 1 or 2.) 2. The photosensitive layer according to claim 1, wherein L ¹ has at least a heterocyclic structure having at least one — (CR═CR) p—wherein R is a hydrogen atom or a methyl group, p is an integer of 2 or more, or an ethylene bond. Resin composition. (C) The photosensitive resin composition of Claim 1 or 2 whose number of ethylene bonds in the compound represented by general formula (O) is 4-14. The photosensitive structure according to any one of claims 1 to 3, wherein each of the heterocyclic structure having one or more aryl groups or ethylene bonds in R ¹ and R ² includes only a single ring as the cyclic structure. Resin composition. Each of R ¹ and R ² is a phenyl group which may have a substituent, or a group represented by the following general formula (O-1). The photosensitive resin composition as described.
Formula (O-1)

(In general formula (O-1), R represents a substituent, and r is an integer of 0 to 2.) The photosensitive resin composition of any one of Claims 1-4 whose L < ¹ > is group represented by the following general formula (O-2) or (O-3).
Formula (O-2)

(In general formula (O-2), S1 is an integer of 1-6.)
General formula (O-3)

(In general formula (O-3), S2 is an integer of 2 to 4.) R ¹ and R ² are each a phenyl group which may have a substituent, or a group represented by the following general formula (O-1), and L ¹ is the following general formula (O-2). Or the photosensitive resin composition of any one of Claims 1-4 which is group represented by (O-3).
Formula (O-1)

(In general formula (O-1), R is a halogen atom or a C1-C3 alkyl group, and r is an integer of 0-2.)
Formula (O-2)

(In general formula (O-2), S1 is an integer of 1-6.)
General formula (O-3)

(In general formula (O-3), S2 is an integer of 2 to 4.)   The photosensitive resin composition of any one of Claims 1-7 which is a chemically amplified photosensitive resin composition. (A) A monomer unit containing a monomer unit protected with an acid-decomposable group, a monomer unit derived from hydroxystyrene protected with an acid-decomposable group or a monomer unit having a protected carboxyl group protected with an acid-decomposable group The photosensitive resin composition of any one of Claims 1-8 containing this. The photosensitive polymer according to any one of claims 1 to 9, wherein (A) the polymer containing a monomer unit protected with an acid-decomposable group contains at least one of the following general formulas (I) to (III). Resin composition.

(In the general formula (I), R ² , R ³ and R ⁴ each represent a hydrogen atom or a methyl group, and R ⁵ represents a linear, branched or cyclic carbon which may have a substituent. Represents an alkyl group of formula 1-6;
In general formula (II), Ra ^{1 to} Ra ⁶ are each a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group. And Ra ² and Ra ³ , Ra ⁴ and Ra ⁵ may be bonded to each other to form a ring. Ra ⁷ represents a hydrogen atom or a methyl group, Ra ⁸ represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and n1 represents an integer of 0 to 4;
In general formula (III), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is Represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may combine to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group Represents. ) (A) The photosensitive resin composition of any one of Claims 1-10 in which the polymer containing the monomer unit protected by the acid-decomposable group further has a monomer unit derived from a hydroxy group styrene. . (B) The photosensitive resin composition of any one of Claims 1-11 whose photo-acid generator is an oxime sulfonate compound or an onium salt compound. (1) The process of applying the photosensitive resin composition of any one of Claims 1-12 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 peeling off the resist pattern.   The manufacturing method of the pattern of Claim 13 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.   15. The pattern manufacturing method according to claim 13, wherein the substrate is an ITO substrate, a molybdenum substrate, a silicon substrate, a Cu substrate, or an Al substrate. The manufacturing method of an organic electroluminescent display apparatus or a liquid crystal display device containing the manufacturing method of the pattern of any one of Claims 13-15. The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-12.

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