JPWO2005027145A1 - Radiation sensitive resin composition - Google Patents

Abstract

According to the present invention, a negative comprising a water dispersion of a polythiophene complex which is a complex of poly (3,4-disubstituted thiophene) and a polyanion, and a water-soluble or water-dispersible radiation-sensitive resin. A type radiation sensitive resin composition is provided.

Description

  The present invention relates to a negative radiation-sensitive resin composition comprising a composite composed of poly (3,4-disubstituted thiophene) and a polyanion and a radiation-sensitive resin, and a conductive thin film using the same. And a substrate having the pattern.

The transparent conductive film is used for coating of a substrate such as a liquid crystal display, an electroluminescence display, a plasma display, an electrochromic display, a transparent electrode such as a solar cell and a touch panel, and an electromagnetic shielding material. The most widely applied transparent conductive film is an indium-tin composite oxide (ITO) deposited film. The ITO film having a predetermined pattern is formed on the substrate as follows, for example. First, an ITO film is formed on a substrate by sputtering, and a coating film of a radiation sensitive resin is formed on this surface. Next, irradiation with radiation such as light is performed through a photomask to cure the resin, then development is performed, then the exposed ITO film is dissolved and removed by etching, and finally the cured resin is peeled off. By doing so, an ITO film having a desired pattern is formed. However, there are problems that a sputtering apparatus that requires vacuum and high temperature is necessary and that the process is complicated. Therefore, a simple patterning method using a wet process (coating method) is desired.
As a method for forming a pattern by a wet process, JP-T-2002-500408 discloses a direct printing of a pattern with a coating liquid composition containing a conductive thin film precursor composition by a screen printing method to remove the solvent or dispersion medium. It is shown that the pattern of the target functional thin film can be formed only by this. However, the resolution is not always sufficient, and the viscosity of the coating composition that can be applied is limited.
Japanese Patent Application Laid-Open No. 2000-208254 discloses a method of patterning polythiophene using an ink jet printing apparatus. However, it is necessary to form a partition wall in advance to prevent dripping of the polythiophene solution. There are also restrictions on surface tension.

（式中、Ｒ^１およびＲ^２はそれぞれ独立して、水素または炭素数１〜４のアルキル基を表すか、あるいは一緒になって任意に置換されてもよい炭素数１〜４のアルキレン基を表す）の反復単位からなる陽イオン形態のポリ（３，４−ジ置換チオフェン）とポリ陰イオンとの複合体であるポリチオフェン複合体の水分散体、および（ｂ）水溶性または水分散性の感放射線性樹脂を含む。
好適な実施態様においては、上記感放射線性樹脂のうちの第１の樹脂は、硬化性エポキシ（メタ）アクリレートであり、該硬化性エポキシ（メタ）アクリレートは、ポリヒドロキシ化合物とエピクロルヒドリンとを反応して得られるポリグリシジルエーテル化合物に、（メタ）アクリル酸を反応させて得られる樹脂である。
好適な実施態様においては、上記感放射線性樹脂のうちの第２の樹脂は、下記一般式（２）

（式中、Ｒ^３は水素原子またはメチル基を表し、Ｒ^４は水素原子または炭素原子数１〜４のアルキル基を表す）で表される化合物と、分子内に水酸基を有する化合物とを強酸触媒の存在下で反応させて得られる樹脂である。
好適な実施態様においては、上記感放射線性樹脂のうちの第３の樹脂は、以下の式（３−Ｉ）で示される単位、（３−ＩＩ）で示される単位、および（３−ＩＩＩ）で示される単位を有し：

（式中、Ｒ^５は、水素またはメチル基であり、分子内の複数のＲ^５は、その各々が同一であっても異なっていてもよく、ｐは１〜１０の整数である）、

（式中、Ｒ^６は、水素またはメチル基であり、Ｘは、水素、アルカリ金属、およびアンモニウム類からなる群より選択される基であり、分子内の複数のＲ^６またはＸは、その各々が同一であっても異なっていてもよい）、

（式中、Ｒ^７およびＲ^８は、それぞれ独立して水素またはメチル基であり、分子内の複数のＲ^７またはＲ^８は、その各々が同一であっても異なっていてもよい）；該感放射線性樹脂中に、該（３−Ｉ）の単位が２モル％〜７３モル％の割合で、該（３−ＩＩ）の単位が８モル％〜８３モル％の割合で、そして、該（３−ＩＩＩ）の単位が１５モル％〜８０モル％の割合で含有される。
好適な実施態様においては、上記感放射線性樹脂のうちの第４の樹脂は、以下の式（４）

（式中、Ｙ⁻は陰イオンを表す）で表される単位を有する。
好適な実施態様においては、上記樹脂組成物は、さらに光重合開始剤および光増感剤の少なくとも一方を含有する。
本発明の導電性薄膜のパターンの形成方法は、上記樹脂組成物でなる塗布液を基板上に塗布することにより塗膜を形成する工程；該塗膜表面にフォトマスクを介して放射線を照射する工程；および照射後の塗膜を水を含む現像液で現像する工程を包含する。
本発明は、上記方法により形成された導電性薄膜のパターンを有する基板を包含する。
好適な実施態様においては、上記導電性薄膜のパターンを有する基板は、ディスプレイの透明電極、トランジスタの電極、太陽電池の電極、配線材料、有機ＥＬデバイス、有機半導体、または電磁波シールド材である。
従って、本発明により以下の目的が達成される：簡易な方法により解像性に優れた導電性薄膜のパターンを形成することの可能なネガ型感放射線性樹脂組成物を提供すること、該組成物を用いた導電性薄膜のパターン形成方法を提供すること、および該方法により得られる導電性薄膜のパターンを有する基板を提供すること。An object of the present invention is to solve the above-described conventional problems. The object of the present invention is to provide a negative radiation-sensitive radiation capable of forming a conductive thin film pattern having excellent resolution by a simple method. The present invention provides a conductive resin composition, a method for forming a pattern of a conductive thin film using the composition, and a substrate having a pattern of a conductive thin film obtained by the method.
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by combining an aqueous dispersion of a specific polythiophene complex and a specific radiation sensitive resin. Was completed.
The negative radiation sensitive resin composition of the present invention comprises (a) the following general formula (1):

(Wherein R ¹ and R ² each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 1 to 4 carbon atoms which may be optionally substituted together) An aqueous dispersion of a polythiophene complex which is a complex of a poly (3,4-disubstituted thiophene) in the cationic form and a polyanion consisting of repeating units of (b)), and (b) a water-soluble or water-dispersible Contains radiation sensitive resin.
In a preferred embodiment, the first resin among the radiation-sensitive resins is a curable epoxy (meth) acrylate, and the curable epoxy (meth) acrylate reacts with a polyhydroxy compound and epichlorohydrin. It is a resin obtained by reacting (meth) acrylic acid with the polyglycidyl ether compound obtained in this manner.
In a preferred embodiment, the second resin among the radiation-sensitive resins is represented by the following general formula (2).

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and a compound having a hydroxyl group in the molecule It is a resin obtained by reacting in the presence of a catalyst.
In a preferred embodiment, the third resin among the radiation-sensitive resins is a unit represented by the following formula (3-I), a unit represented by (3-II), and (3-III) With the units indicated by:

(Wherein R ⁵ is hydrogen or a methyl group, and a plurality of R ⁵ in the molecule may be the same or different, and p is an integer of 1 to 10),

(Wherein R ⁶ is hydrogen or a methyl group, X is a group selected from the group consisting of hydrogen, alkali metals, and ammoniums, and a plurality of R ⁶ or X in the molecule are each Can be the same or different)

Wherein R ⁷ and R ⁸ are each independently hydrogen or a methyl group, and a plurality of R ⁷ or R ⁸ in the molecule may be the same or different from each other; In the radiation sensitive resin, the unit of (3-I) is 2 mol% to 73 mol%, the unit of (3-II) is 8 mol% to 83 mol%, and The unit of (3-III) is contained in a proportion of 15 mol% to 80 mol%.
In a preferred embodiment, the fourth resin among the radiation-sensitive resins is represented by the following formula (4):

(Wherein Y ⁻ represents an anion).
In a preferred embodiment, the resin composition further contains at least one of a photopolymerization initiator and a photosensitizer.
The conductive thin film pattern forming method of the present invention includes a step of forming a coating film by applying a coating liquid comprising the above resin composition on a substrate; irradiating the coating film surface with radiation through a photomask And a step of developing the coating film after irradiation with a developer containing water.
The present invention includes a substrate having a pattern of a conductive thin film formed by the above method.
In a preferred embodiment, the substrate having the conductive thin film pattern is a transparent electrode of a display, an electrode of a transistor, an electrode of a solar cell, a wiring material, an organic EL device, an organic semiconductor, or an electromagnetic wave shielding material.
Therefore, the following objects are achieved by the present invention: To provide a negative radiation-sensitive resin composition capable of forming a pattern of a conductive thin film excellent in resolution by a simple method, the composition To provide a conductive thin film pattern forming method using an object, and to provide a substrate having a conductive thin film pattern obtained by the method.

  FIG. 1 is a schematic view showing a process of forming a conductive thin film pattern on a substrate using the resin composition of the present invention.

（式中、Ｒ^１およびＲ^２はそれぞれ独立して、水素または炭素数１〜４のアルキル基を表すか、あるいは一緒になって任意に置換されてもよい炭素数１〜４のアルキレン基を表す）。
上記（１）式において、Ｒ^１およびＲ^２の炭素数１〜４のアルキル基としては、好適にはメチル基、エチル基、ｎ−プロピル基などが挙げられる。Ｒ^１およびＲ^２が一緒になって形成される炭素数１〜４のアルキレン基としては、１，２−アルキレン基、１，３−アルキレン基などが挙げられ、好適にはメチレン基、１，２−エチレン基、１，３−プロピレン基が挙げられる。これらのうち、１，２−エチレン基が特に好適である。この炭素数１〜４のアルキル基は置換されていてもよく、置換基としては、炭素数１〜１２のアルキル基、フェニル基などが挙げられる。置換された炭素数１〜４のアルキレン基の具体例としては、１，２−シクロヘキシレン基、２，３−ブチレン基などが挙げられる。このようなアルキレン基の代表例としては、Ｒ^１およびＲ^２が一緒になって形成される、炭素数１〜１２のアルキル基で置換された１，２−アルキレン基が挙げられる。このような基は、エテン、プロペン、ヘキセン、オクテン、デセン、ドデセン、スチレンなどのα−オレフィン類を臭素化して得られる１，２−ジブロモアルカン類から誘導される。
上記ポリ陰イオンを構成し得る化合物としては、ポリマー状カルボン酸類（例えば、ポリアクリル酸、ポリメタクリル酸、およびポリマレイン酸）、ポリマー状スルホン酸類（例えば、ポリスチレンスルホン酸およびポリビニルスルホン酸）などが挙げられる。これらのカルボン酸類およびスルホン酸類はまた、ビニルカルボン酸またはビニルスルホン酸類と、他の重合可能なモノマー類（例えば、アクリレート類およびスチレンなど）との共重合体であっても良い。ポリ陰イオンを構成し得る化合物としては、ポリスチレンスルホン酸が特に好適である。上記ポリ陰イオンを構成し得る化合物の数平均分子量は、１，０００から２，０００，０００の範囲が好ましく、より好ましくは、２，０００から５００，０００の範囲であり、最も好ましくは、１０，０００から２００，０００の範囲である。
上記ポリチオフェン複合体の水分散体は、例えば、特許第２６３６９６８号に記載の方法によって製造することができる。さらに好適には、ポリチオフェン複合体の水分散体は、次の方法によって製造され得る。
このポリチオフェン複合体の水分散体の製造方法は、以下の式（１’）で表される３，４−ジ置換チオフェン

（式中、Ｒ^１およびＲ^２は上記（１）式で定義したのと同様である）を、ポリ陰イオンの存在下で、ペルオキソ二硫酸を酸化剤として用いて水系溶媒中で重合させる工程；あるいは、該３，４−ジ置換チオフェンを、ポリ陰イオンの存在下で酸化剤を用いて、水溶性の無機酸および有機酸からなる群より選択される酸を添加し、反応溶液のｐＨを低下させて、水系溶媒中で重合させる工程を含む。上記重合工程におけるポリ陰イオンの仕込量は、上記チオフェン１００質量部に対して、５０から３，０００質量部の範囲が好ましく、より好ましくは１００から１，０００質量部の範囲であり、最も好ましくは、１５０から５００質量部の範囲である。
上記方法に用いられる溶媒は水系溶媒であり、特に好ましくは水である。メタノール、エタノール、２−プロパノール、１−プロパノールなどのアルコール；アセトン、アセトニトリルなどの水溶性の溶媒を水に添加して用いてもよい。
上記方法において、３，４−ジ置換チオフェンの重合反応を行う際の酸化剤としては、以下の化合物が挙げられるが、これらに限定されない：ペルオキソ二硫酸、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸カリウム、ペルオキソ二硫酸アンモニウム、無機酸化第二鉄塩、有機酸化第二鉄塩、過酸化水素、過マンガン酸カリウム、二クロム酸カリウム、過ホウ酸アルカリ塩、銅塩など。これらのうち、ペルオキソ二硫酸、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸カリウム、およびペルオキソ二硫酸アンモニウムが最も好適である。酸化剤の使用量は、上記３，４−ジ置換チオフェン１当量当たり、１から５当量の範囲が好ましく、より好ましくは、２から４当量の範囲である。
本発明の方法においては、重合時における該重合反応系のｐＨが低いこと（好ましくは１．５以下であること）が好ましい。そのため、上記の酸化剤の中で、ペルオキソ二硫酸を選択した場合には、これを反応系に加えるのみで、ｐＨ調整せずに好適に使用することができる。その他の酸化剤を選択した場合には、酸を加えてｐＨを調整する必要がある。反応液のｐＨは、好ましくは１．５以下であり、より好ましくは１．０以下である。
上記酸としては、水溶性の無機酸および有機酸からなる群より選択される酸が使用される。無機酸としては、塩酸、硫酸、硝酸、リン酸などが挙げられる。有機酸としては、ｐ−トルエンスルホン酸、ベンゼンスルホン酸、メタンスルホン酸、トリフルオロメタンスルホン酸などが挙げられる。
さらに、酸化剤として、必要に応じて触媒量の金属イオン、例えば、鉄、コバルト、ニッケル、モリブデン、バナジウムイオンなどを添加しても良い。
重合反応によりポリ（３，４−ジ置換チオフェン）が生成する。このポリ（３，４−ジ置換チオフェン）は陽イオンの形態であり、反応系に存在するポリ陰イオンとともに複合体を形成していると考えられる。本明細書では、上記複合体を「ポリ（３，４−ジ置換チオフェン）とポリ陰イオンとの複合体」、「ポリチオフェン複合体」、あるいは単に「複合体」と記載する場合がある。
ポリチオフェン複合体のうち、ポリ（３，４−エチレンジオキシチオフェン）とポリスチレンスルホン酸との複合体が好適である。特に、上記方法により製造したポリ（３，４−エチレンジオキシチオフェン）とポリスチレンスルホン酸との複合体の水分散体を用いるのが最も好適である。
ＩＩ．感放射線性樹脂
本発明の組成物に含有される（ｂ）の水溶性または水分散性の感放射線性樹脂は、特に限定されないが、以下に示す樹脂（ｂ．１）〜（ｂ．４）の４つのタイプの樹脂が好適である。
（ＩＩ−Ｉ）樹脂（ｂ．１）
この樹脂は、硬化性エポキシ（メタ）アクリレートであり、ポリヒドロキシ化合物とエピクロルヒドリンとを反応して得られるポリグリシジルエーテル化合物に、（メタ）アクリル酸を反応させて得られる。
上記ポリヒドロキシ化合物は、特に制限はないが、例えば、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ソルビトール、ソルビタン、ペンタエリスリトール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコールおよびこれらの混合物が挙げられる。
これらのポリヒドロキシ化合物とエピクロルヒドリンとからポリグリシジルエーテル化合物が得られ、これに（メタ）アクリル酸を反応させることにより、（メタ）アクリル酸に由来する不飽和結合を分子末端に有するポリマー（硬化性エポキシ（メタ）アクリレート）が得られる。硬化性エポキシ（メタ）アクリレートの製造方法についての詳細は、特開２００２−１９４０５２号公報に記載されている。
（ＩＩ−ＩＩ）樹脂（ｂ．２）
この樹脂は、下記一般式（２）

（式中、Ｒ^３は水素原子またはメチル基を表し、Ｒ^４は水素原子または炭素原子数１〜４のアルキル基を表す）で表される化合物（（メタ）アクリルアミド誘導体）と、分子内に水酸基を有する化合物とを強酸触媒の存在下で反応させて得られる。
上記（メタ）アクリルアミド誘導体の具体例としては、Ｎ−メチロール（メタ）アクリルアミド、アルコキシ（炭素数１〜４）メチル（メタ）アクリルアミドなどが挙げられる。
上記の分子内に水酸基を持つ化合物としては、ペンタエリスリトール、トリス（２−ヒドロキシエチル）イソシアヌレートなどが挙げられる。強酸触媒としては、硫酸、塩酸、硝酸、ｐ−トルエンスルホン酸などが挙げられる。
（メタ）アクリルアミド誘導体と分子内に水酸基を有する化合物とから得られる樹脂は、特開２００２−３４１５２９号公報に記載されている。
（ＩＩ−ＩＩＩ）樹脂（ｂ．３）
この樹脂は、以下の式（３−Ｉ）で示される単位、（３−ＩＩ）で示される単位、および（３−ＩＩＩ）で示される単位を有する：

（式中、Ｒ^５は、水素またはメチル基であり、分子内の複数のＲ^５は、その各々が同一であっても異なっていてもよく、ｐは１〜１０の整数である）、

（式中、Ｒ^６は、水素またはメチル基であり、Ｘは、水素、アルカリ金属、およびアンモニウム類からなる群より選択される基であり、分子内の複数のＲ^６またはＸは、その各々が同一であっても異なっていてもよい）、

（式中、Ｒ^７およびＲ^８は、それぞれ独立して水素またはメチル基であり、分子内の複数のＲ^７またはＲ^８は、その各々が同一であっても異なっていてもよい）。
この樹脂中には、上記（３−Ｉ）の単位が２モル％〜７３モル％の割合で、（３−ＩＩ）の単位が８モル％〜８３モル％の割合で、そして、（３−ＩＩＩ）の単位が１５モル％〜８０モル％の割合で含有される。
この樹脂は、例えば、少なくとも（メタ）アクリル酸と、２−ヒドロキシエチル（メタ）アクリレートおよびポリオキシエチレンモノ（メタ）アクリレートの少なくとも一方とを単位として含有する共重合体に、グリシジル（メタ）アクリレートを所定の割合で付加させることにより得られる。このような樹脂は特開２００１−２７０９１９号公報に記載されている。
（ＩＩ−ＩＶ）樹脂（ｂ．４）
この樹脂は、以下の式（４）で示される単位を有する。

上記式において、Ｙ⁻は陰イオンを示す。好適なＹ⁻の例としては、塩化物イオン、臭素化物イオン、ヨウ化物イオン、低級アルコキシ硫酸イオン、ｐ−トルエンスルホン酸イオンなどが挙げられる。このような樹脂は、例えば、特開平８−３２０５５３号公報に記載されている。
ＩＩＩ．感放射線性樹脂組成物
本発明の感放射線性樹脂組成物は、上記（ａ）のポリチオフェン複合体の水分散体および（ｂ）の水溶性または水分散性の感放射線性樹脂を含み、必要に応じて、（ｃ）光重合開始剤および光増感剤のうちの少なくとも一方、（ｄ）重合性モノマー、（ｅ）溶媒、（ｆ）上記（ｂ）以外の水溶性ポリマー、（ｇ）水溶性化合物、（ｈ）中和剤、および（ｉ）添加剤を含む。
本発明の樹脂組成物中の、上記（ａ）のポリチオフェン複合体と（ｂ）の感放射線性組成物の含有割合は特に制限されないが、固形分の質量比で５：９５〜９５：５が好ましく、さらに好ましくは２５：７５〜７５：２５の範囲である。上記複合体の含有量が過少であると十分な導電性が付与できず、逆に、感放射線性樹脂の量が過少であると、導電性は高くなるが、最終的に形成されるパターンの解像度が低下する。本発明の組成物は、水を必須成分として含有する。上記ポリチオフェン複合体の水分散体が水を含有するが、必要に応じてさらに水を組成物中に含有させることができる。
本発明の組成物中に含有され得る上記（ｃ）の光重合開始剤および光増感剤は特に限定されない。光重合開始剤または光増感剤としては、例えば、次の化合物が挙げられる：ベンゾフェノン、４−ヒドロキシベンゾフェノン、ビス−Ｎ，Ｎ−ジメチルアミノベンンゾフェノン、ビス−Ｎ，Ｎ−ジエチルアミノベンゾフェノン、４−メトキシ−４’−ジメチルアミノベンゾフェノンなどのベンゾフェノン類；チオキサントン、２，４−ジエチルチオキサントン、イソプロピルチオキサントン、クロロチオキサントン、イソプロポキシクロロチオキサントンなどのチオキサントン類；エチルアントラキノン、ベンズアントラキノン、アミノアントラキノン、クロロアントラキノン、アントラキノン−２−スルホン酸塩、アントラキノン−２，６−ジスルホン酸塩などのアントラキノン類；アセトフェノン類；ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテルなどのベンゾインエーテル類；２，４，６−トリハロメチルトリアジン類、１−ヒドロキシシクロヘキシルフェニルケトン、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−クロロフェニル）−４，５−ジ（ｍ−メトキシフェニル）イミダゾール二量体、２−（ｏ−フルオロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２，４−ジ（ｐ−メトキシフェニル）−５−フェニルイミダゾール二量体、２−（２，４−ジメトキシフェニル）−４，５−ジフェニルイミダゾール二量体などの、２，４，５−トリアリールイミダゾール二量体類；ベンジルジメチルケタール、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−１−プロパノン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、フェナントレンキノン、９，１０−フェナンスレンキノン、メチルベンゾイン、エチルベンゾインなどベンゾイン類；９−フェニルアクリジン、１，７−ビス（９，９’−アクリジニル）ヘプタンなどのアクリジン誘導体；ビスアシルフォスフィンオキサイドなど。これらの化合物は、単独で、あるいは２種以上組合せて用いられ得る。
上記（ｄ）の重合性モノマーは、樹脂組成物の感度、および最終的に基板上に形成される薄膜の耐熱性、耐水性、耐溶剤性、および耐擦傷性を向上させる目的で、該組成物中に含有される。このような重合性モノマーは特に制限はないが、例えば、次のモノマーが利用可能である：ポリエチレングリコール（メタ）アクリレート（エチレン基の数が２〜１４の化合物）、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエトキシ（メタ）アクリレート、トリメチロールプロパンプロポキシトリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート（プロピレン基の数が２〜１４の化合物）、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ビスフェノールＡポリオキシエチレンジ（メタ）アクリレート、ビスフェノールＡジオキシエチレンジ（メタ）アクリレート、ビスフェノールＡトリオキシエチレンジ（メタ）アクリレート、ビスフェノールＡデカオキシエチレンジ（メタ）アクリレート、多価カルボン酸（無水フタル酸など）と水酸基およびエチレン性不飽和基を有する化合物（β−ヒドロキシエチル（メタ）アクリレートなど）とのエステル化物、（メタ）アクリル酸のアルキルエステル｛（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸ブチルエステル、（メタ）アクリル酸２−エチルヘキシルエステルなど｝、エポキシ化合物の（メタ）アクリル酸付加物（エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、テトラエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、テトラプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ソルビトールトリグリシジルエーテル、グリセリントリグリシジルエーテルなど）、不飽和有機酸（マレイン酸など）およびそれらの無水物、アクリルアミド類（Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド、Ｎ−イソプロピルメタクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミドなど）、スチレン類（スチレン、ヒドロキシスチレンなど）、Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニルイミダゾールなど。これらの化合物は、単独で、あるいは２種以上組合せて用いられ得る。
上記（ｅ）の溶媒としては、水以外の、水と混和する溶剤が挙げられる。そのような溶媒は、特に制限されない。溶媒としては、例えば、次の化合物が挙げられる：メタノール、エタノール、２−プロパノール、１−プロパノールなどのアルコール類；エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコールなどのエチレングリコール類；エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテルなどのグリコールエーテル類；エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテートなどのグリコールエーテルアセテート類；プロピレングリコール、ジプロピレングリコール、トリプロピレングリコールなどのプロピレングリコール類；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、ジプロピレングリコールジエチルエーテルなどのプロピレングリコールエーテル類；プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテートなどのプロピレングリコールエーテルアセテート類；Ｎ−メチルホルムアミド；Ｎ−メチルピロリドン；ジメチルアセトアミド；ジメチルスルホキシド；アセトン；およびアセトニトリル。これらの化合物は、単独で、あるいは２種以上組合せて用いられ得る。
上記（ｆ）の（ｂ）以外の水溶性ポリマーは、成膜性を向上させる目的で、組成物中に含有される。このような水溶性ポリマーは特に制限はなく、例えば、次の化合物が挙げられる：ポリビニルアルコール、変性ポリビニルアルコール（ポリビニルアルコール・ポリアクリレートブロック共重合体、グラフト化ポリビニルアルコールなど）、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ポリビニルピロリドン、ビニルピロリドン−ビニルイミダゾール共重合体、水溶性アルキド樹脂、（メタ）アクリル酸を含む共重合体の塩（ナトリウム塩、アミン塩など）、側鎖にエチレン性二重結合を有する水溶性ポリマーなど。
上記（ｇ）の水溶性化合物は、最終的に得られる薄膜の導電性を向上させる目的で、組成物中に含有される。このような水溶性化合物は、特に制限はなく、以下に挙げるような化合物が挙げられる：Ｎ−メチルピロリドン、２−ピロリドン、Ｎ−ビニルピロリドンなどのピロリドン系化合物；Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルアセトアミドなどのアミド基含有化合物；グリセロール、１，３−ブタンジオール、エチレングリコール、ジエチレングリコールモノエチルエーテルなどの多価アルコール類；ジメチルスルホキシドなど。
上記（ｈ）の中和剤は、ポリチオフェン複合体と感放射線性樹脂との相溶性を向上させる目的で含有される、塩基性の化合物である。このような中和剤としては、次の化合物が挙げられる：アンモニア、トリエチルアミン、Ｎ，Ｎ−ジメチルアミノエタノール、２−アミノ−２−メチルプロパノール、ジエタノールアミン、トリエタノールアミン、水酸化ナトリウム、水酸化カリウムなど。
上記（ｉ）の添加剤としては、重合禁止剤、可塑剤、消泡剤、界面活性剤、カップリング剤などが挙げられ、いずれも当該分野で通常利用される化合物あるいは材料を用いることができる。
本発明により、導電性薄膜パターンを基板上に形成するには、例えば図１（Ａ）に示すように、まず、上記本発明のネガ型感放射線性樹脂組成物でなる塗布液を基板１上に付与し、塗膜（感放射線性樹脂組成物層２）を形成する。基板としては、無機材料でなる基板および有機材料でなる基板のいずれもが利用され得る。無機材料でなる基板としては、シリコンウェハー、ガラス板などがあり；有機材料でなる基板としては、ポリエステル、ポリイミド、ポリアミド、ポリスルホン、ポリカーボネート、ポリ塩化ビニル、ポリエチレン、ポリプロピレン、これらのポリマーを構成するモノマーを重合単位として含有する共重合体、フェノール樹脂、エポキシ樹脂、ＡＢＳ樹脂などの樹脂、あるいは、これらの樹脂のブレンドでなる基板（樹脂製のフィルム、シートなど）が挙げられる。
上記塗布液を基板上に付与するには、スピンコーティング、ロールコーティング、ディップコーティング、スリットコーティング、ブレードコーティング、スプレーコーティングなどの方法が採用される。形成された塗膜は、通常、加熱し、乾燥させる。このようにして形成された感放射線性樹脂組成物層２の膜厚は、特に限定されないが、０．０１〜１．０μｍが好ましく、さらに好ましくは０．０５〜０．６μｍの範囲である。膜厚が薄すぎると十分な導電性が付与できず、逆に、膜厚が厚すぎると導電性は高くなるが、透明性が低下し、パターンの解像度も低下する。
この樹脂組成物層表面に、目的とする導電性薄膜のパターンとは逆のパターンの遮光層を有するフォトマスク３を載置し、これを介して放射線を照射する（図１（Ｂ））。ここで、「放射線」とは、可視光線、紫外線、遠紫外線、Ｘ線、電子線、分子線、γ線、シンクロトロン放射線、プロトンビームなどの総称である。照射前の感放射線性樹脂組成物は水系溶剤に可溶あるいは分散可能であるが、照射された部分（露光部分）２１は、硬化して該溶剤に不溶となる（図１（Ｃ））。そのため、水系溶媒でなる現像液で現像することにより遮光部分（未露光部分）２２を溶解して除去し、目的とする導電性薄膜のパターン２０を形成することができる（図１（Ｄ））。
上記現像液は、水を必須成分として含有し、必要に応じてその他の成分を含有する。例えば、現像性を向上する目的で、有機溶剤、有機アミン、無機アルカリ、界面活性剤、消泡剤などが含有され、あるいは、導電性の向上を目的として、有機酸、無機酸などを含有させることもできる。現像方法は、スプレー式、パドル式、浸漬式などで行うことができる。必要に応じて、超音波の照射を併用することができる。
このように、本発明のネガ型の感放射線性樹脂組成物を用いると、所望のパターンを有する導電性薄膜を、ウェットプロセスにより、基板上に高精度で簡便に形成することが可能となる。従来、ウェットプロセスによる導電性薄膜のパターンの形成方法として、スクリーン印刷法、インクジェットプリンティングなどが知られているが、前者は塗布液の粘度調整が必要であることと、得られるパターンの解像度が低いという問題点があり、後者は塗布液の粘度および表面張力に制約があることと、予め塗液の垂れを防止のための隔壁を形成する必要があるという問題点がある。本発明により、このような問題が解決され、上述のように、簡便な方法で解像度のよい導電性薄膜のパターンが形成され得る。
この組成物により得られた導電性薄膜のパターンは、充分な解像度、導電性、および透明性を有している。従って、該パターンを有する基板は、ディスプレイの透明電極、トランジスタの電極、太陽電池の電極、配線材料、有機ＥＬデバイス（パターンが正孔注入層として機能する）、有機半導体、電磁波シールド材などとして広く利用され得る。The negative radiation sensitive resin composition of the present invention contains (a) an aqueous dispersion of a polythiophene complex, and (b) a water-soluble or water-dispersible radiation-sensitive resin. Hereinafter, these will be described sequentially.
I. Polythiophene complex The polythiophene complex contained in the composition of the present invention comprises a poly (3,4-disubstituted thiophene) having a repeating unit represented by the following general formula (1) and a polyanion: Is a complex of:

(Wherein R ¹ and R ² each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 1 to 4 carbon atoms which may be optionally substituted together) To express).
In the above formula (1), preferred examples of the alkyl group having 1 to 4 carbon atoms of R ¹ and R ² include a methyl group, an ethyl group, and an n-propyl group. Examples of the alkylene group having 1 to 4 carbon atoms formed by combining R ¹ and R ² include a 1,2-alkylene group and a 1,3-alkylene group. Examples include 2-ethylene group and 1,3-propylene group. Of these, 1,2-ethylene groups are particularly preferred. The alkyl group having 1 to 4 carbon atoms may be substituted, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms and a phenyl group. Specific examples of the substituted alkylene group having 1 to 4 carbon atoms include 1,2-cyclohexylene group and 2,3-butylene group. A typical example of such an alkylene group is a 1,2-alkylene group substituted with an alkyl group having 1 to 12 carbon atoms, wherein R ¹ and R ² are formed together. Such groups are derived from 1,2-dibromoalkanes obtained by brominating α-olefins such as ethene, propene, hexene, octene, decene, dodecene, styrene and the like.
Examples of the compound capable of constituting the poly anion include polymeric carboxylic acids (for example, polyacrylic acid, polymethacrylic acid, and polymaleic acid), and polymeric sulfonic acids (for example, polystyrene sulfonic acid and polyvinyl sulfonic acid). It is done. These carboxylic acids and sulfonic acids may also be a copolymer of vinyl carboxylic acid or vinyl sulfonic acid and other polymerizable monomers (eg, acrylates and styrene). As a compound capable of constituting a polyanion, polystyrene sulfonic acid is particularly suitable. The number average molecular weight of the compound that can constitute the polyanion is preferably in the range of 1,000 to 2,000,000, more preferably in the range of 2,000 to 500,000, and most preferably 10 , 000 to 200,000.
The aqueous dispersion of the polythiophene complex can be produced, for example, by the method described in Japanese Patent No. 2636968. More preferably, the aqueous dispersion of the polythiophene complex can be produced by the following method.
The method for producing an aqueous dispersion of this polythiophene complex is a 3,4-disubstituted thiophene represented by the following formula (1 ′).

(Wherein R ¹ and R ² are the same as defined in the above formula (1)), in the presence of a polyanion, polymerizing in an aqueous solvent using peroxodisulfuric acid as an oxidizing agent. Or an acid selected from the group consisting of a water-soluble inorganic acid and an organic acid is added to the 3,4-disubstituted thiophene using an oxidizing agent in the presence of a polyanion, and the pH of the reaction solution is increased. And a step of polymerizing in an aqueous solvent. The amount of polyanion charged in the polymerization step is preferably in the range of 50 to 3,000 parts by weight, more preferably in the range of 100 to 1,000 parts by weight, and most preferably with respect to 100 parts by weight of the thiophene. Is in the range of 150 to 500 parts by weight.
The solvent used in the above method is an aqueous solvent, particularly preferably water. Alcohols such as methanol, ethanol, 2-propanol, and 1-propanol; water-soluble solvents such as acetone and acetonitrile may be added to water.
In the above method, examples of the oxidizing agent for conducting the polymerization reaction of 3,4-disubstituted thiophene include, but are not limited to, the following compounds: peroxodisulfuric acid, sodium peroxodisulfate, potassium peroxodisulfate, Ammonium peroxodisulfate, inorganic ferric oxide salt, organic ferric oxide salt, hydrogen peroxide, potassium permanganate, potassium dichromate, alkali perborate, copper salt and the like. Of these, peroxodisulfuric acid, sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate are most preferred. The amount of the oxidizing agent used is preferably in the range of 1 to 5 equivalents, more preferably in the range of 2 to 4 equivalents per equivalent of the 3,4-disubstituted thiophene.
In the method of the present invention, it is preferred that the pH of the polymerization reaction system during polymerization is low (preferably 1.5 or less). Therefore, when peroxodisulfuric acid is selected from the above oxidizing agents, it can be suitably used by adding it to the reaction system without adjusting the pH. When other oxidizing agents are selected, it is necessary to adjust the pH by adding an acid. The pH of the reaction solution is preferably 1.5 or less, more preferably 1.0 or less.
As the acid, an acid selected from the group consisting of water-soluble inorganic acids and organic acids is used. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like. Examples of the organic acid include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like.
Furthermore, a catalytic amount of metal ions, for example, iron, cobalt, nickel, molybdenum, vanadium ions, etc., may be added as an oxidizing agent as required.
Poly (3,4-disubstituted thiophene) is produced by the polymerization reaction. This poly (3,4-disubstituted thiophene) is in the form of a cation and is considered to form a complex with the polyanion present in the reaction system. In the present specification, the complex may be described as “a complex of poly (3,4-disubstituted thiophene) and a polyanion”, “polythiophene complex”, or simply “complex”.
Of the polythiophene composites, a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is preferable. In particular, it is most preferable to use an aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid produced by the above method.
II. Radiation-sensitive resin Although the water-soluble or water-dispersible radiation-sensitive resin (b) contained in the composition of the present invention is not particularly limited, the following resins (b.1) to (b.4) The four types of resins are preferred.
(II-I) Resin (b.1)
This resin is a curable epoxy (meth) acrylate, and can be obtained by reacting (meth) acrylic acid with a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin.
The polyhydroxy compound is not particularly limited. For example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, Examples include sorbitan, pentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and mixtures thereof.
A polyglycidyl ether compound is obtained from these polyhydroxy compounds and epichlorohydrin, and by reacting this with (meth) acrylic acid, a polymer having an unsaturated bond derived from (meth) acrylic acid at the molecular end (curability) Epoxy (meth) acrylate) is obtained. Details of the method for producing the curable epoxy (meth) acrylate are described in JP-A No. 2002-194052.
(II-II) Resin (b.2)
This resin has the following general formula (2)

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and a molecule ((meth) acrylamide derivative) It is obtained by reacting a compound having a hydroxyl group in the presence of a strong acid catalyst.
Specific examples of the (meth) acrylamide derivative include N-methylol (meth) acrylamide, alkoxy (C1-4) methyl (meth) acrylamide and the like.
Examples of the compound having a hydroxyl group in the molecule include pentaerythritol and tris (2-hydroxyethyl) isocyanurate. Examples of the strong acid catalyst include sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid and the like.
A resin obtained from a (meth) acrylamide derivative and a compound having a hydroxyl group in the molecule is described in JP-A-2002-341529.
(II-III) Resin (b.3)
This resin has a unit represented by the following formula (3-I), a unit represented by (3-II), and a unit represented by (3-III):

(Wherein R ⁵ is hydrogen or a methyl group, and a plurality of R ⁵ in the molecule may be the same or different, and p is an integer of 1 to 10),

(Wherein R ⁶ is hydrogen or a methyl group, X is a group selected from the group consisting of hydrogen, alkali metals, and ammoniums, and a plurality of R ⁶ or X in the molecule are each Can be the same or different)

(Wherein R ⁷ and R ⁸ are each independently hydrogen or a methyl group, and a plurality of R ⁷ or R ⁸ in the molecule may be the same or different).
In the resin, the unit of (3-I) is in a proportion of 2 mol% to 73 mol%, the unit of (3-II) is in a proportion of 8 mol% to 83 mol%, and (3- III) units are contained in a proportion of 15 mol% to 80 mol%.
This resin is, for example, a copolymer containing at least (meth) acrylic acid and at least one of 2-hydroxyethyl (meth) acrylate and polyoxyethylene mono (meth) acrylate as a unit, and glycidyl (meth) acrylate. Is added at a predetermined ratio. Such a resin is described in JP-A-2001-270919.
(II-IV) Resin (b.4)
This resin has a unit represented by the following formula (4).

In the above formula, Y ⁻ represents an anion. Examples of suitable Y ⁻ include chloride ion, bromide ion, iodide ion, lower alkoxysulfate ion, p-toluenesulfonate ion and the like. Such a resin is described in, for example, JP-A-8-320553.
III. Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention comprises the water dispersion of the polythiophene complex (a) and the water-soluble or water-dispersible radiation-sensitive resin (b). Accordingly, (c) at least one of a photopolymerization initiator and a photosensitizer, (d) a polymerizable monomer, (e) a solvent, (f) a water-soluble polymer other than (b) above, (g) a water-soluble polymer A chemical compound, (h) a neutralizing agent, and (i) an additive.
The content ratio of the polythiophene complex of (a) and the radiation-sensitive composition of (b) in the resin composition of the present invention is not particularly limited, but the mass ratio of solid content is 5:95 to 95: 5. More preferably, it is the range of 25: 75-75: 25. If the content of the composite is too small, sufficient conductivity cannot be imparted. Conversely, if the amount of the radiation-sensitive resin is too small, the conductivity is increased, but the pattern formed finally The resolution decreases. The composition of the present invention contains water as an essential component. The aqueous dispersion of the polythiophene complex contains water, but water can be further contained in the composition as necessary.
The photopolymerization initiator and photosensitizer of the above (c) that can be contained in the composition of the present invention are not particularly limited. Examples of the photopolymerization initiator or photosensitizer include the following compounds: benzophenone, 4-hydroxybenzophenone, bis-N, N-dimethylaminobenzozonone, bis-N, N-diethylaminobenzophenone, Benzophenones such as 4-methoxy-4′-dimethylaminobenzophenone; thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone; ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone Anthraquinones such as anthraquinone-2-sulfonate and anthraquinone-2,6-disulfonate; acetophenones; benzoin methyl ether, benzoy Benzoin ethers such as ethyl ether and benzoin phenyl ether; 2,4,6-trihalomethyltriazines, 1-hydroxycyclohexyl phenyl ketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2,4,5, such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer Triarylimidazole dimers; benzyldimethyl ketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- 1-propan-1-one, phenanthrenequinone, 9,10-phenanthrenequinone, methylbenzoin, ethylbenzoin and other benzoins; 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc. Acridine derivatives; bisacylphosphine oxide and the like. These compounds may be used alone or in combination of two or more.
The polymerizable monomer (d) is used for the purpose of improving the sensitivity of the resin composition and the heat resistance, water resistance, solvent resistance, and scratch resistance of the thin film finally formed on the substrate. Contained in the product. Such a polymerizable monomer is not particularly limited. For example, the following monomers can be used: polyethylene glycol (meth) acrylate (a compound having 2 to 14 ethylene groups), trimethylolpropane di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxy (meth) acrylate, trimethylolpropane propoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol Di (meth) acrylate (compound having 2 to 14 propylene groups), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A Reoxyethylene di (meth) acrylate, bisphenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, polycarboxylic acid (phthalic anhydride) Etc.) and an esterified product of a compound having a hydroxyl group and an ethylenically unsaturated group (such as β-hydroxyethyl (meth) acrylate), an alkyl ester of (meth) acrylic acid {(meth) acrylic acid methyl ester, (meth) acrylic Acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, etc.}, (meth) acrylic acid adducts of epoxy compounds (ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ester) Ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, sorbitol triglycidyl ether, glycerin triglycidyl ether, etc.), unsaturated organic acids (such as maleic acid) and their anhydrides, acrylamides (N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methylmethacrylamide, N-ethyl Tacrylamide, N-isopropylmethacrylamide, N-methylolmethacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, etc.), styrenes (styrene, hydroxystyrene, etc.), N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylimidazole and the like. These compounds may be used alone or in combination of two or more.
Examples of the solvent (e) include solvents miscible with water other than water. Such a solvent is not particularly limited. Examples of the solvent include the following compounds: alcohols such as methanol, ethanol, 2-propanol and 1-propanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; ethylene glycol monomethyl Glycol ethers such as ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; propylene glycol, dipropylene glycol, Tripropylene Propylene glycols such as coal; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether Propylene glycol ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate; N-methylformamide N- methylpyrrolidone; dimethylacetamide; dimethylsulfoxide; acetone; and acetonitrile. These compounds may be used alone or in combination of two or more.
The water-soluble polymer other than the above (f) (b) is contained in the composition for the purpose of improving the film formability. Such a water-soluble polymer is not particularly limited, and examples thereof include the following compounds: polyvinyl alcohol, modified polyvinyl alcohol (polyvinyl alcohol / polyacrylate block copolymer, grafted polyvinyl alcohol, etc.), hydroxymethyl cellulose, hydroxyethyl cellulose , Hydroxypropylcellulose, polyvinylpyrrolidone, vinylpyrrolidone-vinylimidazole copolymer, water-soluble alkyd resin, copolymer salt containing (meth) acrylic acid (sodium salt, amine salt, etc.), ethylenic double in side chain Water-soluble polymer having a bond.
The water-soluble compound (g) is contained in the composition for the purpose of improving the conductivity of the finally obtained thin film. Such water-soluble compounds are not particularly limited, and include the following compounds: pyrrolidone compounds such as N-methylpyrrolidone, 2-pyrrolidone and N-vinylpyrrolidone; N-methylformamide, N, N -Amide group-containing compounds such as dimethylformamide and dimethylacetamide; polyhydric alcohols such as glycerol, 1,3-butanediol, ethylene glycol and diethylene glycol monoethyl ether; dimethyl sulfoxide and the like.
The neutralizing agent (h) is a basic compound contained for the purpose of improving the compatibility between the polythiophene complex and the radiation-sensitive resin. Such neutralizers include the following compounds: ammonia, triethylamine, N, N-dimethylaminoethanol, 2-amino-2-methylpropanol, diethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide. Such.
Examples of the additive (i) include a polymerization inhibitor, a plasticizer, an antifoaming agent, a surfactant, a coupling agent, and the like, and any of compounds or materials that are usually used in the field can be used. .
In order to form a conductive thin film pattern on a substrate according to the present invention, for example, as shown in FIG. 1 (A), first, a coating liquid comprising the negative radiation-sensitive resin composition of the present invention is first applied on the substrate 1. To form a coating film (radiation sensitive resin composition layer 2). As the substrate, both a substrate made of an inorganic material and a substrate made of an organic material can be used. Examples of substrates made of inorganic materials include silicon wafers and glass plates; examples of substrates made of organic materials include polyester, polyimide, polyamide, polysulfone, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, and monomers constituting these polymers. And a substrate (resin film, sheet, etc.) made of a resin such as a copolymer, a phenol resin, an epoxy resin, an ABS resin, or a blend of these resins.
In order to apply the coating solution onto the substrate, methods such as spin coating, roll coating, dip coating, slit coating, blade coating, and spray coating are employed. The formed coating film is usually heated and dried. Although the film thickness of the radiation sensitive resin composition layer 2 formed in this way is not specifically limited, 0.01-1.0 micrometer is preferable, More preferably, it is the range of 0.05-0.6 micrometer. If the film thickness is too thin, sufficient conductivity cannot be imparted. Conversely, if the film thickness is too thick, the conductivity increases, but the transparency decreases and the pattern resolution also decreases.
On the surface of the resin composition layer, a photomask 3 having a light shielding layer having a pattern opposite to the pattern of the target conductive thin film is placed, and radiation is irradiated through the photomask 3 (FIG. 1B). Here, “radiation” is a general term for visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation, proton beams, and the like. The radiation-sensitive resin composition before irradiation is soluble or dispersible in an aqueous solvent, but the irradiated portion (exposed portion) 21 is cured and becomes insoluble in the solvent (FIG. 1C). Therefore, the light-shielding portion (unexposed portion) 22 is dissolved and removed by developing with a developer composed of an aqueous solvent, and the target conductive thin film pattern 20 can be formed (FIG. 1D). .
The developer contains water as an essential component and other components as necessary. For example, an organic solvent, an organic amine, an inorganic alkali, a surfactant, an antifoaming agent, or the like is contained for the purpose of improving developability, or an organic acid or an inorganic acid is contained for the purpose of improving conductivity. You can also. The developing method can be performed by a spray method, a paddle method, an immersion method, or the like. If necessary, ultrasonic irradiation can be used in combination.
Thus, when the negative radiation sensitive resin composition of the present invention is used, a conductive thin film having a desired pattern can be easily and accurately formed on a substrate by a wet process. Conventionally, a screen printing method, ink jet printing, or the like is known as a method for forming a conductive thin film pattern by a wet process. However, the former requires adjustment of the viscosity of the coating liquid and the resolution of the obtained pattern is low. The latter has the problems that the viscosity and surface tension of the coating solution are limited and that it is necessary to form a partition wall in advance to prevent the coating solution from dripping. According to the present invention, such a problem is solved, and a conductive thin film pattern with good resolution can be formed by a simple method as described above.
The pattern of the conductive thin film obtained by this composition has sufficient resolution, conductivity, and transparency. Therefore, the substrate having the pattern is widely used as a transparent electrode of a display, an electrode of a transistor, an electrode of a solar cell, a wiring material, an organic EL device (the pattern functions as a hole injection layer), an organic semiconductor, an electromagnetic wave shielding material, etc. Can be used.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In this example, “parts” all indicate “parts by mass”.
1. Materials used The following materials were used in this example.
1.1 Substrate A PET film (total light transmittance: 87.8%) was used.
1.2 Aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid In a 1,887 part aqueous solution containing 20.8 parts of polystyrene sulfonic acid having a weight average molecular weight of 75000, 49 parts of a 1% by mass iron (III) sulfate aqueous solution, 8.8 parts of 3,4-ethylenedioxythiophene, and 117 parts of a 10.9% by mass peroxodisulfuric acid aqueous solution were added. The reaction mixture was stirred at 18 ° C. for 23 hours to obtain an aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid. To this, 154 parts of cation exchange resin and 232 parts of anion exchange resin were added and stirred for 2 hours, and then the ion exchange resin was filtered off. Thus, a desalted aqueous dispersion containing a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid at a ratio of 1.4% by mass was obtained.
2. Resolution of pattern of conductive thin film “TOPPAN-TEST-CHART-NO1-P / NL7401” manufactured by Toppan Printing Co., Ltd. was used as a photomask. With reference to 36 stages of line and space of 0.877 to 50.000 μm, the line width of the obtained pattern was evaluated by optical microscope observation.
3. Surface resistivity and total light transmittance of conductive thin film pattern In each of Examples 5 to 8, exposure was performed without placing a photomask on the coating film on the substrate, and a substrate having a conductive thin film on the entire surface was formed. Obtained. The surface resistivity and total light transmittance of this conductive thin film were measured, and these were used as the surface resistivity and total light transmittance of the pattern of the conductive thin film, respectively. The surface resistivity was measured according to JIS K7194 using Loresta-GP (MCP-T600) manufactured by Mitsubishi Chemical Corporation. The total light transmittance was measured using a haze computer HGM-2B manufactured by Suga Test Instruments Co., Ltd. according to JIS K7150.
(Synthesis Example 1) Synthesis of Resin (b.1) Polyglycidyl ether (epoxy equivalent 149 WPE, total chlorine content 0. 0) obtained by reacting epichlorohydrin with ethylene oxide 3 mol adduct of glycerin as polyglycidyl ether. 7 mass%) was prepared. A reactor equipped with a stirrer and a thermometer was charged with 250.0 g of this polyglycidyl ether, 120.8 g of acrylic acid, 0.6 g of tetramethylammonium chloride as a catalyst, and 0.6 g of hydroquinone monomethyl ether as a polymerization inhibitor. A viscous solution of the radiation sensitive resin was obtained by stirring at -80 ° C for 20 hours.
[Example 1]
89.6 g of a desalted aqueous dispersion containing a complex of poly (3,4-ethylenedioxythiophene) prepared in the above section 1.2 and polystyrenesulfonic acid, 3.6 g of N-methylformamide, By mixing 2.7 g of the viscous solution of the radiation sensitive resin obtained in Synthesis Example 1, 0.1 g of thioxanthone, and 4.0 g of demineralized water, a coating solution of the negative radiation sensitive resin composition was obtained. .
(Synthesis Example 2) Synthesis of Resin (b.2) 68 g of pentaerythritol, 151.5 g of N-methylolacrylamide, and 0.25 g of hydroquinone monomethyl ether were placed in a flask and dissolved by heating, and then 1.69 g of p-toluenesulfonic acid. And stirred for 1.5 hours while feeding air. Water was added thereto and neutralized with aqueous ammonia to obtain a condensation product (40% by mass aqueous solution).
[Example 2]
85 g of a desalted water dispersion containing a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid prepared in the above section 1.2, 0.9 g of 10% by mass ammonia water, N -3.5 g of methylformamide, 0.59 g of the condensation product obtained in Synthesis Example 2, 1.38 g of a 20% aqueous solution of polyvinyl alcohol, 0.017 g of benzyldimethyl ketal, 0.001 g of methylhydroquinone, 0.96 g of methanol, and By mixing 0.05 g of polyethylene glycol diacrylate, a coating solution of a negative radiation sensitive resin composition was obtained.
(Synthesis Example 3) Synthesis of Resin (b.3) 43.5 g of 2-hydroxyethyl acrylate, 130.5 g of methacrylic acid, and 6.8 g of dimethyl 2,2′-azobis (2-methylpropionate) were added to propylene glycol. After dissolving in 87.0 g, it was added dropwise over 45 hours to 457.4 g of propylene glycol maintained at 80 ° C. under a nitrogen stream. After aging for 4 hours, the reaction temperature was raised to 100 ° C. and aging was performed for 2 hours to obtain a transparent viscous polymer solution. This polymer solution was cooled again to 80 ° C., and 13.0 g of pyridine and 0.6 g of N-nitrosophenylhydroxylamine / ammonium salt dissolved in 32.0 g of propylene glycol were added thereto, and then glycidyl methacrylate. 116.0g was dripped over 30 minutes, and it hold | maintained at 80 degreeC for 6 hours, and obtained the pale red viscous polymer solution.
1000 ml of ethyl acetate was put into a reaction vessel equipped with a stirrer, and 100 g of the viscous polymer solution was added dropwise thereto. After dispersing for 1 hour, it was filtered and dried to obtain a white powder. 10.74 g of this white powder, 0.83 g of 10% NaOH aqueous solution, 17.94 g of propylene glycol and 30.00 g of demineralized water were mixed to obtain a transparent and viscous polymer solution.
[Example 3]
87 g of a desalted aqueous dispersion containing a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid prepared in the above section 1.2, 0.9 g of 10% by mass ammonia water, N -3.5 g of methylformamide, 3.0 g of the transparent viscous polymer solution obtained in Synthesis Example 3, 2.6 g of demineralized water, and 1- [4- (2-hydroxyethoxy) -phenyl] -2- 0.077 g of hydroxy-2-methyl-1-propan-1-one was mixed and dissolved to obtain a coating solution of a negative radiation sensitive resin composition.
[Example 4]
66.6 g of a desalted aqueous dispersion containing a complex of poly (3,4-ethylenedioxythiophene) prepared in the above section 1.2 and polystyrenesulfonic acid, 2.7 g of N-methylformamide, SPP-H-13 (negative water-soluble radiation sensitive resin manufactured by Toyo Gosei Co., Ltd., solid content 13.4%; included in resin (b.4)) 6.5 g, plus coat RY-2 (corresponding A surfactant (manufactured by Chemical Industry Co., Ltd.) 0.7 g and 23.5 g of demineralized water were mixed and dissolved to obtain a coating solution of a negative radiation-sensitive resin composition.
[Example 5]
The coating liquid obtained in Example 1 was used as a No. 1 coating. It applied on PET film (board | substrate) using the wire bar of 8, and was dried at 100 degreeC for 2 minutes. A uni-cure system (TYPE: UVX-01212S1CS01: manufactured by Ushio Electric Co., Ltd.), in which a photomask is placed on the formed coating film and a metal halide lamp is mounted, is passed through the photomask to 1,500 mJ / cm. Contact exposure was performed at an exposure amount of ² . Next, the substrate having this coating film was immersed in water at 23 ° C. for 1 minute to dissolve and remove unexposed portions (light-shielded portions), and washed with water, thereby forming a pattern of a conductive thin film.
The resolution of the pattern of the obtained conductive thin film was 50 μm, the surface resistivity was 1,100 Ω / □, and the total light transmittance was 81.0%.
[Example 6]
The coating liquid obtained in Example 2 was prepared as It applied on PET film (board | substrate) using 12 wire bars, and was dried at 60 degreeC for 5 minute (s). A photomask was placed on the formed coating film, and a UniCure system (TYPE: UVX-01212S1CS01: manufactured by Ushio Electric Co., Ltd.) equipped with a metal halide lamp was used, and 45 mJ / cm ^{2 was} passed through the photomask. Contact exposure was performed with an exposure amount. Next, the substrate having this coating film was immersed in an aqueous developer at 23 ° C. (mixed solution of 86.7 parts by mass of desalted water, 3.3 parts by mass of monoethanolamine, and 10.0 parts by mass of diethylene glycol monobutyl ether) for 1 minute. Then, the pattern of the conductive thin film was formed by dissolving and removing the unexposed portion and washing with water in a water shower.
The resolution of the pattern of the obtained conductive thin film was 15 μm, the surface resistivity was 580Ω / □, and the total light transmittance was 75.0%.
[Example 7]
The coating liquid obtained in Example 3 was used as a No. 3 coating. It applied on PET film (board | substrate) using 12 wire bars, and was dried at 60 degreeC for 3 minute (s). A photomask was placed on the formed coating film, and a UniCure system (TYPE: UVX-01212S1CS01: manufactured by Ushio Electric Co., Ltd.) equipped with a metal halide lamp was used, and 45 mJ / cm ^{2 was} passed through the photomask. Contact exposure was performed with an exposure amount. Subsequently, the substrate having this coating film was treated with an aqueous developer at 23 ° C. (86.7 parts by mass of desalted water, 3.3 parts by mass of monoethanolamine, 10.0 parts by mass of diethylene glycol monobutyl ether, and 5. After immersing in 0 part by weight of a mixed solution) for 1 minute, a non-exposed portion was dissolved and removed with a water shower, and washed with water to form a conductive thin film pattern.
The resolution of the pattern of the obtained conductive thin film was 10 μm, the surface resistivity was 580Ω / □, and the total light transmittance was 75.1%.
[Example 8]
The coating solution obtained in Example 4 was prepared as No. 4 It applied on PET film (board | substrate) using the wire bar of 8, and was dried at 100 degreeC for 2 minutes. Using a UniCure system (TYPE: UVX-01212S1CS01: manufactured by Ushio Electric Co., Ltd.) on which a photomask was placed on the formed coating film and a metal halide lamp was attached, 500 mJ / cm ² was passed through the photomask. Contact exposure was performed with an exposure amount. Next, the substrate having this coating film was immersed in water at 23 ° C. for 1 minute to dissolve and remove unexposed portions, and washed with water to form a conductive thin film pattern.
The resolution of the pattern of the obtained conductive thin film was 30 μm, the surface resistivity was 1,200 Ω / □, and the total light transmittance was 84.3%.
(Comparative Example 1)
Pentaerythritol triacrylate 1.0 g, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one 0.03 g, and Pluscoat RY-2 (corresponding 0.5 g (surfactant manufactured by Chemical Industry Co., Ltd.) was vigorously stirred and mixed. While stirring this mixed liquid, 80.0 g of a desalted aqueous dispersion containing a complex of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid prepared in the above section 1.2, and N-methylformamide (3.0 g) was added and mixed to obtain a coating solution of a negative radiation sensitive resin composition.
(Comparative Example 2)
The coating solution obtained in Comparative Example 1 was designated as No. It applied on PET film (board | substrate) using the wire bar of 8, and was dried at 100 degreeC for 2 minutes. A uni-cure system (TYPE: UVX-01212S1CS01: manufactured by Ushio Electric Co., Ltd.) in which a photomask was placed on the formed coating film and a metal halide lamp was mounted was used, and 3,000 mJ / cm was passed through the photomask. Contact exposure was performed at an exposure amount of ² . Next, the substrate having this coating film was immersed in water at 23 ° C. for 1 minute to dissolve and remove unexposed portions, and washed with water to form a conductive thin film pattern.
The pattern of the obtained conductive thin film could not be resolved even with the maximum photomask pattern of 50 μm used. The surface resistivity was 1,800Ω / □, and the total light transmittance was 80.0%.

  According to the present invention, a negative radiation sensitive resin composition capable of easily and accurately forming a conductive thin film having a desired pattern on a substrate is obtained. The pattern of the conductive thin film obtained by this composition has sufficient resolution, conductivity, and transparency. Therefore, the substrate having the pattern can be widely used as a transparent electrode of a display, an electrode of a transistor, an electrode of a solar cell, a wiring material, an organic EL device, an organic semiconductor, an electromagnetic wave shielding material, and the like.

Claims (9)

(A) The following general formula (1)

(Wherein R ¹ and R ² each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 1 to 4 carbon atoms which may be optionally substituted together) An aqueous dispersion of a polythiophene complex, which is a complex of a poly (3,4-disubstituted thiophene) in the cationic form and a polyanion consisting of repeating units of: (b) water-soluble or water-dispersible Radiation sensitive resin,
A negative-type radiation-sensitive resin composition. The radiation sensitive resin is a curable epoxy (meth) acrylate, and the curable epoxy (meth) acrylate is converted to a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin with (meth) acrylic acid. The resin composition according to claim 1, wherein the resin composition is obtained by reacting. The radiation sensitive resin is represented by the following general formula (2)

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and a compound having a hydroxyl group in the molecule The resin composition of Claim 1 which is resin obtained by making it react in presence of a catalyst. The radiation-sensitive resin has a unit represented by the following formula (3-I), a unit represented by (3-II), and a unit represented by (3-III):

(Wherein R ⁵ is hydrogen or a methyl group, and a plurality of R ⁵ in the molecule may be the same or different, and p is an integer of 1 to 10),

(Wherein R ⁶ is hydrogen or a methyl group, X is a group selected from the group consisting of hydrogen, alkali metals, and ammoniums, and a plurality of R ⁶ or X in the molecule are each Can be the same or different)

(Wherein R ⁷ and R ⁸ are each independently hydrogen or a methyl group, and a plurality of R ⁷ or R ⁸ in the molecule may be the same or different from each other),
In the radiation sensitive resin, the unit of (3-I) is 2 mol% to 73 mol%, the unit of (3-II) is 8 mol% to 83 mol%, and The unit of (3-III) is contained in a proportion of 15 mol% to 80 mol%,
The resin composition according to claim 1. The radiation sensitive resin is represented by the following formula (4):

The resin composition of Claim 1 which has a unit represented by (In formula, Y < ^- > represents an anion). Furthermore, the resin composition in any one of Claim 1 to 5 containing at least one of a photoinitiator and a photosensitizer. A step of forming a coating film by applying a coating liquid comprising the resin composition according to claim 1 on a substrate; a step of irradiating the coating film surface with radiation through a photomask; and A method for forming a pattern of a conductive thin film, comprising a step of developing a film after irradiation with a developer containing water. A substrate having a pattern of a conductive thin film formed by the method according to claim 7. The board | substrate which has the pattern of the electroconductive thin film of Claim 8 which is the transparent electrode of a display, the electrode of a transistor, the electrode of a solar cell, a wiring material, an organic EL device, an organic semiconductor, or an electromagnetic wave shielding material.

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