TW201239046A - Optical and thermal energy crosslinkable material for organic thin film transistor insulation layer - Google Patents

Optical and thermal energy crosslinkable material for organic thin film transistor insulation layer Download PDF

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TW201239046A
TW201239046A TW101103744A TW101103744A TW201239046A TW 201239046 A TW201239046 A TW 201239046A TW 101103744 A TW101103744 A TW 101103744A TW 101103744 A TW101103744 A TW 101103744A TW 201239046 A TW201239046 A TW 201239046A
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thin film
film transistor
insulating layer
organic thin
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TW101103744A
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Chinese (zh)
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Isao Yahagi
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Sumitomo Chemical Co
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/13—Morphological aspects
    • C08G2261/135—Cross-linked structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/76—Post-treatment crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/92—TFT applications
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene

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  • Thin Film Transistor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

An objective of this invention is to provide a material for organic thin film transistor insulation layer capable of manufacturing an organic thin film transistor having small absolute value of threshold voltage and hysteresis. The material for organic thin film transistor insulation layer of this invention includes a high polymer compound (A) containing a (meth) acryloyl group and two or more first functional groups in one molecule, wherein the first functional group will generate a second functional group capable of reacting with active hydrogen by irradiation of electromagnetic wave or action of heat.

Description

201239046 六、發明說明： 【發明所屬之技術領域】 本务明係關於一種適於形成有機薄膜電晶體所具有 之絕緣層的材料^ 【先前技術】 有機薄膜電晶體由於能以較無機半導體低溫製造，故 可使用塑膠基板或薄膜作為其基板，藉由使用如此之基 板，可製得相較於由無機半導體所構成之電晶體更 性之輕量、不易損狀元件。又，，村藉由❹㈣2 料之/谷液之塗佈成印刷法之成膜而製作元件，亦可以低成 本於大面積之基板製造多數之元件。 再者，由於電晶體之研究可使用的材料種類豐富，故 若使用於分子構造不同之材料的研究，則可製造具有範圍 廣泛特性之變化性的元件。 於有機薄膜電晶體之1種的電場效應型有機薄膜電晶 體，施加於閘極電極之電壓係隔著閘極絕緣層作用於半導 體層，而控制汲極電流的開、關。因此，於閘極電極與半 導體層之間形成有閘極絕緣層。 又，於電場效應型有機薄膜電晶體之製造所使用之有 機半導體化合物’容易受到溫度、氧等環境的影響，故電 晶體的特性容易發生起因於濕度、氧等之經時劣化。 因此’於除去有機半導體化合物所成之下閘極（bonom gate)型有機薄膜電晶體元件構造，必須以覆蓋元件構造整 體之方式形成保護層，以保護有機半導體化合物與外部空 323900 201239046 氣的接觸。另一方面’於上閘極（切p gate)型有機薄膜電 泰 晶體元件構造，有機半導體化合物係藉由閘極絕緣層之塗 敷而保護。 如此，有機薄膜電晶體中形成有覆蓋有機半導體層之 保護層及閘椏絕緣層等，故可使用絕緣層材料。於本說明 書，將上述保護層及閘極絕緣層等有機薄膜電晶體之絕緣 層或絕緣膜稱為有機薄膜電晶體絕緣層。又，將形成有機 薄膜電晶體絕緣層時所使用之材料稱為有機薄膜電晶體絕 緣層材料。又，此處所稱之材料，係指包含高分子化合物、 含高分子化合物之組成物、樹脂及樹脂組成物等無定形材 料的概念。 對於有機薄膜電晶體絕緣層材料，要求絕緣性及作成 薄膜時之絕緣破壞強度優異的特性。又，特別是於下閘極 型之電场效應電晶體’半導體層係與閘極絕緣層重疊而形 成。因此，對於有機薄膜電晶體閘極絕緣層材料，要求用 以形成與有機半導體密合之界面之與有機半導體的親和 性、使由該有機薄膜電晶體閘極絕緣層材料所形成之膜之 有機半導體層側之表面為平坦的特性。 作為因應如此要求之技術，於專利文獻1記载有使用 組合環氧樹脂與矽烷耦合劑作為有機薄膜電晶體閘極絕緣 層材料。於該技術中，使環氧樹脂之硬化反應時所生成之 羥基與矽烷耦合劑反應。其係因上述羥基可提高間極絕緣 層材料之吸濕性，而不損及電晶體性能之安定性之故。 於非專利文獻1記載將聚乙烯酚（polyvinyl phenc>1) 323900 5 201239046 與三聚氰胺化合物熱交聯所成之樹脂使用於閘極絕緣層。 該技術係於三聚氰胺化合物藉由交聯除去聚乙烯酚所含之 羥基，同時提高膜強度。具有該閘極絕緣層之铜^苯 (pentacene)TFT係磁滞（hySteresis)小，對閘極偏壓 (gate bias)應力顯示耐久性。 於非專利文獻2係記載於閘極絕緣層使用將聚乙烯酚 及乙稀盼與甲基丙稀酸甲·聚合之共聚物。該技術係使 乙烯酚之羥基與甲基兩烯酸甲酯之羧基相互作用以使膜整 體的極性降低。具有該閘極絕緣層之稠五苯TFT係磁滯 小，顯示安定之電性特性。 [先前技術文獻] [專利文獻] 專利文獻1 :日本特開2007-305950 [非專利文獻] 非專利文獻 1 : Appl. PhyS. Lett. 89，093507(2006) 非專利文獻 2: Appl. phys. Lett. 92，183306(2008) 【發明内容】 (發明欲解決之課題） 然而，若考量如有機電激發光元件（有機EL元件）等 之發光元件的實用化’則必須更提升有機薄膜電晶體之動 作精度’而具有上述以往之閘極絕緣層之有機薄膜電晶 體，臨限電壓（Vth)之絕對值及磁滯大。 本發明之目的在於提供一種有機薄膜電晶體絕緣層 材料，其可製造臨限電壓之絕對值及磁滯小之有機薄膜電 323900 6 201239046 (解決課題之手段） 有鑑於以上情事，進行各種探討的結果發現，藉由使 用含雙鍵之可形成交聯結構之特定之樹脂組成物形成閘極 絕緣層，可縮小有機薄膜電晶體之臨限電壓（Vth)之絕對值 及磁滯，而完成本發明。 亦即，本發明係提供一種有機薄膜電晶體絕緣層材 料，其含有高分子化合物（A)，其含有式（1)所表示之官能 基及2個以上之第1官能基，201239046 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a material suitable for forming an insulating layer of an organic thin film transistor. [Prior Art] Organic thin film transistor can be manufactured at a lower temperature than inorganic semiconductors. Therefore, a plastic substrate or a film can be used as the substrate, and by using such a substrate, a lighter and less susceptible element can be obtained than a transistor composed of an inorganic semiconductor. Further, the village can produce a component by coating a film of a coating method by using a coating of bismuth (4), and it is also possible to manufacture a large number of components on a large-area substrate. Furthermore, since the types of materials that can be used for the study of the crystal crystal are abundant, if it is used for the study of materials having different molecular structures, it is possible to manufacture an element having a wide range of characteristics and variability. In the electric field effect type organic thin film transistor of one type of organic thin film transistor, the voltage applied to the gate electrode acts on the semiconductor layer via the gate insulating layer to control the opening and closing of the drain current. Therefore, a gate insulating layer is formed between the gate electrode and the semiconductor layer. Further, the organic semiconductor compound used in the production of the electric field effect type organic thin film transistor is susceptible to environmental influences such as temperature and oxygen. Therefore, the characteristics of the crystal are likely to be deteriorated with time and humidity such as humidity and oxygen. Therefore, in order to remove the structure of the organic thin film transistor element formed by the organic semiconductor compound, it is necessary to form a protective layer in such a manner as to cover the entire structure of the element to protect the contact of the organic semiconductor compound with the external air 323900 201239046 gas. . On the other hand, the organic semiconductor compound is protected by the application of the gate insulating layer in the structure of the upper gate (cut gate) type organic thin film. As described above, the organic thin film transistor is formed with a protective layer covering the organic semiconductor layer, a gate insulating layer, and the like, so that an insulating layer material can be used. In the present specification, an insulating layer or an insulating film of an organic thin film transistor such as the protective layer and the gate insulating layer is referred to as an organic thin film transistor insulating layer. Further, the material used in forming the organic thin film transistor insulating layer is referred to as an organic thin film transistor insulating layer material. Further, the term "material" as used herein refers to a concept including an amorphous material such as a polymer compound, a polymer compound-containing composition, a resin, and a resin composition. The organic thin film transistor insulating layer material is required to have excellent properties such as insulating properties and dielectric breakdown strength when a film is formed. Further, in particular, the electric field effect transistor 'semiconductor layer of the lower gate type is formed by overlapping the gate insulating layer. Therefore, for the organic thin film transistor gate insulating layer material, an affinity for forming an interface with the organic semiconductor and an organic semiconductor, and a film formed of the organic thin film transistor gate insulating material are required to be organic. The surface on the side of the semiconductor layer is flat. As a technique for such a request, Patent Document 1 discloses the use of a combination epoxy resin and a decane coupling agent as an organic thin film transistor gate insulating layer material. In this technique, a hydroxyl group formed during the hardening reaction of an epoxy resin is reacted with a decane coupling agent. It is because the above hydroxyl group can improve the hygroscopicity of the material of the interlayer insulating layer without impairing the stability of the performance of the transistor. Non-Patent Document 1 discloses that a resin obtained by thermally crosslinking polyvinyl phenol (polyvinyl phenc > 1) 323900 5 201239046 and a melamine compound is used for a gate insulating layer. This technique is based on the fact that the melamine compound removes the hydroxyl groups contained in the polyvinylphenol by crosslinking, while increasing the film strength. The pentacene TFT having the gate insulating layer has a small hysteresis and exhibits durability against gate bias stress. Non-Patent Document 2 describes a copolymer in which a polyethylene phenol and a vinyl methacrylate are polymerized in a methyl insulating layer. This technique allows the hydroxyl group of the vinyl phenol to interact with the carboxyl group of the methyl methacrylate to reduce the polarity of the film as a whole. The pentacene TFT having the gate insulating layer has a small hysteresis and exhibits electrical properties of stability. [Prior Art Document] [Patent Document] Patent Document 1: JP-A-2007-305950 [Non-Patent Document] Non-Patent Document 1: Appl. PhyS. Lett. 89, 093507 (2006) Non-Patent Document 2: Appl. phys. Lett. 92, 183306 (2008) [Problem to be Solved by the Invention] However, in consideration of the practical use of a light-emitting element such as an organic electroluminescence element (organic EL element), it is necessary to further enhance the organic thin film transistor. The organic thin film transistor having the above-described conventional gate insulating layer has a large absolute value and hysteresis of the threshold voltage (Vth). An object of the present invention is to provide an organic thin film transistor insulating layer material which can produce an organic film having an absolute value of a threshold voltage and a small hysteresis. 323900 6 201239046 (Means for Solving the Problem) In view of the above, various discussions are made. As a result, it has been found that by forming a gate insulating layer using a specific resin composition containing a double bond capable of forming a crosslinked structure, the absolute value and hysteresis of the threshold voltage (Vth) of the organic thin film transistor can be reduced, and the present invention is completed. invention. That is, the present invention provides an organic thin film transistor insulating layer material comprising a polymer compound (A) containing a functional group represented by the formula (1) and two or more first functional groups.

[式中，匕表示氫原子或曱基。] 該第1官能基係藉由電磁波或熱的作用，而生成與活 性氫反應第2官能基之官能基。 於某一形態中，上述高分子化合物（A)進一步含有式 (2)所表示之重複單元， 323900 7 201239046[wherein, 匕 represents a hydrogen atom or a fluorenyl group. The first functional group generates a functional group that reacts with the living hydrogen to form a second functional group by electromagnetic waves or heat. In one embodiment, the polymer compound (A) further contains a repeating unit represented by the formula (2), 323900 7 201239046

(Raa)u(Raa)u

(R)s-b (Rf)b (2) [式中，R2表示氫原子或曱基。R表示氩原子或碳數1 至20之一價之有機基。Rf表示氟原子或具有氟原子之碳 數1至20之一價之有機基。Raa表示連結高分子化合物之 主鏈與側鏈之可具有氟原子之連結部分。u表示0或1之 整數，b表示1至5之整數。當R為複數個時，該等可為 相同或相異。當Rf為複數個時，該等可為相同或相異。]。 於某一形態中，上述第1官能基係選自以封端劑封端 之異氰酸酯基及以封端劑封端之異硫氰酸基所構成群中之 至少1種之基。 於某一形態中，上述以封端劑封端之異氰酸酯基及以 封端劑封端之異硫氰酸基，係式（3)所表示之基， N={5 R6 (3) [式中，Xa表示氧原子或硫原子，Rs及R6相同或相異， 表示氫原子或碳數1至20之一價之有機基。]。 323900 8 201239046 於某一形態中，上述以封端劑封端之異氰酸酯基及以 封端劑封端之異硫氰酸基，係式（4)所表示之基，(R) s-b (Rf)b (2) wherein R 2 represents a hydrogen atom or a fluorenyl group. R represents an argon atom or an organic group having a carbon number of from 1 to 20. Rf represents a fluorine atom or an organic group having a carbon number of from 1 to 20 which is a fluorine atom. Raa represents a linking moiety which may have a fluorine atom in the main chain and the side chain of the linking polymer compound. u represents an integer of 0 or 1, and b represents an integer of 1 to 5. When R is a plurality, these may be the same or different. When Rf is plural, the numbers may be the same or different. ]. In one embodiment, the first functional group is selected from the group consisting of at least one of a group consisting of an isocyanate group blocked with a blocking agent and an isothiocyanate group blocked with a blocking agent. In one embodiment, the isocyanate group blocked with a blocking agent and the isothiocyanate group blocked with a blocking agent are represented by the formula (3), N={5 R6 (3) In the above, Xa represents an oxygen atom or a sulfur atom, and Rs and R6 are the same or different, and represent a hydrogen atom or an organic group having a carbon number of 1 to 20. ]. 323900 8 201239046 In one embodiment, the isocyanate group blocked with a blocking agent and the isothiocyanate group blocked with a blocking agent are represented by the formula (4).

[式中，Xb表示氧原子或硫原子，R7至R9相同或相異， 表示氫原子或碳數1至20之一價之有機基。]。 於某一形態中，上述高分子化合物（A)進一步含有2 個以上之具有1個活性氫之構造單元、或具有2個以上之 活性氫之構造單元。 於某一形態中，上述有機薄膜電晶體絕緣層材料進一 步含有選自屬於含2個以上活性氫之低分子化合物之活性 氫化合物、及屬於含2個以上活性氫之高分子化合物之活 性氫化合物所構成群中之至少1種活性氫化合物。 於某一形態中，上述有機薄膜電晶體絕緣層材料進一 步含有選自含2個以上之式（6)所表示之官能基之低分子 化合物及含有含該官能基之重複單元之高分子化合物所構 成群中之至少1種化合物， )^R3[wherein, Xb represents an oxygen atom or a sulfur atom, and R7 to R9 are the same or different, and represent a hydrogen atom or an organic group having a carbon number of from 1 to 20. ]. In one embodiment, the polymer compound (A) further contains two or more structural units having one active hydrogen or structural units having two or more active hydrogens. In one aspect, the organic thin film transistor insulating layer material further contains an active hydrogen compound selected from a low molecular compound containing two or more active hydrogens, and an active hydrogen compound belonging to a polymer compound containing two or more active hydrogens. At least one active hydrogen compound in the group. In one aspect, the organic thin film transistor insulating layer material further contains a low molecular compound selected from two or more functional groups represented by the formula (6) and a polymer compound containing a repeating unit containing the functional group. Constituting at least one compound in the group, )^R3

——N (6) 323900 9 201239046 [式中，R3及R4分別獨立地表示氫原子或碳數1至20 之一價之有機基。該一價之有機基中之氫原子可經氟原子 取代。R3中之碳原子與R4中之碳原子，亦可鍵結而形成5 員環或6員環。]。 又，本發明亦提供一種有機薄膜電晶體絕緣層之形成 方法，係包含下述步驟： 將含有上述任一有機薄膜電晶體絕緣層材料之液塗 佈於基材，以於該基材上形成塗佈層之步驟；以及 對該塗佈層照射電磁波或電子射線之步驟。 又，本發明亦提供一種有機薄膜電晶體絕緣層之形成 方法，其係包含下述步驟： 將含有上述任一有機薄膜電晶體絕緣層材料之液塗 佈於基材，以於該基材上形成塗佈層之步驟； 對該塗佈層照射電磁波或電子射線之步驟；以及 對該塗佈層施加熱之步驟。 於某一形態中，上述電磁波係紫外線。 又，本發明亦提供一種有機薄膜電晶體，其具有使用 上述有機薄膜電晶體絕緣層材料所形成之有機薄膜電晶體 絕緣層。 於某一形態中，上述有機薄膜電晶體絕緣層為閘極絕 緣層。 又，本發明亦提供一種顯示器用構件，係含有上述有 機薄膜電晶體。 又，本發明亦提供一種顯示器，係含有上述顯示器構 323900 10 201239046 件。 (發明的效果） 具有使用本發明之有機薄膜電晶體絕緣層材料所形 成之絕緣層的有機薄膜電晶體，臨限電壓之絕對值及磁滯 /J、0 【實施方式】 本說明書中，所謂「高分子化合物」係意指於分子中 含有複數個重複之相同構造單元的化合物，亦包含所謂之 二聚物。另一方面，所謂「低分子化合物」係意指於分子 中不具有重複之相同構造單元的化合物。 <高分子化合物（A)> 本發明之有機薄膜電晶體絕緣層材料含有高分子化 合物，該高分子化合物具有於自由基種的存在下引起加成 聚合反應之官能基，並且，具有複數個當以電磁波或熱作 用時，生成與活性氫反應第2官能基之第1官能基。於本 說明書中，將於自由基種的存在下引起加成聚合反應之官 能基，稱作「加成聚合反應基」。 又，本發明之有機薄膜電晶體絕緣層材料，，較佳為 含有光聚合起始劑作為自由基種的產生源。 於某一形態，加成聚合反應基係藉由光聚合起始劑吸 收光能而產生之自由基種，使得加成聚合起始之官能基。 加成聚合反應基藉由相互地加成聚合，可於絕緣層之内部 形成交聯構造。 於其他形態，加成聚合反應基係吸收電子射線能量而 323900 11 201239046 產生自由基種，且藉由該自由基種使加成聚合起始之官能 基。 雖然，高分子化合物（A)所含之第1官能基不與活性 氫反應，然而，於第1官能基作用電磁波或熱時，生成之 第2官能基係與活性氫反應。亦即，該第1官能基係藉由 電磁波或熱而脫保護，而生成與活性氫反應之第2官能基 者。第2官能基與活性氫化合物之含活性氫之基反應而鍵 結，藉此可於絕緣層之内部形成交聯構造。本說明書中， 所謂「活性氫」係指鍵結於氧原子、硫原子或氮原子之氫 原子，所謂「活性氫化合物」係具有1個以上此種活性氫 之化合物。 第2官能基於閘極絕緣層之形成步驟中直到加熱為止 係被保護（blocking)，以作為第1官能基存在於有機薄膜 電晶體絕緣層材料中。其結果為可提升有機薄膜電晶體絕 緣層材料的貯藏安定性。 前述高分子化合物相當於例如含有具有加成聚合反 應基之重複單元、與具有上述第1官能基之重複單元之高 分子化合物。 具有加成聚合反應基之重複單元，較佳為上述式（1) 所表示之重複單元。於本發明之有機薄膜電晶體絕緣層材 料所含之高分子化合物，較佳為含有式（1)所表示之官能 基、與2個以上第1官能基之高分子化合物。將此種高分 子化合物標記為高分子化合物（A)。 式（1)中，R!表示氫原子或曱基。於某一形態，L為甲 323900 12 201239046 基。 高分子化合物（A)之一較佳態樣，係具有含有式（1)所 表示之官能基之重複單元與含有第1官能基之重複單元的 高分子化合物。含有式（1)所表示之官能基之重複單元，較 佳為式（1-1)所表示之重複單元、式（1-2)所表示之重複單 元0- N (6) 323900 9 201239046 [wherein R3 and R4 each independently represent a hydrogen atom or an organic group having a carbon number of 1 to 20 valence. The hydrogen atom in the monovalent organic group may be substituted by a fluorine atom. The carbon atom in R3 and the carbon atom in R4 may also be bonded to form a 5-membered ring or a 6-membered ring. ]. Moreover, the present invention also provides a method for forming an organic thin film transistor insulating layer, comprising the steps of: applying a liquid containing any of the above organic thin film transistor insulating layer materials to a substrate to form on the substrate; a step of coating a layer; and a step of irradiating the coating layer with electromagnetic waves or electron rays. Moreover, the present invention also provides a method for forming an organic thin film transistor insulating layer, comprising the steps of: applying a liquid containing any of the above organic thin film transistor insulating layer materials to a substrate, on the substrate a step of forming a coating layer; a step of irradiating the coating layer with electromagnetic waves or electron beams; and a step of applying heat to the coating layer. In one embodiment, the electromagnetic wave is ultraviolet light. Further, the present invention also provides an organic thin film transistor having an organic thin film transistor insulating layer formed using the above organic thin film transistor insulating layer material. In one embodiment, the organic thin film transistor insulating layer is a gate insulating layer. Further, the present invention provides a member for a display comprising the above-described organic thin film transistor. Moreover, the present invention also provides a display comprising the above-mentioned display structure 323900 10 201239046 pieces. (Effects of the Invention) An organic thin film transistor having an insulating layer formed using the organic thin film transistor insulating layer material of the present invention, the absolute value of the threshold voltage and hysteresis / J, 0 [Embodiment] In the present specification, "Polymer compound" means a compound containing a plurality of repeating identical structural units in a molecule, and also includes a so-called dimer. On the other hand, the "low molecular compound" means a compound which does not have the same structural unit of repetition in the molecule. <Polymer Compound (A)> The organic thin film transistor insulating layer material of the present invention contains a polymer compound having a functional group which causes an addition polymerization reaction in the presence of a radical species, and has a plural number When electromagnetic waves or heat are applied, a first functional group that reacts with the active hydrogen to form a second functional group is formed. In the present specification, a functional group which causes an addition polymerization reaction in the presence of a radical species is referred to as an "addition polymerization reaction group". Further, the organic thin film transistor insulating layer material of the present invention preferably contains a photopolymerization initiator as a source of generation of a radical species. In one form, the addition polymerization reaction is a radical species generated by absorption of light energy by a photopolymerization initiator, such that the functional group of the initial polymerization is added. The addition polymerization reaction group can form a crosslinked structure inside the insulating layer by mutual addition polymerization. In other forms, the addition polymerization reaction system absorbs electron beam energy and 323900 11 201239046 generates a radical species, and the radical is initiated by the addition of the radical species. The first functional group contained in the polymer compound (A) does not react with the active hydrogen. However, when the first functional group acts on electromagnetic waves or heat, the second functional group formed reacts with the active hydrogen. That is, the first functional group is deprotected by electromagnetic waves or heat to form a second functional group that reacts with active hydrogen. The second functional group is bonded to the active hydrogen-containing group of the active hydrogen compound to bond, whereby a crosslinked structure can be formed inside the insulating layer. In the present specification, the "active hydrogen" means a hydrogen atom bonded to an oxygen atom, a sulfur atom or a nitrogen atom, and the "active hydrogen compound" is a compound having one or more such active hydrogen. The second functional group is blocked in the formation step of the gate insulating layer until heating, and is present as a first functional group in the organic thin film transistor insulating layer material. As a result, the storage stability of the organic thin film transistor insulating layer material can be improved. The polymer compound corresponds to, for example, a high molecular compound containing a repeating unit having an addition polymerization reaction group and a repeating unit having the above first functional group. The repeating unit having an addition polymerization reaction group is preferably a repeating unit represented by the above formula (1). The polymer compound contained in the organic thin film transistor insulating material of the present invention is preferably a polymer compound containing a functional group represented by the formula (1) and two or more first functional groups. This high molecular compound is labeled as a polymer compound (A). In the formula (1), R! represents a hydrogen atom or a fluorenyl group. In a certain form, L is A 323900 12 201239046 base. A preferred embodiment of the polymer compound (A) is a polymer compound having a repeating unit containing a functional group represented by the formula (1) and a repeating unit containing a first functional group. The repeating unit containing the functional group represented by the formula (1) is preferably a repeating unit represented by the formula (1-1) or a repeating unit represented by the formula (1-2).

[式中，R!表示與上述相同之意。h。表示氫原子或曱 基。Rdd為-NH-所表示之基。c表示0或1。][wherein, R! represents the same meaning as described above. h. Represents a hydrogen atom or a sulfhydryl group. Rdd is the base represented by -NH-. c represents 0 or 1. ]

(1-2) [式中，h表示與上述相同之意。Ru表示氫原子或曱 基。Ree表示連結高分子化合物之主鏈與侧鏈之連結部 分。d表示0或1。] 323900 13 201239046 加成聚合反應基之較佳例為含有雙鍵之基。含有雙鍵 之基，可舉例如丙烯醯基、f基丙烯醯基、丙烯醯胺基。 又:上述第1官能基之較佳例，可舉例如以封端劑封 端之異氰酸酯基及以封端劑封端之異硫氰酸基。 上述以封端劑封端之異氰酸醋基或上述以封端劑封 端之異硫氰酸基，可藉由將於丨分子中僅具有丨個可與異 氰酸醋基或料氰縣反叙活性氫之封端難異氮酸醋 基或異硫氰酸基反應來製造。 上述封端劑與異氰酸s旨基或異硫氰酸基反應後，则 為於1呢以下之溫度解離者。封端劑可舉例如醇系化/ 物、酚系化合物、活性亞曱基系化合物、硫醇系化合物 酸醯胺系化合物、酸亞胺系化合物、咪唑系化合物、尿1 系化合物、肟系化合物、胺系化合物、亞胺系化合物、^ 硫酸氫鹽1咬系化合物、Μ系化合物。該等 可單獨使用亦可混合2種以上使用。較佳之封端劑， 例如肟系化合物、吡唑系化合物。 以下，例示具狀龍劑。料、化合物之例， 如甲醇、乙醇、丙醇、丁醇、2乂基己醇、甲基赛路蘇 丁基賽璐蘇、甲基卡必醇、笨甲基醇、環己醇 4 物之例，可舉例㈣、”、乙祕、丁絲、壬基紛: 二壬基盼、苯乙婦化酴、㈣笨？酸自旨。活性 合物之例，可舉例如丙二酸二甲酯、丙二酸二乙酯：： 乙酸曱醋、乙醯乙酸乙g旨、乙酿丙酮。硫醇系化合物 可舉例如丁基硫醇、十二基硫醇。酸醯胺系化合物之例 323900 14 201239046 可舉例如乙醯苯胺、乙酸醯胺、ε -己内醯胺、（5 -戊内酿 胺、r -丁内醢胺，酸亞胺系化合物之例，可舉例如琥珀酸 亞胺、馬來酸亞胺。σ米嗤類系化合物之例，可舉例如咪β坐、 2 -甲基σ米σ坐。 尿素系化合物之例，可舉例如尿素、硫脲、乙烯脲。 胺系化合物之例，可舉例如二苯基胺、苯胺、咔唑。亞胺 系化合物之例，可舉例如乙烯亞胺、聚乙烯亞胺。亞硫酸 氫鹽之例，可舉例如亞硫酸氫鈉。β比唆系化合物之例，可 舉例如2-經基吼α定、2-經基喧琳。將系化合物之例，可舉 例如甲醛肟、乙醛肟、丙酮肟、曱基乙基酮肟、環己酮肟。 0比0坐系化合物之例，可舉例如3, 5-二曱基0比°坐、3, 5-二乙 基π比嗤。 本發明可使用之經封端劑封端之異氰酸酯基或異硫 氰酸基，以上述式（3)所表示之基或上述式（4)所表示之基 為佳。 式（3)及式（4)中，Xa表示氧原子或硫原子，Xb表示 氧原子或硫原子，R5至R9為相同或相異，表示氛原子或碳 數1至20之一價之有機基。 碳數1至20之一價之有機基，可為直鏈、分枝、環 狀之任一者，可為飽和或不飽和。 碳數1至20之一價之有機基，可舉例如碳數1至20 之直鏈狀烴基、碳數3至20之分枝狀烴基、碳數3至20 之環狀烴基、碳數6至20之芳香族烴基，較佳可舉例如碳 數1至6之直鏈狀烴基、碳數3至6之分枝狀烴基、碳數 323900 15 201239046 3至6之環狀烴基、碳數6至20之芳香族烴基。 碳數1至20之直鏈狀烴基、碳數3至2〇之分枝狀烴 基、碳數3觅20之環狀烴基，該等基中所含之氫原子亦可 經氟原子取代* ° 碳數6至20之芳香族烴基，基中之氣原子亦可經烧 基、氟原子、氯原子、溴原子、碘原子等取代。 碳數1至之一價之有機基之具體例，可舉例如曱 基、乙基、丙基、丁基、戊基、己基、異丙基、異丁基、 三級丁基、環丙基、環丁基、環戊基、環己基、環戊炔基、 環己炔基、二氟曱基、二氟乙基、笨基、萘基、蒽基、甲 苯基、二甲苯基、二甲基笨基、三曱基苯基、乙基苯基、 二乙基苯基、三乙基苯基、丙基苯基、丁基苯基、曱基萘 基、二甲基萘基、三曱基萘基、乙烯基萘基、乙烯萘基、 甲基蒽基、乙基蒽基、氯苯基、溴苯基。 碳數1至20之一價之有機基’以燒基為佳。 於某形態，Rs至R9為氫原子。 以封端劑封端之異氰酸酯基，可舉例如〇-(亞曱基胺 基）羧基胺基、0-(1-亞乙基胺基）羧基胺基、〇_(卜甲基亞 乙基胺基）羧基胺基、〇-[1-曱基亞丙基胺基;|羧基胺基、 (N-3, 5-一甲基。比嗤基裁基）胺基、（n_3-乙基-5-甲基。比嗤 基羰基）胺基、（Ν-3,5-二乙基吡唑基羰基）胺基、（Ν-3-丙 基曱基°比唑基幾基）胺基、（Ν-3-乙基-5-丙基吡唑基羰 基）胺基。 以封端劑封端之異硫氰酸基，可舉例如〇_(亞甲基胺 323900 201239046 基）硫幾基胺基、〇_(1_亞乙基胺基）硫缓基胺基、〇_(l-甲 基亞乙基胺基）硫羧基胺基、0-[1-曱基亞丙基胺基]硫羧基 胺基、（N-3, 5-二甲基吡唑基硫羰基）胺基、（N-3-乙基-5-曱基吡唑基硫羰基）胺基、（N-3, 5-二乙基吡唑基硫羰基） 胺基、（N-3-丙基-5-甲基《比唑基硫羰基）胺基、（N-3-乙基 -5-丙基吡唑基硫羰基）胺基。 第1官能基較佳為以封端劑封端之異氰酸酯基。 高分子化合物（A)之製造方法，可舉例如下述方法： 可將成為含有活性氳之重複單元之原料的聚合性單體、與 成為含有第1官能基之重複單元之原料的聚合性單體，使 用光聚合起始劑或熱聚合起始劑使其共聚合而得共聚物 後，使成為上述式（1)所表示之官能基之原料的化合物之可 與活性氫反應的化合物與該共聚物中之活性氫反應的方 法。 聚合性單體之聚合可使用該技術領域者通常所使用 之方法進行。聚合性單體之聚合方法，可例示如下述方法： 將聚合性單體及聚合起始劑溶解於適當之溶劑，將所得溶 液中之溶存氧以惰性氣體取代，接著，加熱或照射一定時 間之方法。 又，高分子化合物（A)之其他製造方法，可舉例如下 述方法：將成為含有活性氫之重複單元之原料的聚合性單 體、與成為含有第1官能基之重複單元之原料的聚合性單 體，使用光聚合起始劑或熱聚合起始劑使其共聚合而得共 聚物後，於脫水劑的存在下，使成為上述式（1)所表示之官 323900 17 201239046 能基之原料的化合物之可與活性氫反應的化合物t之能與 活性氫脫水反應之化合物與該共聚物中之活性氫反應，使 其脫水聚合的方法。 又，高分子化合物（A)之其他製造方法，可舉例如下 述方法：將成為含有活性氳之重複單元之原料的聚合性單 體、與成為含有第1官能基之重複單元之原料的聚合性單 體，使用光聚合起始劑或熱聚合起始劑使其共聚合而得共 聚物後，於酸觸媒的存在下，使成為以上述式（1)所表示之 官能基之原料的化合物之可與活性氫反應的化合物中之能 與活性氫進行酯交換反應之化合物、與該共聚物中之活性 氫反應，使其酯交換的方法。 成為含有活性氫之重複單元之原料的聚合性單體之 例，可舉例如胺基苯乙烯、羥基苯乙烯、乙烯基苯甲基醇、 曱基丙烯酸胺基乙酯、乙二醇單乙烯醚、丙烯酸4-羥基丁 酯、丙烯酸、曱基丙烯酸、4-乙烯基苯曱酸。 含有第1官能基之聚合性單體之例，可舉例如與以封 端劑封端之異氰酸酯基或該以封端劑封端之異硫氰酸基具 有不飽和鍵之單體。與以封端劑封端之異氰酸酯基或該以 封端劑封端之異硫氰酸基具有不飽和鍵之單體，可藉由將 與異氰酸酯基或異硫氰酸基具有不飽和鍵之化合物的化合 物、與封端劑反應來製造。不飽和鍵，以雙鍵為佳。 具有雙鍵與異氰酸自旨基之化合物之例，可舉例如2-丙烯醯氧基乙基異氰酸酯、2-曱基丙烯醯氧基乙基異氰酸 酉旨、2_(2 曱基丙稀龜氧基乙基）氧基乙基異氛酸醋。 323900 18 201239046 具有雙鍵與異硫氰酸基之化合物之例，可舉例如2-丙烯醯氧基乙基異硫氰酸酯、2-甲基丙烯醯氧基乙基異硫 氰酸酯、2-(2’ -曱基丙烯醯氧基乙基）氧基乙基異硫氰酸 酉旨。 聚合性單體所含之封端劑，較佳可使用上述之封端 劑。於具有以封端劑封端之異氰酸酯基或以封端劑封端之 異硫氰酸基與不飽和鍵之單體的製造中，亦可視需要添加 有機溶劑、觸媒等。 上述具有以封端劑封端之異氰酸酯基與雙鍵之單體 之例，可舉例如曱基丙烯酸2-[0-[1’ -曱基亞丙基胺基] 羧基胺基]乙酯、曱基丙烯酸2-[Ν-[Γ，3’ -二甲基基吡 唑基]羰基胺基]乙酯。 上述具有以封端劑封端之異硫氰酸基與雙鍵之單體 之例，可舉例如曱基丙烯酸2-[0-[1’ -曱基亞丙基胺基] 硫羧基胺基]乙酯、曱基丙烯酸2-[Ν-[1’，3’ -二甲基基 吡唑基]硫羰基胺基]乙酯。 成為含有活性氫之重複單元之原料之聚合性單體之 裝填莫耳比，於與聚合有關之總單體中，為5莫耳％以上 50莫耳％以下，較佳為10莫耳％以上45莫耳％以下，更佳 為20莫耳％以上40莫耳％以下。藉由將上述單體之裝填莫 耳比調節於該範圍，可於絕緣層之内部充分形成交聯構 造，將極性基之含量保持於低程度，而抑制絕緣層之分極。 含有第一官能基之聚合性單體之裝填莫耳比，於與聚 合有關之總單體中，較佳為5莫耳％以上50莫耳％以下，更 323900 19 201239046 佳為5莫耳％以上40莫耳％以下。藉由將上述單體之裝填莫 耳比調節於該範圍，可於絕緣層之内部充分形成交聯構 造，將極性基之含量保持於低程度，而抑制絕緣層之分極。 該光聚合起始劑，可舉例如苯乙酮（acetophenone)、 2，2_二曱氧基_2_苯基苯乙闕、2，2 -二乙氣基苯乙嗣、4_ 異丙基-2-羥基-2-甲基苯丙酮、2-羥基-2-曱基苯丙酮、 4, 4’ -雙（二乙基胺基）二苯基酮、二苯基酮 (benzophenone)、曱基（鄰苯曱醯基）苯甲酸酯、1-苯基 -1,2-丙二酮-2-(0-乙氧基羧基）肟、1-苯基-1,2-丙二酮 -2-(鄰苯甲醯基）肟、安息香、安息香曱醚、安息香***、 安息香異丙醚、安息香異丁醚、安息香辛醚、二苯甲醯 (benzil)、苯曱基二曱基縮酮、苯曱基二乙基縮酮、二乙 醯（diacetyl)等綠基化合物、甲基蒽酿、氣蒽S昆、氯硫雜 蔥酮、2-曱基硫雜蔥酮、2-異丙基硫雜蔥酮等蒽醌衍生物 或硫雜蔥酮衍生物、二硫化二苯、二硫代胺曱酸酯等硫化 合物。 當使用光能作為起始光聚合的能量時，照射於聚合性 單體之光的波長為360nm以上，較佳為360至450nm。 上述熱聚合起始劑，只要可成為自由基聚合之起始劑 之化合物即可，可舉例如2, 2’ -偶氮雙異丁腈、2, 2’ -偶 氮雙異戊腈、2,2’-偶氮雙（2,4-二曱基戊腈）、4,4’-偶 氮雙（4-氰基戊酸）、1，1’ -偶氮雙（環己烷腈）、2,2’ -偶 氮雙（2-甲基丙烷）、2,2’ -偶氮雙（2-曱基丙脒）2鹽酸鹽 等偶氮系化合物；過氧化曱基乙基酮、過氧化甲基異丁基 323900 20 201239046 酮、過氧化環己酮、過氧化乙醯丙酮等過氧化酮類、過氧 化異丁基、過氧化苯曱醯基、過氧化2, 4-二氯苯甲醯基、 過氧化鄰曱基苯甲醯基、過氧化月桂醯基、過氧化對氯苯 曱醯基等過氧化二醯基類；2, 4, 4-三曱基戊基-2-氫過氧化 物、二異丙基苯氫過氧化物、異丙苯基氫過氧化物、三級 丁基氫過氧化物等氫過氧化物類；過氧化二異丙苯、過氧 化三級丁基異丙苯、過氧化二-三級丁基、三（三級丁基過 氧）三畊等過氧化二烷基類；、1，1-二-三級丁基過氧環己 烷、2, 2-二（三級丁基過氧）丁烷等過氧縮酮類；三級丁基 過氧三曱基乙酸酯、三級丁基過氧-2-乙基己酸酯、三級丁 基過氧異丁酸酯、二-三級丁基過氧六氳對酞酸酯、二-三 級丁基過氧壬二酸酯、三級丁基過氧-3, 5, 5-三曱基己酸 酯、三級丁基過氧乙酸酯、三級丁基過氧苯甲酸酯、二-三級丁基過氧三甲基己二酸酯等烷基過氧化酯類；二異丙 基過氧二碳酸酯、二-二級丁基過氧二碳酸酯、三級丁基過 氧異丙基碳酸酯等過氧化碳酸酯類。 成為上述式（1)所表示之官能基之原料的化合物之能 與活性氬反應之化合物之例，可舉例如丙烯酸、曱基丙烯 酸、丙烯醯胺、丙烯醯氣、曱基丙烯醯氯、丙烯酸曱酯、 曱基丙烯酸甲酯。 可使用於高分子化合物（A)之製造之脫水劑之例，可 舉例如Ν，Ν’ -二環己基碳二醯亞胺。 可使用於高分子化合物（Α)之製造之酸觸媒之例，可 舉例如硫酸。 323900 21 201239046 本發明所使用之高分子化合物（A)，亦可於將成為含 有活性氫之重複單元之原料的聚合性單體、成為含有第1 官能基之重複單元以外之聚合性單體在聚合時添加。 追加使用之聚合性單體，可舉例如丙烯酸酯及其衍生 物、曱基丙烯酸酯及其衍生物、苯乙烯及其衍生物、乙酸 乙烯酯及其衍生物、曱基丙烯腈及其衍生物、丙烯腈及其 衍生物、有機敌酸之乙烯醋及其衍生物、有機叛酸之烯丙 酉旨及其衍生物、富馬酸之二烧基醋及其衍生物、馬來酸之 二烷基酯及其衍生物、衣康酸之二烷基酯及其衍生物、有 機羧酸之N-乙烯醯胺衍生物、末端不飽和烴及其衍生物 等、含不飽和烴基之有機鍺衍生物等。 追加使用之聚合性單體的種類，可視對絕緣層所要求 之特性而適當地選擇。由對溶劑之優異财久性或縮小有機 薄膜電晶體之磁滯的觀點考量，含有如苯乙烯或苯乙烯衍 生物等之化合物之膜中，可選擇分子之密度高、可形成硬 膜的單體。又，由對閘極電極或基板之表面等絕緣層之鄰 接面之密合性的觀點考量，可選擇如曱基丙烯酸酯及其衍 生物、丙烯酸酯及其衍生物之類對高分子化合物（A)賦予可 塑性的單體。 丙烯酸酯類及其衍生物，可使用單官能之丙烯酸酯、 或當於使用量有限制時亦可使用多官能之丙烯酸酯。此種 單官能之丙烯酸酯或多官能之丙稀酸酯，可舉例如丙烯酸 曱酉旨、丙稀酸乙S旨、丙烯酸正丙S旨、丙稀酸異丙醋、丙婦 酸正丁酯、丙烯酸異丁酯、丙烯酸二級丁酯、丙烯酸己酯、 323900 22 201239046 丙烯酸辛酯、丙烯酸-2-乙基己酯、丙烯酸癸酯、丙烯酸異 莰酯、丙稀酸環己酯、丙烯酸苯酯、丙烯酸苯甲酯、丙烯 酸-2-羥基乙酯、丙烯酸_2_羥基丙酯、丙烯酸-3-羥基丙 酯、丙烯酸-2-羥基丁酯、丙烯酸-2-羥基苯基乙酯、乙二 醇一丙婦酸自旨、丙二醇二丙稀酸醋、1，4-丁二醇二丙婦酸 西曰、一乙一醇一丙稀酸S旨、三乙二醇二丙稀酸醋、三經甲 基丙烷二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、新戊四醇 五丙烯酸酯、丙烯酸2, 2, 2-三氟乙酯、丙烯酸2, 2, 3, 3, 3-五氟丙酯、丙烯酸2-(全氟丁基）乙酯、丙烯酸3-全氟丁基 -2-羥基丙酯、丙烯酸2-(全氟己基）乙酯、丙烯酸3-全氟 己基-2-羥基丙酯、丙烯酸2-(全氟辛基）乙酯、丙烯酸3_ 全氟辛基-2-羥基丙酯、丙烯酸2-(全氟癸基）乙酯、丙烯 酸2-(全氟-3-甲基丁基）乙g旨、丙烯酸3-(全氟-3-甲基丁 基）-2-羥基丙酯、丙烯酸2-(全氟-5-曱基己基）乙酯、丙 烯酸2-(全氟-3-曱基丁基）-2-羥基丙酯、丙烯酸3-(全氟 -5-曱基己基）-2-羥基丙酯、丙烯酸2-(全氟-7-甲基辛基） 乙醋、丙烯酸3-(全氟-7-甲基辛基）-2-羥基丙酯、丙烯酸 1H，1H，3H-四氟丙酯、丙烯酸1H，1H，5H-八氟戊酯、丙烯酸 1H，1H，7H-十一氟庚醋、丙烯酸1H，1H，9H-十六氟壬醋、丙 烯酸1H-1-(三氟甲基）三氟乙酯、丙烯酸iH，1H，3H_六氟丁 酿、N，N-二甲基丙烯醯胺、N，N-二乙基丙烯醯胺、N_丙烯 醯基嗎福林。 曱基丙烯酸酯類及其衍生物，可使用單官能之甲基丙 烯酸醋、或當於使用量有限制時亦可使用多官能之曱基丙 323900 23 201239046 稀酸醋。此種單官能之甲基丙烯酸酯或多官能之甲基丙婦 酸醋’可舉例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、曱基 丙烯酸正丙醋、曱基丙烯酸異丙酯、甲基丙烯酸正丁酯、 甲基丙烯酸異丁酯、甲基丙烯酸二級丁酯、曱基丙烯酸己 醋、曱基丙烯酸辛酯、甲基丙烯酸一2_乙基己酯、甲基丙烯 酸癸酯、曱基丙烯酸異莰酯、曱基丙烯酸環己酯、甲基丙 烯酸苯酯、甲基丙烯酸苯甲酯、甲基丙烯酸_2_羥基乙酯、 甲基丙烯酸-2-羥基丙酯、曱基丙烯酸_3_羥基丙酯、曱基 丙烯酸-2-羥基丁酯、甲基丙烯酸_2_羥基苯基乙酯、乙二 醇二甲基丙烯酸酯、丙二醇二甲基丙烯酸酯、丨，4_丁二醇 二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二 曱基丙烯酸酯、三羥曱基丙烷二甲基丙烯酸酯、三羥甲基 丙烷三甲基丙烯酸酯、新戊四醇五甲基丙烯酸酯、曱基丙 烯酸2, 2, 2-三氟乙酯、甲基丙烯酸2, 2, 3, 3, 3_五氟丙酯、 曱基丙烯酸2-(全氟丁基）乙酯、曱基丙烯酸3_全氟丁基 -2-羥基丙酯、甲基丙烯酸2-(全氟己基）乙酯、曱基丙烯 酉文3-全氟己基-2-經基丙酯、曱基丙婦酸2-(全氟辛基）乙 酯、曱基丙烯酸3-全氟辛基-2-羥基丙酯、甲基丙烯酸 2-(全氟癸基）乙酯、曱基丙烯酸2-(全氟-3-曱基丁基）乙 酯、甲基丙烯酸3-(全氟-3-曱基丁基）-2-羥基丙酯、甲基 丙烯酸2-(全氟-5-曱基己基）乙酯、甲基丙烯酸2_(全氟 -3-曱基丁基）-2-羥基丙酯、甲基丙烯酸3_(全氟_5_曱基 己基）-2-經基丙酯、甲基丙婦酸2-(全U-曱基辛基）乙 酯、甲基丙烯酸3-(全氟-7-曱基辛基）_2-羥基丙酯、曱基 323900 24 201239046 丙烯酸1H，1H，3H-四氟丙酯、曱基丙烯酸1H，1H，5H-八氟戊 酯、曱基丙烯酸1H，1H，7H-十二氟庚酯、曱基丙烯酸 1H，1H，9H-十六氟壬酯、甲基丙烯酸1H-1-(三氟曱基）三氟 乙酯、曱基丙烯酸1H，1H, 3H-六氟丁酯、N，N-二曱基甲基 丙烯醯胺、N, N-二乙基曱基丙烯醯胺、N-丙烯醯基嗎福林。 苯乙烯及其衍生物之例，可舉例如苯乙烯、2, 4-二曱 基-α -甲基笨乙烯、鄰曱基苯乙烯、間曱基苯乙烯、對曱 基苯乙烯、2, 4-二曱基苯乙烯、2, 5-二甲基苯乙烯、2,6-二曱基苯乙烯、3, 4-二甲基苯乙烯、3,5-二曱基苯乙烯、 2,4, 6-三甲基苯乙烯、2, 4, 5-三曱基苯乙烯、五甲基笨乙 烯、鄰乙基笨乙烯、間乙基苯乙烯、對乙基苯乙烯、鄰氯 苯乙烯、間氯苯乙烯、對氯苯乙烯、鄰溴苯乙烯、間溴苯 乙烯、對溴苯乙烯、鄰曱氧基苯乙烯、間曱氧基苯乙烯、 對甲氧基苯乙烯、鄰羥基苯乙烯、間羥基苯乙烯、對羥基 苯乙烯、2-乙烯基聯苯、3-乙烯基聯笨、4-乙烯基聯苯、 1-乙烯基萘、2-乙烯基萘、4-乙烯基-對聯三苯、1-乙烯基 蒽、α-甲基苯乙烯、鄰異丙烯基甲苯、間異丙烯基甲苯、 對異丙烯基甲苯、2, 4-二甲基-α-甲基苯乙烯、2, 3-二甲 基-α-曱基苯乙烯、3, 5-二甲基-α-甲基苯乙烯、對異丙 基-α-甲基苯乙烯、乙基苯乙烯、α-氯苯乙烯、二乙 烯基苯、二乙烯基聯苯、二異丙基苯、4-胺基苯乙烯。 有機羧酸之乙烯酯及其衍生物之例，可舉何如乙酸乙 烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙稀酯、己二酸 二乙烯酯。 323900 25 201239046 有機叛酸之烯丙醋及其衍生物之例，可舉例如乙酸烯 丙酯、苯甲酸烯丙酯、己二酸烯丙酯、對苯二甲酸二烯丙 酯、間苯二甲酸二烯丙酯、苯二甲酸二烯丙酯。 富馬酸之二烧基醋及其衍生物之例，可舉例如富馬酸 二曱酯、富馬酸二乙酯、富馬酸二異丙酯、富馬酸二-二級 丁酯、富馬酸二異丁酯、富馬酸二-正丁酯、富馬酸二-2-乙基己酯、富馬酸二苯曱酯。 馬來酸之二院基自旨及其衍生物之例，可舉例如馬來酸 二曱酯、馬來酸二乙酯、馬來酸二異丙酯、馬來酸二-二級 丁酯、馬來酸二異丁酯、馬來酸二-正丁酯、馬來酸二-2-乙基己酯、馬來酸二苯曱酯。 衣康酸之二烷基酯及其衍生物之例，可舉例如衣康酸 二曱酯、衣康酸二乙酯、衣康酸二異丙酯、衣康酸二-二級 丁酯、衣康酸二異丁酯、衣康酸二-正丁酯、衣康酸二-2-乙基己酯、衣康酸二苯曱酯。 有機羧酸之N-乙烯醯胺衍生物之例，可舉例如N-曱 基-N-乙烯醯胺。 馬來醯亞胺及其衍生物之例，可舉例如N-苯基馬來醯 亞胺、N-環己基馬來醯亞胺。 末端不飽和烴及其衍生物之例，可舉例如1 - 丁烯、1 -戊烯、1-己烯、1-辛烯、乙烯基環己烷、氣乙烯、烯丙醇。 含不飽和烴基之有機鍺衍生物之例，可舉例如烯丙基 三甲基鍺、烯丙基三乙基鍺、烯丙基三丁基鍺、三曱基乙 婦基錯、三乙基乙烯基鍺。 323900 26 201239046 該等之中，以丙烯酸烷酯、甲基丙烯酸烷酯、苯乙烯、 丙烯腈、甲基丙烯腈、烯丙基三甲基鍺為佳。 南分子化合物（A)重量平均分子量以3〇〇〇至1〇〇〇〇〇〇 為佳，以5000至500000為更佳，可為直鏈狀、分枝狀、 壤狀之任一者。 本發明所使用之高分子化合物（A),可舉例如聚（苯乙 烯-共-[4-(甲基丙烯醯基胺基苯乙烯）]_共4240-0,-甲基亞丙基胺基）羧基胺基]乙基-曱基丙烯酸酯])、聚（苯 乙烯-共-[4-(曱基丙烯醯基胺基笨乙烯）]_共_[2_[1，_ (3 ’5’ -二甲基吡唑基）羰基胺基]乙基-曱基丙烯酸 酯])、聚（苯乙烯-共_[4-(甲基丙烯醯基胺基苯乙嫦）]_共— 丙烯腈-共-[2-[〇-(1，-曱基亞丙基胺基）羧基胺基]乙基_ 曱基丙烯酸醋])、聚（苯乙烯-共_[4_(甲基丙烯醯基胺基苯 乙烯）]-共-丙烯腈-共-[2-[1’ -(3，，5，-二甲基吡唑基） 羰基胺基]乙基-甲基丙烯酸酯])、聚（苯乙烯—共-[4_(曱基 丙烯醯基胺基苯乙烯）]—共-丙烯腈—共-[2-[〇-(ι，_甲基 亞丙基胺基）致基胺基]乙基-甲基丙婦酸g旨]-共-稀丙基甲 基鍺）、聚（苯乙烯-共-[2-甲基丙烯醯氧基乙基—甲基丙烯 酸酉旨]-共-丙婦腈-共-[2-[1’ -(3’，5’ -二曱基0比0坐基） 羰基胺基]乙基-曱基丙烯酸酯]-共-烯丙基甲基鍺）、聚 ([2-曱基丙烯醯氧基乙基-曱基丙烯酸酯]—共-[2-[〇-(1 甲基亞丙基胺基）叛基胺基]乙基-甲基丙烯酸醋])、 聚（[2-甲基丙烯醯氧基乙基-曱基丙烯酸酯]-共-[2-[1，-(3’，5’ -二曱基吡唑基）羰基胺基]乙基-曱基丙烯酸 323900 27 201239046 酯])、聚（苯乙烯-共- [2-曱基丙烯酿氧基乙基-曱基丙烯酸 酯]-共-[2-[0-(Γ -曱基亞丙基胺基）羧基胺基]乙基-甲 基丙烯酸酯])、聚（苯乙烯-共-[2-甲基丙烯醯氧基乙基-曱基丙烯酸酯]-共-[2-[1’ -(3，，5’ -二甲基吡唑基）緵 基胺基]乙基-曱基丙烯酸酯])。 <尚分子化合物（Β)> 本發明之有機薄膜電晶體絕緣層材料中所含之高分 子化合物之較佳態樣’係具有加成聚合反應基、具有氟原 子、具有2個以上之上述第1官能暴的高分子化合物。將 此種局分子化合物，記為尚.分子化合物（Β)。 藉由於有機薄膜電晶體絕緣層材料導入氟，由該材料 所形成之絕緣層極性低、可抑制絕緣層之分極。又，若於 絕緣層之内部形成交聯構造，則可抑制分子構造的移動， 而可抑制絕緣層之分極。若抑制了絕緣層之分極，則例如 當作為閘極絕緣層使用時，有機薄膜電晶體之磁滯降低、 動作精度提升。 _ 子 干又狂钩鼠原子並非取代高分子化合物之主鏈的氫原 ，而是取代側鏈或側基（pendant)的氫原子。若氟原子於 侧鏈或側基取代，麟如有機半導體之獅其他有機材料 親淨f生不會降低，於含該有機材料之層的形成中，有 材料與絕緣層之露出面相接，使層的形成變得容易。 之其=，合物⑻亦可具有含氣原子之基。含氣原子 之基之較佳例’可舉例如氫原 原子經氟料取代之騎、子轉方基、氧 院基方基、特別是氫原子經氟原子取 323900 28 201239046 代之苯基、氫原子經氟原子取代之烷基苯基。 高分子化合物（B)之中，較佳為含有具有含雙鍵之官 能基、2個以上之第1官能基、與含氟原子之基之重複單 元的高分子化合物，更佳為含有式（1)所表示之官能基、2 個以上之第1官能基、與式（2)所表示之重複單元之高分子 化合物’又更佳為含有含式（1)所表示之官能基之重複單 疋、含第1官能基之重複單元、與式（2)所表示之重複單元 之向分子化合物。 式（2)中，R2表示氫原子或甲基。於某一形態，匕為氫 原子。Raa表示連結主鏈與側鏈之可具有氟原子之連結部 刀連結部分只要為具有於使本發明之有機薄腺電晶體絕 緣層材料交聯之環境條件下不顯示反應性之構造之二價之 基即可。連結部分之具體例，可舉例如由碳數丨炱2〇之二 ‘之有機基所構成之鍵、醚鍵（—〇_)、鍵（_c〇_)、酯鍵 GC〇〇—、_〇c〇_)、醯胺鍵（_NHC〇_、—c〇nh—)、胺基甲酸酯 ^咖…㈣勝）及組合該等鍵之鍵等。u表示〇幻 <整數。於某一形態，u為〇。 有趟lf表示氟原子或具有氟原子之碳數1至20之-價之 機基。於某一形態，Rf為氟原子。 b表示1至5之整數。於某一形態4為5。 R表示氫原子或碳數1至20之-價之有 分枝表示之碳數^之—價之有機為直鍵、 、％狀之任一者，可為飽和或不飽和。 323900 如至20之-價之有機基’可舉例如碳數1至2。 29 201239046 之直鏈狀烴基、碳數3至20之分枝狀烴基、碳數3至20 之環狀烴基、碳數6至20之芳香族烴基，較佳可舉例如碳 數1至6之直鏈狀烴基、碳數3至6之分枝狀烴基、碳數 3至6之環狀烴基、碳數6至20之芳香族烴基。 碳數6至20之芳香族烴基，基中之氫原子亦可經烷 基、氣原子、漠原子、蛾原子等取代。 當R為碳數1至20之一價之有機基時，該一價之有 機基不具有氟原子。 碳數1至20之一價之有機基之具體例，可舉例如曱 基、乙基、丙基、丁基、戊基、己基、異丙基、異丁基、 三級丁基、環丙基、環丁基、環戊基、環己基、環戊炔基、 環己炔基、苯基、萘基、蒽基、曱苯基、二曱苯基、二曱 基苯基、三曱基苯基、乙基苯基、二乙基苯基、三乙基苯 基、丙基苯基、丁基苯基、甲基萘基、二曱基萘基、三曱 基萘基、乙烯基萘基、乙烯萘基、曱基蒽基、乙基蒽基、 氯苯基、溴苯基。 碳數1至20之一價之有機基，以烷基為佳。 當Rf為具有氟原子之碳數1至20之有機基時，具有 氟原子之碳數1至20之之一價之有機基，可舉例如三氟甲 基、2, 2, 2-三氟乙基、2, 2, 3, 3, 3-五氟丙基、2-(全氟丁基） 乙基、五氟苯基、三氟曱基苯基等。 上述碳數1至20之二價之有機基，可為直鏈、分枝、 環狀之任一者，可為脂肪族烴基、亦可為芳香族烴基。可 舉例如碳數1至20之二價之直鏈狀脂肪族烴基、碳數3 323900 30 201239046 至2〇之二價之分枝狀脂肪族烴基、碳數3至20之二價之 環狀烴基、可域基等取代之碳數6至2G之二價之芳香族 ^基山其中’較佳為碳數1至6之二價之直鏈狀脂肪族烴 基炭數3至6之二價之分枝狀脂肪族煙基、碳數3至6(1-2) [wherein h represents the same meaning as described above. Ru represents a hydrogen atom or a thiol group. Ree represents a linking portion linking the main chain and the side chain of the polymer compound. d represents 0 or 1. ] 323900 13 201239046 A preferred example of the addition polymerization reaction group is a group containing a double bond. The group containing a double bond may, for example, be an acrylonitrile group, an f-based acrylonitrile group or an acrylamide group. Further, preferred examples of the above first functional group include, for example, an isocyanate group blocked with a blocking agent and an isothiocyanate group blocked with a blocking agent. The above-mentioned isocyanate group blocked with a blocking agent or the above-mentioned isothiocyanate group blocked with a blocking agent can be obtained by using only one of the molecules in the oxime molecule with isocyanate or cyanide. The county anti-synthesis hydrogen is blocked by the reaction of a dihydronitrate or isothiocyanate group. When the above blocking agent is reacted with an isocyanate group or an isothiocyanate group, it is dissociated at a temperature of 1 or less. The blocking agent may, for example, be an alcohol-based compound, a phenol-based compound, an active sulfhydryl-based compound, a thiol-based compound amide amine-based compound, an acid imine-based compound, an imidazole-based compound, a urine-based compound, or an anthraquinone-based compound. A compound, an amine compound, an imine compound, a hydrogensulfate salt 1 bite compound, and an anthraquinone compound. These may be used alone or in combination of two or more. Preferred blocking agents are, for example, an anthraquinone compound or a pyrazole compound. Hereinafter, a sessile agent is exemplified. Examples of materials and compounds, such as methanol, ethanol, propanol, butanol, 2-decylhexyl alcohol, methyl sarbuta butyl acesulfame, methyl carbitol, stupid methyl alcohol, cyclohexanol For example, (4), ", 秘 secret, Dingsi, 壬基纷: 壬 壬 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 And diethyl malonate:: acetic acid vinegar, acetonitrile acetic acid, ethylene glycol, and ethyl acetonide. Examples of the thiol compound include butyl thiol and dodecyl thiol. Examples of acid amide compound 323900 14 201239046 For example, examples of acetanilide, decylamine acetate, ε-caprolactam, (5-pentanelactone, r-butylidene, and acid imine compound) may be mentioned, for example, succinic acid imide. Examples of the samarium bismuth-based compound include, for example, a stilbene and a 2-methyl sigma sigma. Examples of the urea-based compound include urea, thiourea, and ethylene urea. Examples of the compound include diphenylamine, aniline, and carbazole. Examples of the imine compound include, for example, ethyleneimine and polyethyleneimine. Examples of the hydrogen salt include sodium hydrogen sulfite. Examples of the beta ruthenium-based compound include, for example, 2-aminopyridinium and 2-pyrimidine. Examples of the compound are, for example, formaldehyde oxime. , acetaldehyde oxime, acetone oxime, mercaptoethyl ketone oxime, cyclohexanone oxime. Examples of 0 to 0 sitting compounds, for example, 3, 5-dimercapto 0 to °, 3, 5- 2 The base π is 嗤. The isocyanate group or the isothiocyanate group which is blocked by the terminal blocking agent to be used in the invention is preferably a group represented by the above formula (3) or a group represented by the above formula (4). (3) and in the formula (4), Xa represents an oxygen atom or a sulfur atom, Xb represents an oxygen atom or a sulfur atom, and R5 to R9 are the same or different, and represent an organic atom of an atmosphere atom or a carbon number of 1 to 20 The organic group having a carbon number of 1 to 20 may be any of a straight chain, a branch, and a ring, and may be saturated or unsaturated. The organic group having a carbon number of 1 to 20 may be, for example, The linear hydrocarbon group having 1 to 20 carbon atoms, the branched hydrocarbon group having 3 to 20 carbon atoms, the cyclic hydrocarbon group having 3 to 20 carbon atoms, and the aromatic hydrocarbon group having 6 to 20 carbon atoms are preferably, for example, a carbon number of 1. Straight chain hydrocarbon group to 6 a branched hydrocarbon group of 3 to 6 carbon number, 323900 15 201239046, a cyclic hydrocarbon group of 3 to 6, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a linear hydrocarbon group having 1 to 20 carbon atoms, and a carbon number of 3 to 2 a branched hydrocarbon group or a cyclic hydrocarbon group having a carbon number of 3觅20, wherein the hydrogen atom contained in the group may be substituted by a fluorine atom*° an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the gas atom in the group may also be The alkyl group, the fluorine atom, the chlorine atom, the bromine atom, the iodine atom or the like is substituted. Specific examples of the organic group having a carbon number of 1 to 1 are, for example, an anthracenyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. , isopropyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentynyl, cyclohexynyl, difluorodecyl, difluoroethyl, stupid Base, naphthyl, anthracenyl, tolyl, xylyl, dimethylphenyl, tridecylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, butyl Phenylphenyl, decylnaphthyl, dimethylnaphthyl, tridecylnaphthyl, vinylnaphthyl, vinylnaphthyl, methylindenyl, ethylindenyl, chlorophenyl, bromophenyl. The organic group having a carbon number of 1 to 20 is preferably an alkyl group. In a certain form, Rs to R9 are hydrogen atoms. The isocyanate group blocked with a terminal blocking agent may, for example, be a fluorenyl-(fluorenylamino)carboxyamino group, a 0-(1-ethylideneamino)carboxyamino group, or a fluorene-methylethylamino group. Carboxyamino group, 〇-[1-mercaptopropylamino group; |carboxyamino group, (N-3, 5-methyl group, fluorenyl group) amine group, (n_3-ethyl-5) -Methyl. fluorenylcarbonyl)amino, (Ν-3,5-diethylpyrazolylcarbonyl)amine, (Ν-3-propylindolylpyrazolyl)amine, Indole-3-ethyl-5-propylpyrazolylcarbonyl)amino group. The isothiocyanate group blocked with a blocking agent may, for example, be 〇-(methyleneamine 323900 201239046 thiol)thiolamino group, 〇_(1-ethylamino)thiolamino group, 〇_(l-methylethylideneamino)thiocarboxyamino, 0-[1-mercaptopropylamino]thiocarboxyamino, (N-3, 5-dimethylpyrazolylthio Carbonyl)amino, (N-3-ethyl-5-mercaptopyrazolylthiocarbonyl)amino, (N-3, 5-diethylpyrazolylthiocarbonyl)amine, (N-3- Propyl-5-methyl "Bizozolylthiocarbonyl"amino, (N-3-ethyl-5-propylpyrazolylthiocarbonyl)amino. The first functional group is preferably an isocyanate group blocked with a blocking agent. In the method for producing the polymer compound (A), for example, a polymerizable monomer which is a raw material of a repeating unit containing an active oxime and a polymerizable monomer which is a raw material of a repeating unit containing a first functional group can be used. After copolymerization using a photopolymerization initiator or a thermal polymerization initiator to obtain a copolymer, a compound reactive with active hydrogen of a compound which is a raw material of the functional group represented by the above formula (1) is copolymerized with the copolymer. A method of reacting active hydrogen in a substance. The polymerization of the polymerizable monomer can be carried out by a method generally used by those skilled in the art. The polymerization method of the polymerizable monomer can be exemplified by a method of dissolving a polymerizable monomer and a polymerization initiator in a suitable solvent, and replacing the dissolved oxygen in the obtained solution with an inert gas, followed by heating or irradiation for a certain period of time. method. In addition, as another method for producing the polymer compound (A), for example, a polymerizable monomer which is a raw material of a repeating unit containing active hydrogen and a polymerizable material which is a raw material of a repeating unit containing a first functional group may be used. After the monomer is copolymerized with a photopolymerization initiator or a thermal polymerization initiator to obtain a copolymer, in the presence of a dehydrating agent, the material of the 323900 17 201239046 energy base represented by the above formula (1) is obtained. The compound t which reacts with active hydrogen can react with the active hydrogen dehydration reaction with the active hydrogen in the copolymer to cause dehydration polymerization. In addition, as another method for producing the polymer compound (A), for example, a polymerizable monomer which is a raw material of a repeating unit containing an active oxime and a polymerizable material which is a raw material of a repeating unit containing a first functional group may be used. After the copolymer is copolymerized with a photopolymerization initiator or a thermal polymerization initiator to obtain a compound which is a raw material of the functional group represented by the above formula (1) in the presence of an acid catalyst A method of transesterifying a compound capable of transesterifying with active hydrogen in a compound reactive with active hydrogen, and reacting with active hydrogen in the copolymer. Examples of the polymerizable monomer which is a raw material of a repeating unit containing active hydrogen include, for example, aminostyrene, hydroxystyrene, vinylbenzyl alcohol, aminoethyl methacrylate, ethylene glycol monovinyl ether. , 4-hydroxybutyl acrylate, acrylic acid, methacrylic acid, 4-vinyl benzoic acid. Examples of the polymerizable monomer having a first functional group include a monomer having an unsaturated bond which is blocked with an isocyanate group blocked with a blocking agent or an isothiocyanate group blocked with a blocking agent. A monomer having an unsaturated bond with an isocyanate group blocked with a blocking agent or an isothiocyanate group blocked with a blocking agent may have an unsaturated bond with an isocyanate group or an isothiocyanate group. The compound of the compound is produced by reacting with a blocking agent. For unsaturated bonds, double bonds are preferred. Examples of the compound having a double bond and an isocyanate group include, for example, 2-propenyloxyethyl isocyanate, 2-mercaptopropenyloxyethyl isocyanate, and 2-(2-mercaptopropylidene). Thin toluene oxyethyl)oxyethyl oleic acid vinegar. 323900 18 201239046 Examples of the compound having a double bond and an isothiocyanate group include, for example, 2-propenyloxyethyl isothiocyanate and 2-methylpropenyloxyethyl isothiocyanate. 2-(2'-Mercaptopropenyloxyethyl)oxyethyl isothiocyanate. As the blocking agent contained in the polymerizable monomer, the above-mentioned blocking agent can be preferably used. In the production of a monomer having an isocyanate group blocked with a blocking agent or an isothiocyanate group and an unsaturated bond blocked with a blocking agent, an organic solvent, a catalyst or the like may be added as needed. Examples of the monomer having an isocyanate group and a double bond blocked with a blocking agent include, for example, 2-[0-[1'-mercaptopropylamino]carboxyamino]ethyl methacrylate. 2-[Indo-[Γ,3'-dimethylpyrazolyl]carbonylamino]ethyl methacrylate. Examples of the monomer having an isothiocyanate group and a double bond blocked with a terminal blocking agent include, for example, 2-[0-[1'-mercaptopropylamino]thiomethylamino group of methacrylic acid. Ethyl ester, 2-[Ν-[1',3'-dimethylpyrazolyl]thiocarbonylamino]ethyl methacrylate. The molar ratio of the polymerizable monomer which is a raw material of the repeating unit containing active hydrogen is 5 mol% or more and 50 mol% or less, preferably 10 mol% or more, based on the total monomer related to the polymerization. 45 mol% or less, more preferably 20 mol% or more and 40 mol% or less. By adjusting the packing molar ratio of the above monomer to this range, a cross-linking structure can be sufficiently formed inside the insulating layer to keep the content of the polar group low, and the polarization of the insulating layer can be suppressed. The molar ratio of the polymerizable monomer containing the first functional group is preferably 5 mol% or more and 50 mol% or less, more preferably 323900 19 201239046, preferably 5 mol%, of the total monomer related to the polymerization. Above 40% by mole. By adjusting the packing molar ratio of the above monomer to this range, a cross-linking structure can be sufficiently formed inside the insulating layer to keep the content of the polar group low, and the polarization of the insulating layer can be suppressed. The photopolymerization initiator may, for example, be acetophenone, 2,2-dimethoxy-2-phenylphenyridinium, 2,2-diethylphenylphenyridinium, 4-isopropylidene -2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-mercaptopropiophenone, 4,4'-bis(diethylamino)diphenyl ketone, benzophenone, hydrazine (o-phenylindenyl)benzoate, 1-phenyl-1,2-propanedione-2-(0-ethoxycarboxy)anthracene, 1-phenyl-1,2-propanedione -2-(o-benzylidene) anthracene, benzoin, benzoin ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ether, benzil, benzoquinone dimercapto A ketone, a phenyl hydrazino diethyl ketal, a diacetyl oxime (diacetyl), a green compound, a methyl oxime, a gas sulphide, a chlorpyrifos, a 2-mercaptothione, a 2-iso A sulfur compound such as an anthracene derivative such as propyl thiopurine or a squalene derivative, diphenyl disulfide or dithioamine phthalate. When light energy is used as the energy for initial photopolymerization, the wavelength of light irradiated to the polymerizable monomer is 360 nm or more, preferably 360 to 450 nm. The thermal polymerization initiator may be any compound which can be used as a starter for radical polymerization, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobisisoprene, 2 , 2'-azobis(2,4-dimercaptophthalonitrile), 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile) , 2,2'-azobis(2-methylpropane), 2,2'-azobis(2-amidpropionyl) 2 hydrochloride, and the like; azo compounds; , methyl isobutyl phthalate 323900 20 201239046 ketone, cyclohexanone peroxide, acetoxyacetone acetone and other ketone peroxides, isobutyl peroxide, benzoyl peroxide, peroxy 2, 4- a chlorobenzhydryl group, an o-nonylbenzhydryl peroxide group, a ruthenium peroxide, a p-chlorophenyl fluorenyl peroxide, etc.; 2, 4, 4-tridecylpentyl- Hydroperoxides such as 2-hydroperoxide, diisopropylbenzene hydroperoxide, cumyl hydroperoxide, and tertiary butyl hydroperoxide; dicumyl peroxide, peroxidation Tertiary butyl cumene, di-tertiary butyl peroxide, tris(tributyl) Peroxy) dialkyl peroxides such as three tillages; peroxyketals such as 1,1-di-tertiary butylperoxycyclohexane and 2,2-di(tri-butylperoxy)butane Class; tertiary butyl peroxytrimethyl acetate, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxy isobutyrate, di-tertiary butyl peroxy six Terephthalate, di-tertiary butyl peroxydecanoate, tert-butylperoxy-3,5,5-tridecylhexanoate, tertiary butyl peroxyacetate, three Alkyl peroxyesters such as butyl peroxybenzoate, di-tertiary butyl peroxytrimethyl adipate; diisopropyl peroxydicarbonate, di-di-butyl Peroxycarbonates such as oxydicarbonate or tertiary butyl peroxyisopropyl carbonate. Examples of the compound which can react with the active argon of the compound which is a raw material of the functional group represented by the above formula (1) include, for example, acrylic acid, mercaptoacrylic acid, acrylamide, propylene helium, mercaptopropene chloride, acrylic acid. Oxime ester, methyl methacrylate. As an example of the dehydrating agent which can be used for the production of the polymer compound (A), for example, hydrazine, Ν'-dicyclohexylcarbodiimide can be exemplified. An example of an acid catalyst which can be used for the production of a polymer compound (Α) can be exemplified by sulfuric acid. 323900 21 201239046 The polymer compound (A) used in the present invention may be a polymerizable monomer which is a raw material of a repeating unit containing an active hydrogen, and a polymerizable monomer other than a repeating unit containing a first functional group. Added during aggregation. Examples of the additional polymerizable monomer include acrylate and its derivatives, mercapto acrylate and its derivatives, styrene and its derivatives, vinyl acetate and its derivatives, mercapto acrylonitrile and its derivatives. , acrylonitrile and its derivatives, ethylene vinegar and its derivatives of organic acid, acid oleic acid and its derivatives, fumaric acid bismuth vinegar and its derivatives, maleic acid Alkyl esters and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, N-vinylamine derivatives of organic carboxylic acids, terminally unsaturated hydrocarbons and derivatives thereof, organic hydrazines containing unsaturated hydrocarbon groups Derivatives, etc. The type of the polymerizable monomer to be additionally used can be appropriately selected depending on the characteristics required for the insulating layer. From the viewpoint of excellent durability of the solvent or reduction of hysteresis of the organic thin film transistor, a film containing a compound such as styrene or a styrene derivative may have a high density and a hard film-forming single film. body. Further, from the viewpoint of the adhesion to the adjacent surface of the insulating layer such as the surface of the gate electrode or the substrate, a polymer compound such as a mercapto acrylate or a derivative thereof, an acrylate or a derivative thereof can be selected ( A) A monomer that imparts plasticity. As the acrylates and derivatives thereof, a monofunctional acrylate can be used, or a polyfunctional acrylate can be used when the amount used is limited. Such a monofunctional acrylate or polyfunctional acrylate may, for example, be an acrylic acid, an acrylic acid, a acrylic acid, a isopropyl acrylate or a n-butyl propyl acrylate. , isobutyl acrylate, butyl acrylate, hexyl acrylate, 323900 22 201239046 octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isodecyl acrylate, cyclohexyl acrylate, benzene acrylate Ester, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyphenyl ethyl acrylate, B Glycol-propanoid acid, propylene glycol diacrylic acid vinegar, 1,4-butanediol dipropionate citrine, monoethyl alcohol-acrylic acid S, triethylene glycol diacrylic acid vinegar, Trimethyl methacrylate diacrylate, trimethylolpropane triacrylate, neopentyl alcohol pentaacrylate, 2, 2, 2-trifluoroethyl acrylate, acrylic acid 2, 2, 3, 3, 3- Fluoropropyl ester, 2-(perfluorobutyl)ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-(perfluorohexyl)ethyl acrylate, C Acid 3-perfluorohexyl-2-hydroxypropyl ester, 2-(perfluorooctyl)ethyl acrylate, 3-fluoro perfluorooctyl-2-hydroxypropyl acrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluoro-3-methylbutyl)ethyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-fluorenyl acrylate) Ethyl)ethyl ester, 2-(perfluoro-3-mercaptobutyl)-2-hydroxypropyl acrylate, 3-(perfluoro-5-decylhexyl)-2-hydroxypropyl acrylate, 2-(2-acrylic acid) Perfluoro-7-methyloctyl)acetic acid, 3-(perfluoro-7-methyloctyl)-2-hydroxypropyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H acrylic acid , 5H-octafluoropentyl ester, acrylic acid 1H, 1H, 7H-undefluoroheptane vinegar, acrylic acid 1H, 1H, 9H-hexadecane vinegar, 1H-1-(trifluoromethyl)trifluoroethyl acrylate, Acrylic acid iH, 1H, 3H_hexafluorobutene, N,N-dimethylpropenylamine, N,N-diethyl acrylamide, N-propylene hydrazino. For mercapto acrylates and derivatives thereof, monofunctional methacrylates may be used, or polyfunctional thiopropyl 323900 23 201239046 dilute vinegar may be used when the amount of use is limited. Such a monofunctional methacrylate or polyfunctional methyl acetoacetate may, for example, be methyl methacrylate, ethyl methacrylate, propyl acrylate, isopropyl acrylate, or A. N-butyl acrylate, isobutyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, Isodecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid _3_hydroxypropyl ester, 2-hydroxybutyl methacrylate, _2 hydroxyphenyl ethyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, hydrazine, 4 _ Glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimercapto acrylate, trishydroxypropyl propane dimethacrylate, trimethylolpropane trimethacrylate, Pentaerythritol pentamethyl acrylate, 2, 2, 2-trifluoroethyl methacrylate 2, 2, 3, 3, 3_pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 3_perfluorobutyl-2-hydroxypropyl methacrylate, A 2-(perfluorohexyl)ethyl acrylate, decyl propylene oxime 3-perfluorohexyl-2-carbyl propyl ester, decyl propyl benzoate 2-(perfluorooctyl) ethyl ester, methacrylic acid 3 -Perfluorooctyl-2-hydroxypropyl ester, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3-mercaptobutyl)ethyl methacrylate, 3-methacrylic acid (Perfluoro-3-mercaptobutyl)-2-hydroxypropyl ester, 2-(perfluoro-5-decylhexyl)ethyl methacrylate, 2-(perfluoro-3-mercaptobutyl methacrylate) )-2-hydroxypropyl ester, methacrylic acid 3_(perfluoro_5_decylhexyl)-2-ylpropyl propyl ester, methyl propyl benzoate 2-(all U-mercaptooctyl) ethyl ester, A 3-(perfluoro-7-fluorenyloctyl)_2-hydroxypropyl acrylate, fluorenyl 323900 24 201239046 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate Ester, mercapto 1H, 1H, 7H-dodecafluoroheptyl ester, 1H, 1H, 9H-hexadecafluorodecyl methacrylate, 1H-1-(trifluoromethyl) methacrylate Ethyl ester, methacrylic acid 1H, 1H, 3H-hexafluorobutyl ester, N,N-dimercaptomethyl decylamine, N, N-diethyl decyl acrylamide, N-propylene hydrazine forest. Examples of the styrene and its derivatives include, for example, styrene, 2,4-dimercapto-α-methyl stupylene, o-nonylstyrene, m-decyl styrene, p-nonylstyrene, 2, 4-dimercaptostyrene, 2,5-dimethylstyrene, 2,6-dimercaptostyrene, 3,4-dimethylstyrene, 3,5-dimercaptostyrene, 2, 4,6-trimethylstyrene, 2,4,5-trimercaptostyrene, pentamethylstyrene, o-ethyl streptoethylene, m-ethylstyrene, p-ethylstyrene, o-chlorostyrene , m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-nonyloxystyrene, m-decyloxystyrene, p-methoxystyrene, o-hydroxybenzene Ethylene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl- Co-triphenyl, 1-vinyl anthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2, 3-dimethyl-α-mercaptostyrene, 3, 5-dimethyl- -methylstyrene, p-isopropyl-α-methylstyrene, ethylstyrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene, 4-amino Styrene. Examples of the vinyl ester of an organic carboxylic acid and a derivative thereof include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, ethylene benzoate, and divinyl adipate. 323900 25 201239046 Examples of organic oleic acid propylene glycol and its derivatives, for example, allyl acetate, allyl benzoate, allyl adipate, diallyl terephthalate, isophthalic acid Diallyl formate and diallyl phthalate. Examples of the fumaric acid-based dialkyl vinegar and derivatives thereof include didecyl fumarate, diethyl fumarate, diisopropyl fumarate, di- or di-butyl hydride. Diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, diphenyl phthalate. Examples of the second base of the maleic acid and its derivatives include didecyl maleate, diethyl maleate, diisopropyl maleate, and di- or 2-butyl butyl maleate. , diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, diphenyl decyl maleate. Examples of the dialkyl ester of itaconic acid and derivatives thereof include didecyl itaconate, diethyl itaconate, diisopropyl itaconate, di- or dibutyl butylate. Diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate, diphenyl decyl itaconate. Examples of the N-vinylamine derivative of the organic carboxylic acid include N-decyl-N-vinylamine. Examples of the maleidin and its derivatives include N-phenylmaleimide and N-cyclohexylmaleimide. Examples of the terminal unsaturated hydrocarbon and its derivative include, for example, 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, ethylene oxide, and allyl alcohol. Examples of the organic hydrazine derivative containing an unsaturated hydrocarbon group include, for example, allyl trimethyl hydrazine, allyl triethyl hydrazine, allyl tributyl fluorene, trimethyl ethoxylated, triethyl. Vinyl hydrazine. 323900 26 201239046 Among these, alkyl acrylate, alkyl methacrylate, styrene, acrylonitrile, methacrylonitrile, allyl trimethyl hydrazine are preferred. The south molecular compound (A) preferably has a weight average molecular weight of from 3 Å to 1 Torr, more preferably from 5,000 to 500,000, and may be any of a linear chain, a branched form, and a soil. The polymer compound (A) used in the present invention may, for example, be poly(styrene-co-[4-(methacrylamidoaminostyrene)]-total 4240-0,-methylpropyleneamine Carboxyamino]ethyl-mercapto acrylate]), poly(styrene-co-[4-(mercaptopropenylamino) stupyl ethylene]]__[2_[1,_ (3 ' 5'-Dimethylpyrazolylcarbonylamino]ethyl-mercapto acrylate]), poly(styrene-co-[4-(methylpropenylaminophenyl))-- Acrylonitrile-co-[2-[〇-(1,-mercaptopropylamino)carboxyamino]ethyl-mercapto acrylate vinegar]), poly(styrene-co-[4_(methacryl) Mercaptoaminostyrene)]-co-acrylonitrile-co-[2-[1'-(3,5,-dimethylpyrazolyl)carbonylamino]ethyl-methacrylate]) , poly(styrene-co-[4_(mercaptopropenylamino styrene)]-co-acrylonitrile-co-[2-[〇-(ι,_methylpropylidene)) Amino]ethyl-methylpropionic acid g]-co-propylmethylhydrazine), poly(styrene-co-[2-methacryloxyethyl-methacrylic acid] -co-acrylonitrile-total-[2-[1' -(3',5' -dimercapto group 0 to 0-seat) carbonylamino]ethyl-mercapto acrylate]-co-allylmethylhydrazine), poly([2-mercaptopropenyloxyethyl-mercaptoacrylic acid) Ester]-co-[2-[〇-(1 methallylamino) oxylamino]ethyl-methacrylic acid vinegar]), poly([2-methylpropenyloxyethyl- Mercapto acrylate]-co-[2-[1,-(3',5'-dimercaptopyrazolyl)carbonylamino]ethyl-mercaptoacrylic acid 323900 27 201239046 Ester]), poly(styrene) -co-[2-mercaptopropene ethoxyethyl-mercapto acrylate]-co-[2-[0-(indolyl-mercaptopropylamino)carboxylamino]ethyl-methacrylic acid Ester]), poly(styrene-co-[2-methacryloxyethyl-mercapto acrylate]-co-[2-[1'-(3,,5'-dimethylpyrazole) Base) mercaptoamino]ethyl-mercapto acrylate]). <Meter Molecular Compound (Β)> The preferred embodiment of the polymer compound contained in the organic thin film transistor insulating layer material of the present invention has an addition polymerization reaction group, has a fluorine atom, and has two or more. The first functional compound of the first functional emulsion. Such a molecular compound is referred to as a molecular compound (Β). Since the organic thin film transistor insulating layer material is introduced with fluorine, the insulating layer formed of the material has a low polarity and can suppress the polarization of the insulating layer. Further, when a crosslinked structure is formed inside the insulating layer, the movement of the molecular structure can be suppressed, and the polarization of the insulating layer can be suppressed. When the polarization of the insulating layer is suppressed, for example, when used as a gate insulating layer, the hysteresis of the organic thin film transistor is lowered, and the operation accuracy is improved. _ The dry and squirrel atom is not a hydrogen atom that replaces the main chain of the polymer compound, but a hydrogen atom that replaces a side chain or a pendant. If the fluorine atom is substituted with a side chain or a side group, the organic material of the organic semiconductor lion does not decrease, and in the formation of the layer containing the organic material, the material is in contact with the exposed surface of the insulating layer. The formation of the layer is made easy. The compound (8) may also have a group containing a gas atom. Preferred examples of the group containing a gas atom include, for example, a hydrogen atom atom substituted by a fluorine material, a sub-transfer group, an oxygen-based group, and particularly a hydrogen atom obtained by a fluorine atom, 323900 28 201239046 phenyl, An alkylphenyl group in which a hydrogen atom is substituted with a fluorine atom. Among the polymer compounds (B), a polymer compound containing a functional group having a double bond, two or more first functional groups, and a repeating unit having a fluorine atom-containing group is preferable, and a compound formula is more preferable. 1) The functional group represented by the above, the two or more first functional groups, and the polymer compound of the repeating unit represented by the formula (2) are more preferably a repeating single group containing the functional group represented by the formula (1) a fluorene, a repeating unit containing a first functional group, and a molecular compound of a repeating unit represented by the formula (2). In the formula (2), R2 represents a hydrogen atom or a methyl group. In one form, helium is a hydrogen atom. Raa indicates that the connecting portion of the connecting portion of the main chain and the side chain which may have a fluorine atom is a bivalent structure having a structure which does not exhibit reactivity under the environmental conditions for crosslinking the organic thin agglomerate insulating layer material of the present invention. The basis can be. Specific examples of the linking portion include a bond composed of an organic group having a carbon number of 〇2〇, an ether bond (—〇_), a bond (_c〇_), an ester bond GC〇〇, and _. 〇c〇_), amidoxime bond (_NHC〇_, -c〇nh-), urethane^a...(4) win) and the combination of the keys and the like. u means illusion < integer. In a certain form, u is 〇. The 趟lf represents a fluorine atom or a carrier having a valence of a carbon number of 1 to 20 having a fluorine atom. In one form, Rf is a fluorine atom. b represents an integer from 1 to 5. In a certain form 4 is 5. R represents a hydrogen atom or a carbon number of 1 to 20, and has a carbon number of a branch. The organic value of the valence is either a straight bond or a %, and may be saturated or unsaturated. 323900 The organic group at a price of up to 20 may, for example, have a carbon number of 1 to 2. 29 201239046 The linear hydrocarbon group, the branched hydrocarbon group having 3 to 20 carbon atoms, the cyclic hydrocarbon group having 3 to 20 carbon atoms, and the aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably, for example, a carbon number of 1 to 6 a linear hydrocarbon group, a branched hydrocarbon group having 3 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. The aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted by an alkyl group, a gas atom, a desert atom, a moth atom or the like. When R is an organic group having a carbon number of 1 to 20, the monovalent organic group does not have a fluorine atom. Specific examples of the organic group having a carbon number of 1 to 20 include, for example, an anthracenyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a tertiary butyl group, and a cyclopropyl group. Base, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentynyl, cyclohexynyl, phenyl, naphthyl, anthracenyl, fluorenylphenyl, diphenylphenyl, dimethylphenyl, tridecyl Phenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, butylphenyl, methylnaphthyl, dinonylnaphthyl, tridecylnaphthyl, vinylnaphthalene Base, vinylnaphthyl, anthracenyl, ethyl fluorenyl, chlorophenyl, bromophenyl. The organic group having a carbon number of 1 to 20 is preferably an alkyl group. When Rf is an organic group having 1 to 20 carbon atoms having a fluorine atom, an organic group having a fluorine atom having a carbon number of 1 to 20, for example, a trifluoromethyl group, a 2, 2, 2-trifluoro group Ethyl, 2, 2, 3, 3, 3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, pentafluorophenyl, trifluorodecylphenyl, and the like. The divalent organic group having 1 to 20 carbon atoms may be any of a straight chain, a branched chain, and a cyclic group, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. For example, a linear aliphatic hydrocarbon group having a carbon number of 1 to 20, a bivalent aliphatic hydrocarbon group having a carbon number of 3,323,900, 30,300,390,46 to 2, and a divalent ring having a carbon number of 3 to 20 may be mentioned. a divalent aromatic hydrocarbon group having a carbon number of 6 to 2 G substituted with a hydrocarbon group, a domain group, or the like, wherein the preferred one is a divalent linear hydrocarbon having a carbon number of 1 to 6 and a carbon number of 3 to 6 Branched aliphatic nicotine, carbon number 3 to 6

之二價之職絲、可、魏鱗取叙二狀碳數 之芳香族烴基。 U 二價之脂肪族烴基及二價之環狀煙基之㈣例， 例如亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、 伸異丙基、伸異丁基、二甲基伸丙基、伸環丙基、伸^ 基、伸環戊基、伸環己基。 石厌數6至20之二價之芳香族烴基之具體例，可舉例 如伸苯基、伸蔡基、伸蒽基、二甲基伸苯基、三甲基伸苯 基、伸乙基伸苯基、二伸乙基伸苯基、三伸乙基伸苯基、 伸丙基伸苯基、伸丁基伸苯基、甲基伸萘基、二曱基伸蔡 基、三曱基伸萘基、乙職伸萘基、乙稀伸萘基、甲基 蒽基、乙基伸蒽基。 本發明所使用之高分子化合物⑻，例如可藉由下述 ^法製造：將成為含有活性氫之重複單元之原料的聚合性 早體、成為上述式⑵所表示之重複單元之原料的聚合性單 體、含有第1官能基之聚合性單體，使用光聚合起始劑或 熱聚合起始劑使其絲合⑽絲物後，使成為式⑴所表 不之s能基之原料的化合物之可與活性氫反應的化合物、 與該共聚物中之活性氫反應的方法。成為式⑴所表示之官 能基之原料的化合物之可與活性氮反應的化合物，亦可使 323900 31 201239046 用成為式（1)所表示之官能基之原料的化合物之可與活性 氫脫水反應的化合物、或成為式（1)所表示之官能基之原料 的化合物之可與活性氫酯交換反應的化合物。再者，亦可 於聚合時添加成為含有活性氫之重複單元之原料的聚合性 單體、成為上述式（2)所表示之重複單元之原料的聚合性單 體、含有第1官能基之聚合性單體以外之聚合性單體來製 造。 成為含有活性氫之重複單元之原料的聚合性單體、含 有第1官能基之聚合性單體、追加所使用之聚合性單體， 可舉例如上述之聚合性單體。成為式（1)之所表示之官能基 之原料之化合物，可舉例如上述之化合物。 成為式（2)所表示之重複單元之原料的聚合性單體之 例，可舉例如2-三氟曱基苯乙烯、3-三氟曱基苯乙烯、4-三氟曱基苯乙烯、2, 3, 4, 5, 6-五氟苯乙烯、4-氟苯乙烯。 成為式（2)所表示之重複單元之原料的聚合性單體之 使用量，係以使導入高分子化合物（B)之氟原子的量為適量 的方式來調節。 導入高分子化合物（B)之氟原子的量，相對於高分子 化合物（B)之質量，較佳為1至80質量％，更佳為5至70 質量％，又更佳為10至60質量％。氟原子之量若未滿1質 量％，則使電場效應型有機薄膜電晶體之磁滯降低的效果不 足，若超過80質量％則與有機半導體材料之親和性惡化而 難以將活性層積層於其上。 高分子化合物（B)重量平均分子量以3000至1000000 323900 32 201239046 為佳，更佳為5000至500000，可為直鏈、分枝、環狀之 任'—者0 高分子化合物（B)可舉例如聚（苯乙烯-共-[4-(甲基 丙稀酿基胺基苯乙稀）]-共-五氣苯乙稀-共-[2_[0-( 1 — 曱基亞丙基胺基）羧基胺基]乙基-甲基丙烯酸酯])、聚（苯 乙烯-共-[4-(甲基丙烯醯基胺基苯乙烯）]-共-五氟苯乙烯 -共-[2-[1’ -(3，，5’ -二甲基吡唑基）羰基胺基]乙基-曱 基丙烯酸酯])、聚（苯乙烯-共-[4-(曱基丙烯醯基胺基苯乙 婦）]_共-五氟苯乙稀-共-丙稀猜-共-[2-[0-(1’ -曱基亞 丙基胺基）羧基胺基]乙基-甲基丙烯酸酯])、聚（苯乙烯-共-[4-(甲基丙烯醯基胺基苯乙烯）]-共-五氟苯乙烯-共-丙烯腈-共-[2-[1，-(3，，5’ -二曱基0比唑基）羰基胺基] 乙基-曱基丙烯酸酯])、聚（苯乙烯-共-[4-(曱基丙烯醯基 胺基苯乙烯）]-共-五氟苯乙烯-共-丙烯腈-共-[2-[0-(1’ -甲基亞丙基胺基）羧基胺基]乙基-曱基丙烯酸酯]-共 -烯丙基三曱基鍺）、聚（苯乙烯-共-[2-曱基丙烯醯氧基乙 基-甲基丙烯酸S旨]-共-五氟苯乙烯-共-丙稀腈-共-[2-[1 -（3’，5’ -二曱基0比°坐基）毅基胺基]乙基-甲基丙烯 酸酯]-共-烯丙基三曱基鍺）、聚（[2-曱基丙烯醯氧基乙基-曱基丙烯酸酯]-共-五氟苯乙烯-共-[2-[0-(Γ -甲基亞丙 基胺基）羧基胺基]乙基-曱基丙烯酸酯])、聚（[2-甲基丙烯 醯氧基乙基-甲基丙烯酸酯]-共-五氟苯乙烯-共-[2-[1，-(3，，5’ -二甲基吡唑基）羰基胺基]乙基-曱基丙烯 酸醋])、聚（苯乙稀-共-五I苯乙嫦-共-[2-曱基丙稀醢氧 323900 33 201239046 基乙基-曱基丙烯酸酯]-共-[2-[0-(Γ -曱基亞丙基胺基） 羧基胺基]乙基-曱基丙烯酸酯])、聚（苯乙烯-共-五氟苯乙 烯-共-[2-曱基丙烯醯氧基乙基-曱基丙烯酸酯]-共-[2-[1 -(3 , 5 -二曱基。比。坐基）数基胺基]乙基'曱基丙稀 酸酉旨])。 <高分子化合物（C)> 本發明之有機薄膜電晶體絕緣層材料所含之高分子 化合物之較佳態樣，係具有加成聚合反應基、具有2個以 上之上述第1官能基、且具有2個以上之具有1個活性氩 之構造單元或具有2個以上之活性氫之構造單元的高分子 化合物。將此種高分子化合物，記為高分子化合物（C)。 高分子化合物（C)之中，更佳為含有含式（1)所表示之 官能基之重複單元、含有第1官能基之重複單元、與含有 活性氫之重複單元的高分子化合物。 高分子化合物（C)，例如可藉由下述方法製造：將成 為含有活性氫之重複單元之原料的聚合性單體、成為含有 第1官能基之重複單元之原料的聚合性單體，使用光聚合 起始劑或熱聚合起始劑使其共聚合而得共聚物後，使成為 式（1)所表示之官能基之原料的化合物之可與活性氫反應 之化合物、與該共聚物中一部分之活性氬反應的方法。 高分子化合物（C)可舉例如聚（苯乙烯-共-[4-胺基笨 乙婦]-共_[2-[0-(1’ -曱基亞丙基胺基）敌基胺基]乙基-甲基丙烯酸酯])、聚（苯乙烯-共-[4-胺基苯乙烯]-共 -[2-[1’ -（3’，5’ -二曱基°比唾基）叛基胺基]乙基-曱基 323900 34 201239046 丙烯酸酯])、聚（苯乙烯-共—[4_胺基苯乙燦]—共—丙烯腈一 共—[2-[〇-(1，-曱基亞丙基胺基）幾基胺基]乙基~曱基丙 烯酸酯])、聚（苯乙烯-共_[4_胺基苯乙烯]-共-丙婦腈一共 -(3，，5，-二甲基吡唑基）羰基胺基]乙基-曱基 丙烯酸S旨])、聚（苯乙烯-共-[4-胺基苯乙稀]_共-丙烯腈-共-[2-[0-(1，-曱基亞丙基胺基）羧基胺基]乙基-甲基丙 烯酸酯]-共-烯丙基三甲基鍺）、聚（苯乙烯-共-[2-羥基乙 基-甲基丙烯酸酯]-共-丙烯腈-共-[2-[Γ _(3’，5’ -二 曱基吡唑基）羰基胺基]乙基-曱基丙烯酸酯]-共-烯丙基三 曱基鍺）、聚（[2-羥基乙基-曱基丙烯酸酯]-共-[2-[0-(Γ -甲基亞丙基胺基）羧基胺基]乙基-曱基丙烯酸酯])、 聚（[2-羥基乙基-甲基丙烯酸酯]-共-[2-[Γ -（3’，5’ -二曱基吡唑基）羰基胺基]乙基-曱基丙烯酸酯])、聚（苯乙 烯-共-[2-羥基乙基-甲基丙烯酸酯]一共_[2-[〇-(1’ -甲基 亞丙基胺基）敌基胺基]乙基-曱基丙稀酸醋])、聚（苯乙稀一 共-[2-[1，_ (3’，5’ ~二甲基吡唑基）羰基胺基]乙基—甲 基丙烯酸S旨])。 高分子化合物（C)重量平均分子量以3000至1000000 為佳，更佳為5000至500000，可為直鏈、分枝、環狀之 任一者0 <高分子化合物（D)> 本發明之有機薄膜電晶體絕緣層材料所含之高分子 ，合物之較佳之其他態樣，係具杨絲合反應基、具有 氟原子、具有2個以上之上述第i官能基、且具有2個以 323900 35 201239046 上之具有1個活性氫之構造單元或具有2個以上之活性氫 之構造單元的高分子化合物。將此種高分子化合物，記為 高分子化合物（D)。 高分子化合物（D)之中，更佳為含有含式（1)所表示之 官能基之重複單元、含式（2)所表示之官能基之重複單元、 含有第1官能基之重複單元、與含有活性氫之重複單元的 高分子化合物。 高分子化合物（D)，例如可藉由下述方法製造：將成 為含有活性氫之重複單元之原料的聚合性單體、成為式（2) 所表示之重複單元之原料的聚合性單體、成為含有第1官 能基之重複單元之原料的聚合性單體，使用光聚合起始劑 或熱聚合起始劑使其共聚合而得共聚物後，使成為式（1) 所表示之官能基之原料的化合物之可與活性氫反影之化合 物、與該共聚物中一部分之活性氫反應的方法。 高分子化合物（D)，可舉例如聚（苯乙烯：共-[4-胺基 苯乙稀]-共-五參苯乙稀-共-[2-[0-(1’ -甲基亞丙基胺基） 羧基胺基]乙基-甲基丙烯酸酯])、聚（苯乙烯-共-[4-胺基 苯乙稀]-共-五敗苯乙稀_共-[2-[1’ -(3’ ，5’ -二曱基〇比 唑基）羰基胺基]乙基-曱基丙烯酸酯])、聚（苯乙烯-共-[4-胺基苯乙浠]-共-五象苯乙稀-共-丙稀腈-共-[2-[〇-(1’ -曱基亞丙基胺基）羧基胺基]乙基-曱基丙烯酸酯])、聚（苯 乙婦-共_[4-胺基苯乙婦]-共-五氟苯乙稀-共-丙稀腈-共 -[2-[1’ -(3’，5’ -二曱基0比〇坐基）毅基胺基]乙基-甲基 丙烯酸酯])、聚（苯乙烯-共-[4-胺基苯乙烯]-共-五氟苯乙 323900 36 201239046 烯-共-丙烯腈-共-[2-[0-(Γ -曱基亞丙基胺基）羧基胺基] 乙基-甲基丙烯酸酯]-共-烯丙基三曱基鍺）、聚（苯乙烯一 共-[2-羥基乙基-甲基丙烯酸酯]-共-五氟苯乙烯-共-丙烯 腈-共-[2-[1’ -(3，，5’ -二曱基吡唑基）羰基胺基]乙基-曱基丙烯酸酯]-共-烯丙基三曱基鍺）、聚（[2-羥基乙基-甲基丙烯酸酯]-共-五氟苯乙烯-共-[2-[0-(Γ -甲基亞丙 基胺基）羧基胺基]乙基-曱基丙烯酸酯])、聚（[2-羥基乙基 -曱基丙烯酸酯]-共-五氟苯乙烯-共-[2-[1’ -(3’，5’ -二甲基吡唑基）羰基胺基]乙基-曱基丙烯酸酯])、聚（苯乙 烯-共-五氟苯乙烯-共-[2-羥基乙基-曱基丙烯酸酯]-共 -[2-[0- (Γ -甲基亞丙基胺基）羧基胺基]乙基-曱基丙烯 酸酯])、聚（苯乙烯-共-五氟苯乙烯-共-[2-羥基乙基-甲基 丙烯酸S旨]-共-[2-[1’ -(3’，5’ -二曱基》比η坐基）幾基胺 基]乙基-曱基丙烯酸酯])。 高分子化合物（D)重量平均分子量以3000至1000000 為佳’更佳為5000至500000，可為直鏈、分枝、環狀之 任一者0 <活性氫化合物（Ε)> 本發明之有機薄膜電晶體絕緣層材料，亦可含有活性 氫化合物（Ε)。活性氫化合物（Ε)，藉由與高分子化合物（a) 至（D)中所生成之第2官能基反應而與其鍵結，而可於絕緣 層之内部形成交聯構造。於活性氫化合物，含有含2 個以上活性氫之低分子化合物（以下，稱為低分子活性氫化 合物（Ε-1))、及含2個以上活性氫之高分子化合物（以下， 323900 37 201239046 稱為高分子活性氫化合物（E-2))。 活性氫典型的可舉例如胺基、羥基或酼基中所含之氫 原子。活性氫較佳為由上述第1官能基所生成之第2官能 基，其中可與異氰酸酯基、異硫氩酸基產生良好反應之酚 性經基所含之氫、醇性經基所含之氫、芳香族胺基所含之 氫。 低分子活性氫化合物（E-1)之具體例，可舉例如具有 含2個以上活性氫之基鍵結於低分子結構之結構的化合 物。該低分子結構，可舉例如烷基結構或苯環結構。該低 分子化合物之具體例，可舉例如胺系化合物、醇系化合物、 酚系化合物及硫醇系化合物。本說明書中，所謂「烷基結 構」係意指由脂肪族烴所構成之直鏈狀、分枝狀、或環狀 之結構。另一方面，所謂「苯環結構」係意指由芳香族烴 所構成之直鏈狀、分枝狀、或環狀之結構。 胺系化合物之例，可舉例如乙二胺、丙二胺、六亞曱 基二胺、N，N，N’，N’，-四胺基乙基乙二胺、鄰苯二胺、間 苯二胺、對苯二胺、N，N’ -二苯基-對苯二胺、三聚氰胺、 2, 4, 6-三胺基嘧啶、1，5, 9-三氮雜環十二烷、1,3-雙（3-胺基丙基）四甲基二聚矽氧烷、1,4-雙（3-胺基丙基二甲基 碎基）苯、3-(2-胺基乙基胺基丙基）參（三曱基碎氧基）碎 烷。 醇系化合物之例，可舉例如乙二醇、1，2-二羥基丙 烧、甘油、1，4-二甲醇苯。 苯酚系化合物之例，可舉例如1,2-二羥基苯、1，3- 323900 38 201239046 二羥基苯、1，4-二羥基笨（氫醌）、1，2-二羥基萘、間苯二 酚、氟甘油、2, 3, 4-三羥基苯甲醛、3, 4, 5-三羥基苯曱醯 胺。 硫醇系化合物之例，可舉例如乙二硫醇、對苯二硫醇。 含有2個以上活性氳之低分子化合物，以醇系化合 物、紛系化合物、芳香族胺系化合物較佳。 另一方面，高分子活性氳化合物（E-2)中，活性氫可 直接鍵結於構成高分子化合物之主鏈、亦可隔著特定之基 鍵結。又，活性氫亦可含於構成高分子化合物之構造單元， 於該情形，可含於各構造單元，亦可僅含於一部分之構造 單元。再者，活性氫亦可僅鍵結於高分子化合物之末端。 高分子活性氫化合物（E-2)之具體例，可舉例如具有 含2個以上活性氫之基鍵結於高分子結構之結構的化合 物。高分子活性氫化合物（E-2)，以復具有氟原子為佳。其 係因所形成之絕緣層之極性降低之故。又，高分子活性氫 化合物（E-2)，以復具有加成聚合反應基為佳。其係因所形 成之絕緣層之交聯密度增高之故。 高分子活性氫化合物（E-2)，可藉由將含有活性氫之 基及具有雙鍵等不飽和鍵之單體單獨地聚合、或與其他聚 合性單體共聚合形成共聚物來製得。該等聚合性單體之聚 合或共聚合可使用該技術領域者通常使用之方法來進行。 為了於高分子活性氫化合物（E-2)組入氟原子，可使 用成為上述式（2)所表示之重複單元之原料的聚合性單體 作為上述其他之聚合性單體。又，為了於高分子活性氫化 323900 39 201239046 合物（E-2)組入加成聚合反應基，可準備成為上述式（1)所 表示之官能基之原料的化合物之可與活性氫反應之化合 物，將其與高分子活性氫化合物（E - 2 )中之活性氫之一部分 反應。 於該等聚合時，亦可使用光聚合起始劑或熱聚合起始 劑。又，聚合性單體、光聚合起始劑、熱聚合起始劑，亦 可使用與上述相同者。 含有活性氫之基及具有不飽和鍵之單體，可舉例如胺 基苯乙烯、羥基苯乙烯、乙烯基苯曱基醇、甲基丙烯酸胺 基乙酯、乙二醇單乙烯醚、丙烯酸4-羥基丁酯。 含有活性氫之基及具有不飽和鍵之單體，以具有羥基 者或具有胺基者為佳。 又，含有2個以上活性氫之高分子化合物，可藉由將 紛化合物、甲搭，於酸觸媒之存在下縮合來製得，亦可使 用酚醛清漆樹脂。 含有2個以上之含有活性氫之基之高分子化合物之聚 苯乙烯換算的重量平均分子量以1000至1000000為佳， 3000至500000為更佳。藉此，可得絕緣層之平坦性及均 一性良好的效果。換算成聚苯乙烯之重量平均分子量係以 GPC測定。 <具有光二聚合（photodimerization)反應基之化合物> 本發明之有機薄膜電晶體絕緣層材料，亦可含有具複 數個吸收電磁波之能量或電子射線之能量而產生二聚合反 應之官能基的化合物。吸收電磁波之能量或電子射線之能 323900 40 201239046 量而產生二聚合反應之該官能基，於本說明書中稱為「光 一聚合反應基」。此種化合物，可舉例如，含有2個以上光 一聚合反應基之低分子化合物、及含有含光二聚合反應基 之重複單元之高分子化合物。 於某一形態中，光二聚合反應基係組入高分子活性氫 化合物（E-2)。於該情形，含有2個以上光二聚合反應基之 高分子化合物，係作為活性氳化合物導入本發明之有機薄 膜電晶體絕緣層材料。於其他形態中，含有2個以上光二 聚合反應基之化合物，係與活性氫化合物等一同導入本發 明之有機薄膜電晶體絕緣層材料。 為了於高分子活性氫化合物（E-2)組入光二聚合反應 基，上述之其他聚合性單體，可使用成為下述式（5)所表示 之重複單元之原料之聚合性單體，較佳為含有下述式（6) 所表示之官能基與雙鍵之聚合性單體。 光二聚合反應基所吸收之電磁波，若能量過低，則以 光聚合法形成有機薄膜電晶體絕緣層材料時，會有光二聚 合反應基亦產生反應的情形，故以高能量之光為佳。光二 聚合反應基所吸收之較佳之電磁波，為紫外線，例如波長 為400nm以下，較佳為150至380nm之光。 此處所謂之二聚合，係指2個有機化合物之分子化學 性地鍵結。鍵結之分子彼此可為同種或不同種。二聚合之 2個分子中與二聚合有關之官能基彼此之化學結構可為相 同或相異。然而，該官能基以即使不使用觸媒及起始劑等 反應助劑亦能產生二聚合反應之結構、及組合為佳。其係 323900 41 201239046 因若與反應助劑之殘基接觸時則周邊之有機材料有劣化的 可能性之故。 具有光二聚合反應基之重複單元較佳為式（5)所表示 之重複單元，The divalent price of the silk, can, and Wei scales take the aromatic hydrocarbon group of the dichotomous carbon number. (4) Examples of a divalent aliphatic hydrocarbon group and a divalent cyclic nicotyl group, such as methylene, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and Butyl, dimethyl-propyl, cyclopropyl, benzyl, cyclopentyl, and cyclohexyl. Specific examples of the divalent aromatic hydrocarbon group of 6 to 20 are examples of a phenyl group, a phenyl group, a decyl group, a dimethylphenyl group, a trimethylphenyl group, and an ethyl benzene group. Base, diethyl phenyl, triethyl phenyl, propyl phenyl, butyl phenyl, methyl anthranyl, diterpene phenyl, triterpene, naphthyl Base, ethyl phenylene, methyl fluorenyl, ethyl thiol. The polymer compound (8) used in the present invention can be produced, for example, by the following method: a polymerizable precursor which is a raw material of a repeating unit containing active hydrogen, and a polymerizable material which is a raw material of a repeating unit represented by the above formula (2) a monomer or a polymerizable monomer containing a first functional group, which is a compound which is a raw material of the s-energy group represented by the formula (1) after a (10) filament is obtained by using a photopolymerization initiator or a thermal polymerization initiator. A compound reactive with active hydrogen and a method of reacting with active hydrogen in the copolymer. A compound which can react with active nitrogen as a compound which is a raw material of the functional group represented by the formula (1), or a compound which is a raw material of the functional group represented by the formula (1), can be dehydrated with active hydrogen by using 323900 31 201239046 A compound which can be transesterified with an active hydrogen by a compound or a compound which is a raw material of a functional group represented by the formula (1). Further, a polymerizable monomer which is a raw material of a repeating unit containing active hydrogen, a polymerizable monomer which is a raw material of the repeating unit represented by the above formula (2), and a polymerization containing a first functional group may be added during the polymerization. It is produced by a polymerizable monomer other than a monomer. The polymerizable monomer which is a raw material of a repeating unit containing an active hydrogen, the polymerizable monomer which has a 1st functional group, and the polymerizable monomer to be used together may, for example, be the above-mentioned polymerizable monomer. The compound which is a raw material of the functional group represented by the formula (1) may, for example, be the above-mentioned compound. Examples of the polymerizable monomer which is a raw material of the repeating unit represented by the formula (2) include, for example, 2-trifluorodecylstyrene, 3-trifluorodecylstyrene, and 4-trifluorodecylstyrene. 2, 3, 4, 5, 6-pentafluorostyrene, 4-fluorostyrene. The amount of the polymerizable monomer to be used as a raw material of the repeating unit represented by the formula (2) is adjusted such that the amount of the fluorine atom introduced into the polymer compound (B) is an appropriate amount. The amount of the fluorine atom to be introduced into the polymer compound (B) is preferably from 1 to 80% by mass, more preferably from 5 to 70% by mass, still more preferably from 10 to 60% by mass based on the mass of the polymer compound (B). %. When the amount of the fluorine atom is less than 1% by mass, the effect of reducing the hysteresis of the electric field effect type organic thin film transistor is insufficient. When the amount is more than 80% by mass, the affinity with the organic semiconductor material is deteriorated, and it is difficult to laminate the active layer thereto. on. The polymer compound (B) has a weight average molecular weight of preferably 3,000 to 1,000,000 323900 32 201239046, more preferably 5,000 to 500,000, and may be a linear, branched or cyclic one-- 0 polymer compound (B) can be exemplified For example, poly(styrene-co-[4-(methylpropanylaminophenyl)]-co-pentaphenone-co-[2_[0-(1 - decyl propylene amide) Carboxyamino]ethyl-methacrylate]), poly(styrene-co-[4-(methacrylamidoaminostyrene)]-co-pentafluorostyrene-co-[2 -[1' -(3,,5'-dimethylpyrazolyl)carbonylamino]ethyl-mercapto acrylate]), poly(styrene-co-[4-(mercaptopropenylamine) Ethyl benzene ethyl ester)]_co-pentafluorophenylethylene-co-acrylic guess-co-[2-[0-(1'-mercaptopropylamino)carboxyamino]ethyl-methyl Acrylate]), poly(styrene-co-[4-(methacrylamidoaminostyrene)]-co-pentafluorostyrene-co-acrylonitrile-co-[2-[1,-( 3,,5'-dimercapto 0-oxazolyl)carbonylamino]ethyl-mercapto acrylate]), poly(styrene-co-[4-(mercaptopropenylaminostyrene)] -co-pentafluorostyrene-total- Acrylonitrile-co-[2-[0-(1'-methylpropyleneamino)carboxyamino]ethyl-mercapto acrylate]-co-allyl trimethyl fluorene), poly(benzene Ethylene-co-[2-mercaptopropenyloxyethyl-methacrylic acid S]-co-pentafluorostyrene-co-acrylonitrile-co-[2-[1 -(3',5' - bisindolyl 0 to ° sityl) imylamino]ethyl-methacrylate]-co-allyl tridecyl fluorene, poly([2-mercaptopropenyloxyethyl-fluorene] Acrylate]-co-pentafluorostyrene-co-[2-[0-(Γ-methylpropyleneamino)carboxyamino]ethyl-mercapto acrylate]), poly([2- Methyl propylene oxiranyl ethyl-methacrylate]-co-pentafluorostyrene-co-[2-[1,-(3,5'-dimethylpyrazolyl)carbonylamino] Base-mercapto acrylate vinegar]), poly(phenylethylene-co-penta-I phenethyl fluorene-co-[2-mercapto propylene oxime oxy 323900 33 201239046 hydroxyethyl-mercapto acrylate]-co-[ 2-[0-(Γ-mercaptopropylamino)carboxyamino]ethyl-mercapto acrylate]), poly(styrene-co-pentafluorostyrene-co-[2-mercaptopropene醯oxyethyl-mercapto acrylate]-co-[2-[1 -(3,5-didecyl). . Ride-yl) Number yl] ethyl 'Yue unitary purpose based acrylic acid]). <Polymer compound (C)> The preferred embodiment of the polymer compound contained in the organic thin film transistor insulating layer material of the present invention has an addition polymerization group and has two or more of the above first functional groups. Further, it has two or more polymer compounds having one structural unit of one active argon or one structural unit having two or more active hydrogens. Such a polymer compound is referred to as a polymer compound (C). Among the polymer compounds (C), a polymer compound containing a repeating unit containing a functional group represented by the formula (1), a repeating unit containing a first functional group, and a repeating unit containing an active hydrogen is more preferable. The polymer compound (C) can be produced, for example, by using a polymerizable monomer which is a raw material of a repeating unit containing active hydrogen or a polymerizable monomer which is a raw material of a repeating unit containing a first functional group. After the copolymerization reaction agent or the thermal polymerization initiator is copolymerized to obtain a copolymer, a compound which can react with active hydrogen of a compound which is a raw material of the functional group represented by the formula (1), and the copolymer are A part of the method of active argon reaction. The polymer compound (C) may, for example, be poly(styrene-co-[4-amino-phenyl]--[2-[0-(1'-mercaptopropylamino)alkylamino group ]ethyl-methacrylate]), poly(styrene-co-[4-aminostyrene]-co-[2-[1'-(3',5'-dimercapto-pyranyl) ) 叛 胺 ] ] 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 ,-mercaptopropylamino)aminoamino]ethyl-mercapto acrylate]), poly(styrene-co-[4_aminostyrene]-co-acrylonitrile-total-(3 ,,5,-Dimethylpyrazolyl)carbonylamino]ethyl-mercaptoacrylic acid S], poly(styrene-co-[4-aminophenylethylene]-co-acrylonitrile-co- -[2-[0-(1,-nonyl propyleneamino)carboxyamino]ethyl-methacrylate]-co-allyl trimethyl hydrazine), poly(styrene-co- [2-Hydroxyethyl-methacrylate]-co-acrylonitrile-co-[2-[Γ _(3',5'-dimercaptopyrazolyl)carbonylamino]ethyl-mercaptoacrylic acid Ester]-co-allyl trimethyl fluorene), poly([2-hydroxyethyl-mercaptopropene) Acid ester]-co-[2-[0-(indolylaminopropylamino)carboxyamino]ethyl-mercapto acrylate]), poly([2-hydroxyethyl-methacrylate) ]-co-[2-[Γ-(3',5'-dimercaptopyrazolyl)carbonylamino]ethyl-mercapto acrylate]), poly(styrene-co-[2-hydroxyethyl A group of _[2-[〇-(1'-methylpropylidene))-alkylamino]ethyl-mercapto-acrylic acid vinegar]), poly(styrene) -[2-[1,_(3',5' ~Dimethylpyrazolyl)carbonylamino]ethyl-methacrylic acid S]). The polymer compound (C) preferably has a weight average molecular weight of 3,000 to 1,000,000, more preferably 5,000 to 500,000, and may be any of a linear chain, a branch, and a ring. 0 < a polymer compound (D)> The polymer of the organic thin film transistor insulating layer material preferably has another aspect of the compound, which has a Yang silky reactive group, has a fluorine atom, has two or more of the above ith functional groups, and has two A polymer compound having one structural unit of active hydrogen or a structural unit having two or more active hydrogens on 323900 35 201239046. Such a polymer compound is referred to as a polymer compound (D). Among the polymer compounds (D), a repeating unit containing a functional group represented by the formula (1), a repeating unit containing a functional group represented by the formula (2), and a repeating unit containing a first functional group are more preferably used. A polymer compound with a repeating unit containing active hydrogen. The polymer compound (D) can be produced, for example, by a polymerizable monomer which is a raw material of a repeating unit containing active hydrogen, a polymerizable monomer which is a raw material of a repeating unit represented by the formula (2), The polymerizable monomer which is a raw material of the repeating unit containing the first functional group is copolymerized with a photopolymerization initiator or a thermal polymerization initiator to obtain a copolymer, and then the functional group represented by the formula (1) is obtained. A method of reacting a compound of a raw material with a compound which reacts with active hydrogen with a reactive hydrogen of a part of the copolymer. The polymer compound (D) may, for example, be poly(styrene: co-[4-aminophenylethylene]-co-penta-phenylene-co--[2-[0-(1'-methyl) Propylamino)carboxyamino]ethyl-methacrylate]), poly(styrene-co-[4-aminophenylethylene]-co-penta-phene ethene_co-[2-[ 1'-(3',5'-dimercaptoindolozolyl)carbonylamino]ethyl-mercapto acrylate]), poly(styrene-co-[4-aminophenylidene]- - Wuxiang phenethyl-co-acrylonitrile-co-[2-[〇-(1'-mercaptopropylamino)carboxyamino]ethyl-mercapto acrylate]), poly(benzene乙妇-共_[4-Aminophenethyl]-co-pentafluorophenylethylene-co-acrylonitrile-co-[2-[1' -(3',5'-didecyl- 0 ratio 〇 基)) ylamino]ethyl-methacrylate]), poly(styrene-co-[4-aminostyrene]-co-pentafluorobenzene 323900 36 201239046 olefin-co-acrylonitrile -co-[2-[0-(indolyl-mercaptopropylamino)carboxylamino]ethyl-methacrylate]-co-allyl trimethylsulfonate), poly(styrene-co- [2-hydroxyethyl-methacrylate]-co-pentafluorostyrene-co-acrylonitrile-co-[2-[1' -(3,,5 '-Dimercaptopyrazolyl)carbonylamino]ethyl-mercaptoacrylate]-co-allyl trimethylsulfonate, poly([2-hydroxyethyl-methacrylate]-co- Pentafluorostyrene-co-[2-[0-(Γ-methylpropylamino)carboxyamino]ethyl-mercapto acrylate]), poly([2-hydroxyethyl-mercaptoacrylic acid) Ester]-co-pentafluorostyrene-co-[2-[1'-(3',5'-dimethylpyrazolyl)carbonylamino]ethyl-mercapto acrylate]), poly(benzene Ethylene-co-pentafluorostyrene-co-[2-hydroxyethyl-mercapto acrylate]-co-[2-[0-(Γ-methylpropylideneamino)carboxyamino]ethyl- Mercapto acrylate]), poly(styrene-co-pentafluorostyrene-co-[2-hydroxyethyl-methacrylic acid S]-co-[2-[1' -(3',5' - Dimercapto" is more than η-based) alkylamino]ethyl-mercapto acrylate]). The polymer compound (D) preferably has a weight average molecular weight of 3,000 to 1,000,000, more preferably 5,000 to 500,000, and may be any of a linear chain, a branch, and a ring. 0 <Active hydrogen compound (Ε)> The organic thin film transistor insulating layer material may also contain an active hydrogen compound (Ε). The active hydrogen compound (Ε) is bonded to the second functional group formed in the polymer compounds (a) to (D) to form a crosslinked structure inside the insulating layer. The active hydrogen compound contains a low molecular compound containing two or more active hydrogens (hereinafter referred to as a low molecular weight active hydrogen compound (Ε-1)), and a polymer compound containing two or more active hydrogens (hereinafter, 323900 37 201239046) It is called a polymer active hydrogen compound (E-2)). The active hydrogen is typically exemplified by a hydrogen atom contained in an amine group, a hydroxyl group or a thiol group. The active hydrogen is preferably a second functional group formed by the above first functional group, and the hydrogen contained in the phenolic radical which can be favorably reacted with the isocyanate group or the isothiouric acid group, and the alcoholic base group Hydrogen, hydrogen contained in an aromatic amine group. Specific examples of the low molecular weight active hydrogen compound (E-1) include a compound having a structure in which a group containing two or more active hydrogens is bonded to a low molecular structure. The low molecular structure may, for example, be an alkyl structure or a benzene ring structure. Specific examples of the low molecular compound include an amine compound, an alcohol compound, a phenol compound, and a thiol compound. In the present specification, the term "alkyl structure" means a linear, branched or cyclic structure composed of an aliphatic hydrocarbon. On the other hand, the "benzene ring structure" means a linear, branched or cyclic structure composed of an aromatic hydrocarbon. Examples of the amine compound include ethylenediamine, propylenediamine, hexamethylenediamine, N,N,N',N',-tetraaminoethylethylenediamine, o-phenylenediamine, and Phenylenediamine, p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, melamine, 2,4,6-triaminopyrimidine, 1,5,9-triazacyclododecane, 1,3-bis(3-aminopropyl)tetramethyldimercapto, 1,4-bis(3-aminopropyldimethylpyridyl)benzene, 3-(2-aminoethyl) Aminopropyl) ginseng (tridecyloxy) alkane. Examples of the alcohol-based compound include ethylene glycol, 1,2-dihydroxypropane, glycerin, and 1,4-dimethanolbenzene. Examples of the phenol compound include, for example, 1,2-dihydroxybenzene, 1,3-323900 38 201239046 dihydroxybenzene, 1,4-dihydroxy stupid (hydroquinone), 1,2-dihydroxynaphthalene, isophthalic acid. Diphenol, fluoroglycerol, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzamine. Examples of the thiol compound include, for example, ethanedithiol and terephthalic acid. The low molecular compound containing two or more active oximes is preferably an alcohol compound, a conjugate compound or an aromatic amine compound. On the other hand, in the polymer-active ruthenium compound (E-2), the active hydrogen may be directly bonded to the main chain constituting the polymer compound or may be bonded via a specific group. Further, the active hydrogen may be contained in the structural unit constituting the polymer compound, and in this case, it may be contained in each structural unit or may be contained only in a part of the structural unit. Further, the active hydrogen may be bonded only to the end of the polymer compound. Specific examples of the polymer active hydrogen compound (E-2) include a compound having a structure in which a group containing two or more active hydrogens is bonded to a polymer structure. The polymer active hydrogen compound (E-2) preferably has a fluorine atom. This is due to the reduced polarity of the insulating layer formed. Further, the polymer active hydrogen compound (E-2) preferably has an addition polymerization reaction group. This is due to the increased crosslink density of the insulating layer formed. The polymer active hydrogen compound (E-2) can be obtained by separately polymerizing a monomer having an active hydrogen group and an unsaturated bond having a double bond or copolymerizing with another polymerizable monomer to form a copolymer. . The polymerization or copolymerization of the polymerizable monomers can be carried out by a method generally used by those skilled in the art. In order to incorporate a fluorine atom into the polymer active hydrogen compound (E-2), a polymerizable monomer which is a raw material of the repeating unit represented by the above formula (2) can be used as the above other polymerizable monomer. Further, in order to incorporate an addition polymerization reaction group into the polymer active hydrogenation 323900 39 201239046 compound (E-2), a compound which is a raw material of the functional group represented by the above formula (1) can be reacted with active hydrogen. The compound is reacted with a portion of the active hydrogen in the polymer active hydrogen compound (E-2). At the time of the polymerization, a photopolymerization initiator or a thermal polymerization initiator may also be used. Further, the same as the above may be used as the polymerizable monomer, the photopolymerization initiator, and the thermal polymerization initiator. The active hydrogen-containing group and the monomer having an unsaturated bond may, for example, be an amino styrene, a hydroxystyrene, a vinyl benzoyl alcohol, an aminoethyl methacrylate, an ethylene glycol monovinyl ether, or an acrylic acid 4 - Hydroxybutyl ester. The monomer having an active hydrogen group and a monomer having an unsaturated bond is preferably one having a hydroxyl group or having an amine group. Further, a polymer compound containing two or more active hydrogens can be obtained by condensing a compound or a compound in the presence of an acid catalyst, and a novolak resin can also be used. The polystyrene-equivalent weight average molecular weight of the polymer compound containing two or more active hydrogen-containing groups is preferably from 1,000 to 1,000,000, more preferably from 3,000 to 500,000. Thereby, the flatness and uniformity of the insulating layer can be obtained. The weight average molecular weight converted to polystyrene was measured by GPC. <Compound having photodimerization reaction group> The organic thin film transistor insulating layer material of the present invention may further contain a compound having a plurality of functional groups which absorb the energy of electromagnetic waves or the energy of electron beams to generate a dimerization reaction. . The energy of absorbing electromagnetic waves or the energy of electron beams 323900 40 201239046 The functional group which generates a dimerization reaction is referred to as "photopolymerization group" in the present specification. Such a compound may, for example, be a low molecular compound containing two or more photopolymerization groups, and a polymer compound containing a repeating unit containing a photodimerization reaction group. In one embodiment, the photodimerization reaction group incorporates a polymer active hydrogen compound (E-2). In this case, a polymer compound containing two or more photodimerization groups is introduced as an active ruthenium compound into the organic thin film transistor insulating layer material of the present invention. In another embodiment, a compound containing two or more photopolymerization groups is introduced into the organic thin film transistor insulating layer material of the present invention together with an active hydrogen compound or the like. In order to incorporate a photodimerization reaction group into the polymer active hydrogen compound (E-2), a polymerizable monomer which is a raw material of a repeating unit represented by the following formula (5) can be used as the other polymerizable monomer. A polymerizable monomer containing a functional group represented by the following formula (6) and a double bond is preferred. When the electromagnetic wave absorbed by the photopolymerization group is too low, when the organic thin film transistor insulating layer material is formed by photopolymerization, the photodimerization reaction group also reacts, so that high energy light is preferred. The preferred electromagnetic wave absorbed by the photopolymerization group is ultraviolet light, for example, having a wavelength of 400 nm or less, preferably 150 to 380 nm. The term "dimerization" as used herein refers to the chemical bonding of two organic compounds. The molecules of the bond may be the same or different species from each other. The chemical structures of the two polymerization-related functional groups in the two polymerizations may be the same or different from each other. However, it is preferred that the functional group be a structure and a combination which can produce a dimerization reaction even without using a reaction aid such as a catalyst or an initiator. It is 323900 41 201239046 The possibility of deterioration of the surrounding organic material when it comes into contact with the residue of the reaction assistant. The repeating unit having a photodimerization group is preferably a repeating unit represented by the formula (5).

Rl7 HnRl7 Hn

(Rfab)c(Rfab)c

[式中，R12表示氫原子或甲基。R3及R4分別獨立地表 示碳數1至20之一價之有機基。該一價之有機基中之氫原 子可經氟原子取代。R3中之碳原子與R4中之碳原子亦可鍵 結而形成5員環或6員環。Rbb表示連結高分子化合物之主 鏈與側鏈之可具有氟原子之連結部分。c表示0或1之整 數。]。 於某一形態，心為曱基。碳數1至20之一價之有機 基與上述為同意義。當R3中之碳原子與R4中之碳原子鍵結 而形成5員環或6員環時，5員環可舉例如環戊烯。6員環 可舉例如環己烯。 又，於某一形態，r3及r4為相同或相異，係選自曱基 及乙基所構成群之基。[wherein R12 represents a hydrogen atom or a methyl group. R3 and R4 each independently represent an organic group having one carbon number of 1 to 20. The hydrogen atom in the monovalent organic group may be substituted with a fluorine atom. The carbon atom in R3 and the carbon atom in R4 may also be bonded to form a 5-membered ring or a 6-membered ring. Rbb represents a linking moiety which may have a fluorine atom in the main chain and the side chain of the linking polymer compound. c represents an integer of 0 or 1. ]. In a certain form, the heart is the base. The organic group having a carbon number of 1 to 20 is the same as the above. When a carbon atom in R3 is bonded to a carbon atom in R4 to form a 5-membered ring or a 6-membered ring, the 5-membered ring may, for example, be cyclopentene. The 6-membered ring may, for example, be cyclohexene. Further, in a certain form, r3 and r4 are the same or different and are selected from the group consisting of a thiol group and an ethyl group.

Rbb所表示之可具有氟原子之連結部分，只要為具有於 323900 42 201239046 使本發明之有機薄臈電晶體絕緣層材料交聯之環境條件下 不顯示反應性之構造之二價之基即可。連結部分之具體 例’可舉例如由碳數1至20之二價之有機基所構成之鍵、 醚鍵（、酮鍵（~c〇-)、酯鍵（-coo-、-oco-)、醯胺鍵 (NHCO C0NH-)、胺基甲酸酯鍵（_NHC〇〇---0C0NH-)及 組合3亥等鍵之鍵等。e表示〇或1之整數。於某-形態，c 為1。 上述奴數1至20之二價之有機基，可為直鏈、分 環狀之你一土 、 者’可為脂肪族烴基亦可為芳香族烴基。可舉 J厌數1至2〇之二價之直鏈狀脂肪族烴基、碳數3至 2〇之一仏之分枝狀脂肪族烴基、碳數3至20之二價之環 狀t基可經烧基等取代之碳數6至20之二價之芳香族烴 基其中，較佳為碳數1至6之二價之直鏈狀脂肪族烴基、 碳數3至6之二價之分枝狀脂肪族烴基、碳數3至6之二 價之環狀烴基、可經烷基等取代之二價之碳數6至2〇之芳 香族烴基。 二價之脂肪族烴基及二價之環狀烴基之具體例，可舉 例如亞曱基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、 伸異丙基、伸異丁基、二曱基伸丙基、伸環丙基、伸環丁 基、伸環戊基、伸環己基。 碳數6至20之二價之芳香族烴基之具體例，可舉例 如伸苯基、伸萘基、伸蒽基、二曱基伸苯基、三甲基伸苯 基、伸乙基伸苯基、二伸乙基伸苯基、三伸乙基伸苯基、 伸丙基伸苯基、伸丁基伸苯基、曱基伸萘基、二曱基伸萘 323900 43 201239046 乙烯伸萘基、曱基伸 基、三曱基伸萘基、乙烯基伸萘基、 蒽基、乙基伸蒽基。 〃光二聚合反應基之較佳例，為馬來酿亞胺基之3位之 氫原子及4位之氫原子分別以烷基或芳基取代之基、上述 式（6)所表示之基，特佳為馬來醯亞胺基之3位之氫原子及 4位之氫原子分別以烷基或芳基取代之基、式（？）所表示之 基。式（Ό中’R，較佳為丙烷-i，3一二基、丁烷、，斗-二基。The linking portion represented by Rbb may have a fluorine atom, and may be a divalent group having a structure which does not exhibit reactivity under environmental conditions in which the organic thin germanium dielectric insulating layer material of the present invention is crosslinked at 323900 42 201239046. . Specific examples of the linking portion may be, for example, a bond composed of a divalent organic group having 1 to 20 carbon atoms, an ether bond (, a ketone bond (~c〇-), an ester bond (-coo-, -oco-). , a guanamine bond (NHCO C0NH-), a urethane bond (_NHC〇〇---0C0NH-), and a bond such as a combination of 3, etc. e represents an integer of 〇 or 1. In a certain form, c The organic base of the above-mentioned slave number of 1 to 20 may be a straight chain or a ring-shaped one, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. a divalent linear aliphatic hydrocarbon group of 2 valence, a branched aliphatic hydrocarbon group having 3 to 2 carbon atoms, and a cyclic t group having a carbon number of 3 to 20 may be substituted by an alkyl group or the like. A divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a divalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, and carbon. a divalent cyclic hydrocarbon group of 3 to 6 and a divalent carbon 6 to 2 ring aromatic hydrocarbon group which may be substituted by an alkyl group, etc. Specific examples of the divalent aliphatic hydrocarbon group and the divalent cyclic hydrocarbon group, For example, anthracene, ethyl, propyl, and butyl Base, pentyl group, hexyl group, isopropyl group, isobutyl group, dimercaptopropyl group, propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group. Carbon number 6 to 20 Specific examples of the divalent aromatic hydrocarbon group include, for example, a phenylene group, an anthranyl group, a fluorenyl group, a diphenyl group, a phenyl group, a trimethylphenyl group, an ethylidene group, and a diethyl phenyl group. , Ethylene ethyl phenyl, propyl phenyl, butyl phenyl, fluorenylnaphthyl, fluorenyl phthalocyanine 323900 43 201239046 Ethylene, naphthyl, fluorenyl, tridecyl, naphthyl, vinyl a preferred example of the fluorene dimerization group, which is a hydrogen atom at the 3-position of the maleimine group and a hydrogen atom at the 4-position, respectively, substituted with an alkyl group or an aryl group. The group represented by the above formula (6) is particularly preferably a group represented by the formula (?) in which a hydrogen atom at the 3-position of the maleimine group and a hydrogen atom at the 4-position are respectively substituted with an alkyl group or an aryl group. The formula (R in the 'R, preferably propane-i, 3-diyl, butane, and bucket-diyl.

[式中，R’表示烷二基。] 當光二聚合反應基為馬來醢亞胺基之3位之氫原子及 4位之氫原子分別以烧基或芳基取代之基、或式（γ)所表示 之基時’若照射紫外線或電子射線則產生2 + 2環化反應， 同時由於氫抽離反應而產生碳自由基，與含有雙鍵之官能 基反應而使有機薄膜電晶體絕緣層材料交聯。 可使用於本發明之含有2個以上式（6)所表示之官能 基之低分子化合物，例如，可藉由使含有2個以上胺基之 低分子化合物、與成為式（6)所表示之官能基之原料的酸肝 反應來製造。 具有2個以上光二聚合反應基之低分子化合物，可舉 例如1，2-伸乙基雙馬來醯亞胺、1，6-六亞甲基雙馬來醯亞 323900 44 201239046 胺、1，2-伸乙基雙（3，，4’ -二曱基馬來醯亞胺）、1，6-六 亞甲基雙（3’，4’ -二曱基馬來醯亞胺）、1,2-伸乙基雙 (3’ -苯基馬來醯亞胺）、1，6-六亞曱基雙（3’ -苯基馬來醯 亞胺）、1，2-伸苯基雙馬來醯亞胺、1，3-伸苯基雙馬來醯亞 胺、1,4-伸苯基雙馬來醯亞胺、1,2-伸苯基雙（3’，4’ -二曱基馬來醯亞胺）、1，3-伸苯基雙（3’，4’ -二曱基馬來 醯亞胺）、1,4-伸苯基雙（3’，4’ -二曱基馬來醯亞胺）、 1，2-伸苯基雙（3’ -苯基馬來醯亞胺）、1，3-伸苯基雙（3’ -苯基馬來醯亞胺）、1,4-伸苯基雙（3’ -苯基馬來醯亞胺）。 本發明可使用之含有含式（6)所表示之官能基之重複 單元的高分子化合物，例如，可藉由將含有式（6)所表示之 官能基與雙鍵之聚合性單體單獨地聚合、或與其他聚合性 單體共聚合形成共聚物來製得。於該等之聚合時，亦可使 用光聚合起始劑或熱聚合起始劑。又，其他聚合性單體、 光聚合起始劑、熱聚合起始劑，亦可使用與上述同樣者。 具有式（6)所表示之官能基與雙鍵之聚合性單體，例 如，可藉由使含有胺基與雙鍵之化合物、與成為式（6)所表 示之官能基之原料的酸酐反應來製造。 含有式（6)所表示之官能基與雙鍵之聚合性單體之 例，可舉例如N-(3’ -曱基丙烯醯氧基丙基）-3,4-二曱基 馬來醯亞胺、N-(3’ -曱基丙烯醯氧基丙基）-1-環己烷 -1，2-二羧醯亞胺。 可使用於本發明之含有含上述式（6)所表示之官能基 之重複單元的高分子化合物，可藉由將含有胺基之聚合性 323900 45 201239046 單體單獨地聚合之聚合物，與成為式（6)所表示之官能基之 原料的酸酐反應來製造。又，亦可藉由將含有胺基之聚合 性單體與其他聚合性單體共聚合以製造共聚物後，使該共 聚物與成為式（6)所表示之官能基之原料的酸酐反應來製 造。於該等之聚合時，亦可使用光聚合起始劑或熱聚合起 始劑。 本發明可使用之含有含上述式（6)所表示之官能基之 重複單元的高分子化合物，可舉例如聚（苯乙烯-共-五氟苯 乙稀"共_[N-(3-甲基丙婦酿氧基丙基_3 , 4 _二曱基馬 來酿亞胺）])、聚（苯乙稀-共-五氟苯乙烯-共-[N-(3-甲基 丙烯醯氧基丙基-1’ -環己烯-Γ，2’ -二羧醯亞胺）])、聚 (苯乙稀-共-五氣苯乙稀-共- [N-(3_曱基丙稀酿氧基丙基 -3’，4’ -二甲基馬來醯亞胺）])-共-丙烯腈、聚（苯乙烯-共-五氟苯乙稀-共-[N-(3_曱基丙烤酿氧基丙基-1 •環己 烯-1’，2’ -二羧醯亞胺）])-共-丙烯腈、聚（苯乙烯-共-五敗苯乙稀-共-[N_(3*~曱基丙稀酿氧基丙基_3 ，4 _二 曱基馬來醯亞胺）])-共-烯丙基三曱基鍺）、聚（苯乙烯-共-五I苯乙稀-共-[N-(3-曱基丙稀酿氧基丙基_1 _環己稀 -1’，2’ -二羧醯亞胺）])-共-烯丙基三曱基鍺）。 <有機薄膜電晶體絕緣層材料> 高分子化合物（A)至（D)，當與光聚合起始劑或光二聚 合反應基組合時，皆為光及熱能交聯性，可作為本發明之 有機薄膜電晶體絕緣層材料使用。高分子化合物（A)及（B) 並不具有活性氫。然而，藉由於大氣中等含水分之環境進 323900 46 201239046 行加熱，第2官能基可與水反應，而高分子化合物（A)及（B) 亦可熱交聯。 本發明之有機薄膜電晶體絕緣層材料之一較佳態樣， 係含有高分子化合物（A)與活性氫化合物（E)之組成物。該 組成物之中，以含有高分子化合物（B)與活性氫化合物（E) 之組成物較佳。 高分子化合物（A)與活性氳化合物（E)之混合比例，較 佳為可由高分子化合物（A)生成之第2官能基、與活性氳化 合物（E)中之含活性氫之基的莫耳比為60/100至150/100 之比例。更佳為70/100至120/100之比例，又更佳為 90/100.至110/100之比例。若以該莫耳比未滿60/100之 比例混合則活性氫過剩，使磁滯之降低效果變小，而若以 超過150/100之比例混合則與活性氳反應之官能基過剩， 而使臨限電壓之絕對值增大。 本發明之有機薄膜電晶體絕緣層材料之較佳之其他 態樣為高分子化合物（C)。高分子化合物（C)之中，以高分 子化合物（D)為佳。由於高分子化合物（C)及高分子化合物 (D)具有含第1官能基與活性氫之基，故可單獨使用於本發 明之有機薄膜電晶體絕緣層材料。 於本發明之有機薄膜電晶體絕緣層材料，含有鍵結於 高分子化合物（A)至（D)或活性氳化合物（E)之有機基及官 能基。該等有機基及官能基之含量，可考量對有機薄膜電 晶體絕緣層材料所要求之特性，藉由調節具有機基及官能 基之重複單元的量來適當地決定。 323900 47 201239046 較佳之一態樣，以本發明之有機薄膜電晶體絕緣層材 料所含之高分子化合物所具有之重複單元之合計數為基 準，含有加成聚合反應基之重複單元的莫耳分率為0.01 至0. 7，較佳為0. 05至0. 6，更佳為0. 1至0. 5。含有加 成聚合反應基之重複單元的莫耳分率若未滿0.01則硬化 會不充分，而若超過0. 7則高分子化合物之保存安定性會 變差。 含有第1官能基之重複單元的莫耳分率為0.01至 0. 7，較佳為0. 05至0. 6，更佳為0. 1至0. 5。含有第1 官能基之重複單元的莫耳分率若未滿0.01則硬化會不充 分，而若超過0. 7則會對電晶體特性造成不良影響。活性 氫的量係以與第1官能基反應之量不會過與不足的量為基 準來決定。 又，含有光二聚合反應基之重複單元的莫耳分率為 0. 7以下，較佳為0. 05至0. 6，更佳為0. 1至0. 5。含有 光二聚合反應基之重複單元的莫耳分率若超過0. 7則會對 電晶體特性造成不良影響。 導入高分子化合物之氟的量，相對於高分子化合物全 體的量，較佳為50質量％以下，更佳為1至40質量％，又 更佳為5至35質量％。氟的量若超過50質量％，則與有機 半導體材料的親和性惡化而難以於其上積層。 於本發明之有機薄膜電晶體絕緣層材料，亦可含有用 以混合或調節濃度之溶劑、用以使高分子化合物（A)至（D) 交聯所使用之交聯劑、與該交聯劑組合使用之添加劑等。 323900 48 201239046 所使用之溶劑有四氫呋喃或二***等醚溶劑；己烷等脂肪 族烴溶劑；環己烷等脂環式烴溶劑；戊烯等不飽和烴溶劑； 二曱苯等芳香族烴溶劑；丙酮等酮溶劑；乙酸丁酯等乙酸 酯溶劑；異丙醇等醇溶劑；氯仿等鹵素溶劑或該等之混合 溶劑。又，添加劑可使用用以促進交聯反應之觸媒、整平 劑、黏度調節劑等。 本發明之有機薄膜電晶體絕緣層材料’係有機薄膜電 晶體所含之絕緣層之形成時所使用之組成物。有機薄膜電 晶體之絕緣層中，較佳為使用於保護層及閘極絕緣層的形 成。有機薄膜電晶體絕緣層材料，較佳為有機薄膜電晶體 保護層組成物、有機薄膜電晶體閘極絕緣層組成物，更佳 為有機薄膜電晶體閘極絕緣層組材料。 <有機薄膜電晶體> 第1圖係顯示本發明之一實施形態之下閘極上接觸型 有機薄膜電晶體之構造的模式截面圖。該有機薄膜電晶體 具備：基板1、形成於基板1上之閘極電極2、形成於閘極 電極2上之閘極絕緣層3、形成於閘極絕緣層3上之有機 半導體層4、於有機半導體層4上夾持通道部所形成之源 極電極5及汲極電極6、與覆蓋元件全體之保護層7。 下閘極上接觸型有機薄膜電晶體，例如於基板上形成 閘極電極，於閘極電極上形成閘極絕緣層，於閘極絕緣層 上形成有機半導體層，於有機半導體層上形成源極電極、 汲極電極，並形成保護層而製造。本發明之有機薄膜電晶 體絕緣層材料，作為有機薄膜電晶體閘極絕緣層組材料， 323900 49 201239046 可使用於閘極絕緣層的形成。又，作為有機薄膜電晶體保 護層材料，亦可使用於保護層的形成。 第2圖係顯示本發明之一實施形態之下閘極下接觸型 有機薄膜電晶體之構造的模式截面圖。該有機薄膜電晶體 具備：基板1、形成於基板1上之閘極電極2、形成於閘極 電極2上之閘極絕緣層3、於閘極絕緣層3上夾持通道部 所形成之源極電極5及汲極電極6、形成於源極電極5及 汲極電極6上之有機半導體層4、與覆蓋元件整體之保護 層7。 下閘極下接觸型有機薄膜電晶體，例如於基板上形成 閘極電極，於閘極電極上形成閘極絕緣層，於閘極絕緣層 上形成源極電極、汲極電極，於源極電極、汲極電極上形 成有機半導體層，並形成保護層而製造。本發明之有機薄 膜電晶體絕緣層材料，作為有機薄膜電晶體閘極絕緣層材 料，可使用於閘極絕緣層的形成。又，作為有機薄膜電晶 體保護層材料，亦可使用於保護層的形成。 ••一 · 閘極絕緣層或保護層的形成，可藉由於有機薄膜電晶 體絕緣層材料視需要添加溶劑等以調製絕緣層塗佈液，將 絕緣層塗佈液塗佈於位於閘極絕緣層或保護層之下之層的 表面，使其乾燥、硬化而進行。該絕緣層塗佈液所使用之 有機溶劑，只要不溶解有機薄膜電晶體絕緣層材料者即 可，並無特別限制，較佳為常壓下之沸點為100°c至200 °C之有機溶劑。該有機溶劑之例，可舉例如2-庚酮（沸點 151°C)、丙二醇單曱醚乙酸酯（沸點146°C)。於該絕緣層 323900 50 201239046 塗佈液，亦可視需要添加整平劑、界面活性劑、硬化觸媒 等。本發明之有機薄膜電晶體絕緣層材料，作為有機薄膜 電晶體閘極絕緣層組成物，亦可使用於閘極絕緣層之形成。 該絕緣層塗佈液，可藉旋塗法、模塗機、網版印刷、 喷墨等周知之方法塗佈於閘極電極上。所形成之塗佈層可 視需要進行乾燥。此處，所謂之乾燥係意指將塗佈之樹脂 組成物所含之溶劑除去。 使塗佈層乾燥，接著使其硬化。硬化係意指有機薄膜 電晶體閘極絕緣層材料交聯。電晶體閘極絕緣層材料之交 聯，例如可藉由對塗佈層照射電磁波或電子射線、或施加 熱來進行。 當對塗佈層照射電磁波或施加熱時，由高分子化合物 (A)或（B)之第1官能基生成第2官能基，該第2官能基與 活性氫化合物（E)之含活性氫之基反應，而有機薄膜電晶體 閘極絕緣層材料交聯。或者，由高分子化合物（C )或（D )之 第1官能基生成第2官能基，該第2官能基與分子内之含 活性氳之基反應，而有機薄膜電晶體閘極絕緣層材料交聯。 當對塗佈層照射電磁波或電子射線時，高分子化合物 (A)至（D)所具有之加成聚合反應基加成聚合，而有機薄膜 電晶體閘極絕緣層材料交聯。 當高分子化合物（A)至（D)所含之第1官能基為藉由電 磁波的照射，而生成與活性氫反應之第2官能基之官能基 時，有機薄膜電晶體閘極絕緣層，較佳為以包含下述步驟 之形成方法形成：將含有機薄膜電晶體閘極絕緣層材料之 323900 51 201239046 液塗佈於基材上以於該基材切餘佈層之步驟；以及對 該塗佈層照射電磁波或電子射線之步驟。 當高分子化合物（A)至（D)所含之第i官能基為藉由熱 的作用，而生成與活性氫反應之第2官能基之官能基時， 較佳為以包含下述步驟之形成方法形成有機薄膜電晶體間 極絕緣層.將含有機薄膜電晶體閘極絕緣層材料之液塗佈 於基材上以於該基材上形成塗佈層之步驟；以及對該塗佈 層照射電磁波或電子射線之步驟。更佳為以包含下述步驟 之形成方法形成有機薄膜電晶體閘極絕緣層：將含有機薄 膜電晶體閘極絕緣層材料之液塗佈於基材上以於該基材上 形成塗佈層之步驟；對該塗佈層照射電磁波或電子射線之 步驟；及對該塗佈層施加熱之步職。 藉由進行對塗佈層照射電磁波或電子射線之步驟、與 對塗佈層施加熱之步驟兩者，可提升絕緣層之交聯密度。 特別是當將有機薄膜電晶體閘極絕緣層材料使用於閘極絕 緣層時，有機薄膜電晶體之臨限電壓（Vth)之絕對值及磁滯 邊小。其係推測為藉由提升絕緣層之交聯密度，可進一步 抑制施加電壓時之分極’而使有機薄膜電晶體之臨限電壓 之絕對值及磁滯變小。 當對塗佈層施加熱時，係將塗佈層加熱至約至250 C (較佳為約1〇〇至23CTC)之溫度維持約5至120分鐘（較 佳為約10至60分鐘）。加熱溫度若過低或加熱時間過短則 絕緣層之交聯會不充分，加熱溫度過高或加熱時間過長則 絕緣層可能會損傷。 323900 52 201239046 當對塗佈層照射電磁波時’可考量絕緣層之交聯及損 傷程度來調節照射條件。將施加微波以加熱時，可考量絕 緣層之交聯及損傷程度來調節施加條件。 照射之電磁波之波長以450nm以下為佳，更佳為150 至410nm。所照射之電磁波之波長若超過450ηιη則有機薄 膜電晶體絕緣層材料的交聯會變得不充分。電磁波以紫外 線為佳。 紫外線之照射，例如可使用半導體之製造時所使用之 曝光裝置或用以使UV硬化性樹脂硬化所使用之UV燈來進 行。電子射線之照射，例如可使用超小型電子射線照射管 來進行。加熱可使用加熱器及烘箱等來進行。其他照射條 件及加熱條件，可視加成聚合反應基及所使用之光聚合起 始劑之種類及量等而適當地決定。 於閘極絕緣層，亦可形成自我組織化單分子膜層。該 自我組織化單分子膜層，例如可藉由以於有機溶劑中溶解 1至10重量％之烷基氣矽烷化合物或烷基烷氧基矽烷化合 物之溶液，對閘極絕緣層進行處理而形成。 烧基氯石夕烧化合物之例，可舉例如甲基三氯石夕烧、乙 基三氣矽烷、丁基三氯矽烷、癸基三氯矽烷、十八基三氣 矽烷。 烷基烷氧基矽烷化合物之例，可舉例如甲基三甲氧基 矽烷、乙基三甲氧基矽烷、丁基三曱氧基矽烷、癸基三甲 氧基矽烷、十八基三曱氧基矽烷。 基板1、閘極電極2、源極電極5、没極電極6及有機 323900 53 201239046 半導體層4’可藉由-般所❹之材料及枝構成 之材料，可使用樹脂、或塑膠之板、或薄膜、玻^ 板等。電極之材料’係使用鉻、金、鈒.、如 h 銀、紹、I目等，以蒗 鍍法、濺鍍法、印刷法、喷墨法等周知之 … 成電極〇 用以形成有機半導體層4之有機半導體化合 7Γ共扼聚合物’例如可使用聚吡η各類、印 ’' 來蒌吩類、聚笑脸[wherein R' represents an alkanediyl group. When the photodimerization group is a hydrogen atom at the 3 position of the maleimine group and a hydrogen atom at the 4-position is substituted with a group of a group or an aryl group, or a group represented by the formula (γ), Or an electron ray produces a 2 + 2 cyclization reaction, and at the same time, a carbon radical is generated due to the hydrogen extraction reaction, and the organic thin film transistor insulating layer material is crosslinked by reacting with a functional group containing a double bond. The low molecular compound containing two or more functional groups represented by the formula (6) which can be used in the present invention can be represented, for example, by a low molecular compound containing two or more amine groups and represented by the formula (6). The acid-hepatic reaction of the raw material of the functional group is produced. A low molecular compound having two or more photodimerization groups, for example, 1,2-extended ethyl bismaleimide, 1,6-hexamethylene double malayan 323900 44 201239046 amine, 1, 2-extended ethyl bis(3,4'-dimercaptomaleimine), 1,6-hexamethylenebis(3',4'-dimercaptomaleimide), 1 , 2-extended ethyl bis(3'-phenylmaleimide), 1,6-hexamethylene bis(3'-phenylmaleimide), 1,2-phenylene double Maleimide, 1,3-phenylene bismaleimide, 1,4-phenylene bismaleimide, 1,2-phenylene bis (3',4'-di Mercaptopurine imine), 1,3-phenylene bis(3',4'-dimercaptomaleimide), 1,4-phenylene bis (3',4'-di Indole-based maleimide), 1,2-phenylenebis(3'-phenylmaleimide), 1,3-phenylenebis(3'-phenylmaleimide) , 1,4-phenylene bis(3'-phenylmaleimide). The polymer compound containing a repeating unit containing a functional group represented by the formula (6) which can be used in the present invention can be used, for example, by separately polymerizing a monomer having a functional group represented by the formula (6) and a double bond. It is obtained by polymerization or copolymerization with other polymerizable monomers to form a copolymer. A photopolymerization initiator or a thermal polymerization initiator may also be used in the polymerization. Further, other polymerizable monomers, photopolymerization initiators, and thermal polymerization initiators may be used in the same manner as described above. The polymerizable monomer having a functional group represented by the formula (6) and a double bond can be, for example, reacted with an acid anhydride of a compound containing an amine group and a double bond and a raw material which is a functional group represented by the formula (6) To manufacture. Examples of the polymerizable monomer containing a functional group represented by the formula (6) and a double bond may, for example, be N-(3'-mercaptopropenyloxypropyl)-3,4-diindenylmazepine. Imine, N-(3'-mercaptopropenyloxypropyl)-1-cyclohexane-1,2-dicarboxylimine. The polymer compound containing the repeating unit containing the functional group represented by the above formula (6), which can be used in the present invention, can be polymerized by polymerizing a monomer having an amine group-containing polymerizable 323900 45 201239046 monomer. The acid anhydride of the raw material of the functional group represented by the formula (6) is produced by reacting an acid anhydride. Further, by copolymerizing a polymerizable monomer containing an amine group with another polymerizable monomer to produce a copolymer, the copolymer may be reacted with an acid anhydride which is a raw material of a functional group represented by the formula (6). Manufacturing. A photopolymerization initiator or a thermal polymerization initiator may also be used in the polymerization. The polymer compound containing a repeating unit containing the functional group represented by the above formula (6) which can be used in the present invention may, for example, be poly(styrene-co-pentafluorophenylethyl)<total_[N-(3- Methyl propyl oxypropyl _3 , 4 _ dimercapto mercapto imine)]), poly(styrene-co-pentafluorostyrene-co-[N-(3-methyl propylene)醯oxypropyl-1'-cyclohexene-oxime, 2'-dicarboxylimenide)]), poly(styrene-co-penta-phenethyl---[N-(3_曱) Propylene oxypropyl-3',4'-dimethylmaleimide)])-co-acrylonitrile, poly(styrene-co-pentafluorophenylethylene-co-[N- (3_ mercapto propyl ethoxypropyl-1 • cyclohexene-1', 2'-dicarboxy quinone imine)])-co-acrylonitrile, poly(styrene-co-penta-phenylene Rare-common-[N_(3*~ mercaptopropoxy propyl-3-3,4-diindenylmaleimide)])-co-allyltrimethylsulfonium), poly(benzene Ethylene-co-penta-I phenethyl-co-[N-(3-mercaptopropenyloxypropyl-1 _cyclohexyl-1',2'-dicarboxy quinone imine)])- -allyltrimethylhydrazine). <Organic thin film transistor insulating layer material> The polymer compounds (A) to (D), when combined with a photopolymerization initiator or a photodimerization group, are both light and thermal energy crosslinkability, and can be used as the present invention. The organic thin film transistor insulating layer material is used. The polymer compounds (A) and (B) do not have active hydrogen. However, the second functional group can react with water by heating in an atmosphere of moderate atmospheric moisture, and the polymer compounds (A) and (B) can also be thermally crosslinked. One of the materials of the organic thin film transistor insulating layer of the present invention preferably comprises a composition of the polymer compound (A) and the active hydrogen compound (E). Among the compositions, a composition containing the polymer compound (B) and the active hydrogen compound (E) is preferred. The mixing ratio of the polymer compound (A) and the active hydrazine compound (E) is preferably a second functional group which can be produced from the polymer compound (A) and a reactive hydrogen-containing group in the active hydrazine compound (E). The ear ratio is in the ratio of 60/100 to 150/100. More preferably, the ratio is from 70/100 to 120/100, and more preferably from 90/100 to 110/100. If the molar ratio is less than 60/100, the active hydrogen is excessive, so that the effect of reducing the hysteresis is reduced, and if it is mixed at a ratio of more than 150/100, the functional group reactive with the active hydrazine is excessive. The absolute value of the threshold voltage increases. A preferred other aspect of the organic thin film transistor insulating layer material of the present invention is the polymer compound (C). Among the polymer compounds (C), a high molecular compound (D) is preferred. Since the polymer compound (C) and the polymer compound (D) have a group containing a first functional group and an active hydrogen, they can be used alone in the organic thin film transistor insulating layer material of the present invention. The organic thin film transistor insulating layer material of the present invention contains an organic group and a functional group bonded to the polymer compound (A) to (D) or the active fluorene compound (E). The content of the organic group and the functional group can be appropriately determined by adjusting the properties required for the organic thin film transistor insulating layer material by adjusting the amount of the repeating unit having a machine group and a functional group. 323900 47 201239046 In a preferred embodiment, the molar fraction of the repeating unit containing the addition polymerization reaction group is based on the total number of repeating units of the polymer compound contained in the organic thin film transistor insulating layer material of the present invention. 5至0. 5。 The ratio is from 0.01 to 0. When the molar fraction of the repeating unit containing the addition polymerization reaction group is less than 0.01, the hardening may be insufficient, and if it exceeds 0.7, the storage stability of the polymer compound may be deteriorated. 5至。。。。。。。。。。。。。。。。。。。。。。。。。。。。 If the molar fraction of the repeating unit containing the first functional group is less than 0.01, the hardening may not be sufficient, and if it exceeds 0.7, the effect on the crystal characteristics may be adversely affected. The amount of active hydrogen is determined based on the amount of the reaction with the first functional group, which is not excessive or insufficient. 5至优选。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 If the molar fraction of the repeating unit containing a photodimerization reaction group exceeds 0.7, the effect on the crystal characteristics may be adversely affected. The amount of fluorine to be introduced into the polymer compound is preferably 50% by mass or less, more preferably 1 to 40% by mass, still more preferably 5 to 35% by mass based on the total amount of the polymer compound. When the amount of fluorine exceeds 50% by mass, the affinity with the organic semiconductor material is deteriorated, and it is difficult to laminate thereon. The organic thin film transistor insulating layer material of the present invention may further contain a solvent for mixing or adjusting the concentration, a crosslinking agent used for crosslinking the polymer compounds (A) to (D), and crosslinking with the crosslinking agent. Additives used in combination with agents. 323900 48 201239046 The solvent used is an ether solvent such as tetrahydrofuran or diethyl ether; an aliphatic hydrocarbon solvent such as hexane; an alicyclic hydrocarbon solvent such as cyclohexane; an unsaturated hydrocarbon solvent such as pentene; and an aromatic hydrocarbon solvent such as diphenylbenzene. A ketone solvent such as acetone; an acetate solvent such as butyl acetate; an alcohol solvent such as isopropyl alcohol; a halogen solvent such as chloroform or a mixed solvent thereof. Further, as the additive, a catalyst, a leveling agent, a viscosity modifier or the like for promoting the crosslinking reaction can be used. The organic thin film transistor insulating layer material of the present invention is a composition used in the formation of an insulating layer contained in an organic thin film transistor. In the insulating layer of the organic thin film transistor, it is preferably used for the formation of the protective layer and the gate insulating layer. The organic thin film transistor insulating layer material is preferably an organic thin film transistor protective layer composition, an organic thin film transistor gate insulating layer composition, and more preferably an organic thin film transistor gate insulating layer material. <Organic thin film transistor> Fig. 1 is a schematic cross-sectional view showing the structure of a gate-on-contact type organic thin film transistor according to an embodiment of the present invention. The organic thin film transistor includes a substrate 1, a gate electrode 2 formed on the substrate 1, a gate insulating layer 3 formed on the gate electrode 2, and an organic semiconductor layer 4 formed on the gate insulating layer 3. The organic semiconductor layer 4 has a source electrode 5 and a drain electrode 6 formed by a channel portion, and a protective layer 7 covering the entire device. The lower gate contact type organic thin film transistor, for example, forming a gate electrode on the substrate, forming a gate insulating layer on the gate electrode, forming an organic semiconductor layer on the gate insulating layer, and forming a source electrode on the organic semiconductor layer , a drain electrode, and a protective layer is formed. The organic thin film dielectric insulating layer material of the present invention can be used for the formation of a gate insulating layer as an organic thin film transistor gate insulating layer material, 323900 49 201239046. Further, as the material of the organic thin film transistor protective layer, it can also be used for the formation of a protective layer. Fig. 2 is a schematic cross-sectional view showing the structure of a gate lower contact type organic thin film transistor according to an embodiment of the present invention. The organic thin film transistor includes a substrate 1, a gate electrode 2 formed on the substrate 1, a gate insulating layer 3 formed on the gate electrode 2, and a source formed by sandwiching the channel portion on the gate insulating layer 3. The electrode 5 and the drain electrode 6, the organic semiconductor layer 4 formed on the source electrode 5 and the drain electrode 6, and the protective layer 7 covering the entire element. a lower gate contact type organic thin film transistor, for example, a gate electrode is formed on a substrate, a gate insulating layer is formed on the gate electrode, and a source electrode and a drain electrode are formed on the gate insulating layer at the source electrode An organic semiconductor layer is formed on the gate electrode, and a protective layer is formed and manufactured. The organic thin film transistor insulating layer material of the present invention can be used as an organic thin film transistor gate insulating material for the formation of a gate insulating layer. Further, as the material of the organic thin film dielectric protective layer, it can also be used for the formation of a protective layer. ••1· The gate insulating layer or the protective layer can be formed by applying a solvent or the like to the organic thin film transistor insulating layer material to prepare an insulating layer coating liquid, and applying the insulating layer coating liquid to the gate insulating layer. The surface of the layer below the layer or the protective layer is dried and hardened. The organic solvent used for the insulating layer coating liquid is not particularly limited as long as it does not dissolve the organic thin film transistor insulating layer material, and is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C under normal pressure. . Examples of the organic solvent include 2-heptanone (boiling point: 151 ° C) and propylene glycol monoterpene ether acetate (boiling point: 146 ° C). In the insulating layer 323900 50 201239046 coating liquid, a leveling agent, a surfactant, a hardening catalyst, etc. may be added as needed. The organic thin film transistor insulating layer material of the present invention can also be used as a gate insulating layer for the composition of the organic thin film transistor gate insulating layer. The insulating layer coating liquid can be applied to the gate electrode by a known method such as spin coating, die coater, screen printing, or ink jet. The resulting coating layer can be dried as needed. Here, the term "drying" means removing the solvent contained in the applied resin composition. The coating layer is dried and then hardened. Hardening means that the organic thin film transistor gate insulating material is crosslinked. The crosslinking of the dielectric gate insulating layer material can be carried out, for example, by irradiating the coating layer with electromagnetic waves or electron rays, or applying heat. When the coating layer is irradiated with electromagnetic waves or heat is applied, a second functional group is formed from the first functional group of the polymer compound (A) or (B), and the active hydrogen of the second functional group and the active hydrogen compound (E) is generated. The base reaction, while the organic thin film transistor gate insulating material is crosslinked. Alternatively, a second functional group is formed from the first functional group of the polymer compound (C) or (D), and the second functional group reacts with an active ruthenium-containing group in the molecule, and the organic thin film transistor gate insulating layer material Cross-linking. When the coating layer is irradiated with electromagnetic waves or electron rays, the addition polymerization groups of the polymer compounds (A) to (D) are subjected to addition polymerization, and the organic thin film transistor gate insulating layer material is crosslinked. When the first functional group contained in the polymer compounds (A) to (D) is a functional group of a second functional group which reacts with active hydrogen by irradiation with electromagnetic waves, the organic thin film transistor gate insulating layer, Preferably, the method comprises the steps of: forming a solution of the 323900 51 201239046 liquid containing the organic thin film transistor gate insulating material on the substrate to cut the remaining layer of the substrate; The step of irradiating the coating layer with electromagnetic waves or electron rays. When the ith functional group contained in the polymer compounds (A) to (D) is a functional group which generates a second functional group which reacts with active hydrogen by the action of heat, it is preferred to include the following steps. Forming method to form an organic thin film transistor interlayer insulating layer. A step of coating a liquid containing an organic thin film transistor gate insulating layer material on a substrate to form a coating layer on the substrate; and coating the coating layer The step of illuminating electromagnetic waves or electron rays. More preferably, the organic thin film transistor gate insulating layer is formed by a method comprising the steps of: coating a liquid containing an organic thin film transistor gate insulating material on a substrate to form a coating layer on the substrate. a step of irradiating the coating layer with electromagnetic waves or electron rays; and applying a heat to the coating layer. The crosslinking density of the insulating layer can be increased by performing both the step of irradiating the coating layer with electromagnetic waves or electron rays and the step of applying heat to the coating layer. In particular, when the organic thin film transistor gate insulating layer material is used for the gate insulating layer, the absolute value of the threshold voltage (Vth) of the organic thin film transistor and the hysteresis edge are small. It is presumed that by increasing the crosslink density of the insulating layer, the polarization of the applied voltage can be further suppressed, and the absolute value and hysteresis of the threshold voltage of the organic thin film transistor can be made small. When heat is applied to the coating layer, the coating layer is heated to a temperature of about 250 C (preferably about 1 Torr to 23 CTC) for about 5 to 120 minutes (more preferably about 10 to 60 minutes). If the heating temperature is too low or the heating time is too short, the crosslinking of the insulating layer may be insufficient. If the heating temperature is too high or the heating time is too long, the insulating layer may be damaged. 323900 52 201239046 When the coating layer is irradiated with electromagnetic waves, the irradiation conditions can be adjusted by considering the degree of crosslinking and damage of the insulating layer. When microwaves are applied for heating, the conditions of application can be adjusted by considering the degree of crosslinking and damage of the insulating layer. The wavelength of the electromagnetic wave to be irradiated is preferably 450 nm or less, more preferably 150 to 410 nm. If the wavelength of the electromagnetic wave to be irradiated exceeds 450 nm, the crosslinking of the organic thin film transistor insulating layer material may become insufficient. The electromagnetic wave is preferably ultraviolet. The irradiation of ultraviolet rays can be carried out, for example, by using an exposure apparatus used in the production of a semiconductor or a UV lamp used for curing a UV curable resin. The irradiation of the electron beam can be performed, for example, using an ultra-small electron beam irradiation tube. Heating can be performed using a heater, an oven, or the like. The other irradiation conditions and heating conditions are appropriately determined depending on the type and amount of the addition polymerization reaction group and the photopolymerization initiator to be used. In the gate insulating layer, a self-organized monomolecular film layer can also be formed. The self-organized monomolecular film layer can be formed, for example, by treating a gate insulating layer by dissolving 1 to 10% by weight of an alkyl gas silane compound or an alkyl alkoxy decane compound in an organic solvent. . Examples of the chlorinated chlorite compound include methyltrichlorosilane, ethyltrioxane, butyltrichloromethane, decyltrichlorodecane, and octadecyltrioxane. Examples of the alkyl alkoxydecane compound include methyl trimethoxy decane, ethyl trimethoxy decane, butyl trimethoxy decane, decyl trimethoxy decane, and octadecyl tridecyl decane. . Substrate 1, gate electrode 2, source electrode 5, electrodeless electrode 6 and organic 323900 53 201239046 The semiconductor layer 4' can be made of a material such as a material and a branch, and a resin or a plastic plate can be used. Or film, glass plate, etc. The material of the electrode is made of chromium, gold, tantalum, such as h silver, sho, I mesh, etc., and is known by iridium plating, sputtering, printing, inkjet, etc. The organic semiconductor compound 7 layer conjugated polymer of layer 4 can be used, for example, polypyrrole type, printed '' 蒌 类 、, poly smiley face

類、聚烯丙胺類、苐類、聚咔唑類、聚叫W 71木賴、聚（董+絮；产 烯）類等。又，對有機溶劑具有溶解性之你八^ 丁本。 -刀于物質，例如 可使用稠五苯等多環芳香族之衍生物、賦花主 (phthalocyanine)衍生物、茈衍生物、四硫富瓦缔 (tetrathiafulvalene)衍生物、四氰酉昆二甲 (tetracyanoquinodimethane)衍生物、富勒稀(加1 ) 類、碳奈米管類等。具體而言，可舉例如2,丨3〜笨==6一 唑-4, 7-二（伸乙基硼酸酯）、與2, 6_二溴 4— I二 基鲁環五[2，卜b;3,4-b，]_4吩之縮4Γ9，^酿 正辛基第-2, 7-二(伸乙基硼酸酯）、盘5 γ ^ /、心 ο -二溴—2, 2’ - 聯噻吩之縮合物等。 有機半導體之形成，例如可藉由對有機半導體化合物 視需要添加溶劑等以調製有機半導體塗佈液，將該有=半 導體塗佈液塗佈於閘極絕緣層上’使該有機半導=塗^ 乾燥來進行。於本發明，構成閘極絕緣層之樹脂具有苯产， 而與有機半導體化合物有親和性。因此， /、 衣， 區土 - 藉由上述塗佈乾 燥法’於有機半導體與閘極絕緣層之間形成均一， 界面。 且平i一之 323900 54 201239046 有機半導體塗佈液所使用之溶劑，只要可溶解或分散 有機半導體者即可，並無特別限制，較佳為常壓下之沸點 為50至200°C之溶劑。 該溶劑之例，可舉例如氯仿、曱苯、苯甲醚、2-庚酮、 丙二醇單曱醚乙酸酯。該有機半導體塗佈液，與上述絕緣 層塗佈液同樣地可藉旋塗法、模塗機、網版印刷、喷墨等 周知之方法塗佈於閘極絕緣層上。 本發明之有機薄膜電晶體，於保護有機薄膜電晶體、 或提高表面之平滑性的目的下，亦可以保護材料塗敷。 使用本發明之有機薄膜電晶體絕緣層材料所製造之 絕緣層，於其上可積層平坦之膜等，可容易地形成積層結 構。又，於該絕緣層上亦可搭載有機電激發光元件。 使用本發明之有機薄膜電晶體絕緣層材料，可製作具 有較佳之有機薄膜電晶體之顯示器用構件。使用具有該有 機薄膜電晶體之顯示器用構件，可製作具備顯示器用構件 之顯示器。 本發明之有機薄膜電晶體絕緣層材料，亦可使用於形 成絕緣層以外之電晶體所含之層、有機電激發光元件所含 之層的用途。 實施例 以下，以實施例說明本發明，但本發明並不限於實施 例。 合成例1 (高分子化合物1之合成） 323900 55 201239046 於50ml耐壓容器（Ace製）中置入笨乙烯（和光純藥 製）1. 88g、2, 3, 4, 5, 6-五氟苯乙烯（Aldrich 製）l. 5〇g、甲 基丙烯酸2-羥基乙酯（Aldrich製）2· 01g、2-(〇-[i，_甲其 亞丙基胺基]叛基胺基）乙基-曱基丙稀酸g旨（昭和電工製， 商品名「KarenzMOI-BM」）2. 47g、2, 2’ -偶氮雙（2-甲基丙 腈）〇.〇4g、1，4-二噚烷（和光純藥製）18.43g,以氬氣起泡 後，密栓，於60°C之油浴中聚合20小時。聚合結束後， 將反應混合物移置安裝有三通旋塞之200ml的三口燒瓶 中’將1,4-二噚烷30ml、攪拌子置入燒瓶内後，將燒槪 内之氣體以氮取代。於燒瓶内，加入曱基丙烯酸（和光純藥 製）1. 47g、N，Ν’ -二環己基碳二醯亞胺（和光純藥製） 3. 53g、觸媒量之4-二曱基胺基吡啶（和光純藥製），於氮 環境下攪拌24小時使其反應。反應結束後，將析出物過濾 取出，將濾液以異丙醇再沉澱，進行真空乾燥而製得高分 子化合物1。高分子化合物1具有下述重複單元。括弧旁 之數字表示重複單元之莫耳分率。Classes, polyallylamines, anthraquinones, polycarbazoles, poly-called W 71 wood Lai, poly (Dong + floc; alkene) and the like. Also, you have solubility in organic solvents. - a knife, for example, a polycyclic aromatic derivative such as condensed pentabenzene, a phthalocyanine derivative, an anthracene derivative, a tetrathiafulvalene derivative, tetracyanate quinone (tetracyanoquinodimethane) derivatives, fullerene (plus 1), carbon nanotubes, and the like. Specifically, for example, 2, 丨3~ stupid ==6-azole-4,7-di(ethylethyl borate), and 2,6-dibromo-4-didiruthene-5 [2] , b b; 3, 4-b,] _4 之 Γ 4Γ9, ^ brewing n-octyl-2, 7-di (extended ethyl borate), disk 5 γ ^ /, heart ο - dibromo - a condensate of 2, 2'-bithiophene, and the like. For the formation of the organic semiconductor, for example, an organic semiconductor coating liquid can be prepared by adding a solvent or the like to the organic semiconductor compound, and the semiconductor coating liquid can be applied to the gate insulating layer to make the organic semiconductor semiconducting coating. ^ Dry to carry out. In the present invention, the resin constituting the gate insulating layer has a benzene production and has affinity with an organic semiconductor compound. Therefore, /, clothing, and soil - by the above-described coating drying method, a uniform interface is formed between the organic semiconductor and the gate insulating layer. Further, the solvent used in the organic semiconductor coating liquid is not particularly limited as long as it can dissolve or disperse the organic semiconductor, and is preferably a solvent having a boiling point of 50 to 200 ° C under normal pressure. . Examples of the solvent include chloroform, toluene, anisole, 2-heptanone, and propylene glycol monoterpene ether acetate. The organic semiconductor coating liquid can be applied to the gate insulating layer by a spin coating method, a die coater, screen printing, or ink jet method in the same manner as the above-described insulating layer coating liquid. The organic thin film transistor of the present invention can also protect the material coating for the purpose of protecting the organic thin film transistor or improving the smoothness of the surface. The insulating layer produced by using the organic thin film transistor insulating layer material of the present invention can have a flat film or the like laminated thereon, and a laminated structure can be easily formed. Further, an organic electroluminescence element may be mounted on the insulating layer. Using the organic thin film transistor insulating layer material of the present invention, a member for a display having a preferred organic thin film transistor can be produced. A display member having a member for display can be produced by using a member for a display having the organic thin film transistor. The organic thin film transistor insulating layer material of the present invention can also be used for forming a layer contained in a transistor other than the insulating layer or a layer included in the organic electroluminescent device. EXAMPLES Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. Synthesis Example 1 (Synthesis of Polymer Compound 1) 323900 55 201239046 Into a 50 ml pressure vessel (made by Ace), stupid ethylene (manufactured by Wako Pure Chemical Industries, Ltd.) was placed 1. 88 g, 2, 3, 4, 5, 6-pentafluoro Styrene (manufactured by Aldrich) 1.5 g, 2-hydroxyethyl methacrylate (manufactured by Aldrich) 2·01 g, 2-(〇-[i,_methylideneamino group] tetamine group) Ethyl-mercapto-acrylic acid g (product name "Karenz MOI-BM", manufactured by Showa Denko) 2. 47g, 2, 2'-azobis(2-methylpropionitrile) 〇.〇4g, 1, 18.43 g of 4-dioxane (manufactured by Wako Pure Chemical Industries, Ltd.), foamed with argon, and then condensed in a 60 ° C oil bath for 20 hours. After the completion of the polymerization, the reaction mixture was placed in a 200 ml three-necked flask equipped with a three-way cock. After placing 30 ml of 1,4-dioxane and a stirrer into the flask, the gas in the crucible was replaced with nitrogen. 1. 47g, N, Ν'-dicyclohexylcarbodiimide (made by Wako Pure Chemical Industries Co., Ltd.) 3. 53g, catalyst amount of 4-dimercapto group Aminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.) was stirred under a nitrogen atmosphere for 24 hours to cause a reaction. After completion of the reaction, the precipitate was taken out by filtration, and the filtrate was reprecipitated with isopropyl alcohol and vacuum dried to obtain a polymer compound 1. The polymer compound 1 has the following repeating unit. The number next to the brackets indicates the molar fraction of the repeating unit.

高分子化合物1 201239046Polymer compound 1 201239046

所得之高分子化合物1之由標準聚苯乙烯所求得之重 量平均分子量為106000(島津製GPC，Tskgel super HM-H 一根+ Tskgel super H2000 — 根，移動相= THF)。 合成例2 (高分子化合物2之合成） 於50ml耐壓容器（Ace製）中置入2, 3, 4, 5, 6-五氟苯 乙烯（Aldrich製）5· 00g、4-胺基苯乙烯（東京化成製） 2. 04g、2, 2’ -偶氮雙（2-曱基丙腈）〇. 〇4g、1，4-二噚烷（和 光純藥製）16. 52g，以氬氣起泡後，密栓，於601：之油浴 中聚合20小時。聚合結束後，將反應混合物移置安裝有三 通旋塞之200ml的三口燒瓶中，將ι，4-二曙烷30ml、攪 拌子置入燒瓶内後，將燒瓶内之氣體以氮取代。於燒瓶内， 加入甲基丙烯酸（和光純藥製）〇. 37g、N，N，-二環己基碳二 醯亞胺（和光純藥製）〇. 86g、觸媒量之4-二甲基胺基吡啶 (和光純藥製），於氮環境下攪拌24小時使其反應。反應結 束後，將析出物過濾取出，再將濾出之析出物以丙二醇單 甲醚乙酸酯30ml洗淨3次。將所有濾液置入300ml之茄形 燒瓶，以旋轉蒸發器濃縮而製得高分子化合物2之丙二醇 單曱醚乙酸酯溶液。該溶液中之固體成分之濃度為18.3 重量％。高分子化合物2具有下述重複單元。括弧旁之數字 表示重複單元之莫耳分率。 323900 57 201239046The obtained polymer compound 1 had a weight average molecular weight of 106,000 as determined by standard polystyrene (GPC by Shimadzu, Tskgel super HM-H + Tskgel super H2000 - root, mobile phase = THF). Synthesis Example 2 (Synthesis of Polymer Compound 2) 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 5·00 g, 4-aminobenzene was placed in a 50 ml pressure vessel (manufactured by Ace). Ethylene (manufactured by Tokyo Chemical Industry Co., Ltd.) 2. 04g, 2, 2'-azobis(2-mercaptopropionitrile) 〇. 4g, 1,4-dioxane (made by Wako Pure Chemical Industries Co., Ltd.) 16. 52g, argon After the gas was bubbled, the plug was condensed and polymerized in an oil bath of 601: 20 hours. After the completion of the polymerization, the reaction mixture was placed in a 200 ml three-necked flask equipped with a three-way cock, and 30 ml of iota, 4-dioxane and a stirrer were placed in a flask, and the gas in the flask was replaced with nitrogen. In the flask, methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added. 37 g, N, N,-dicyclohexylcarbodiimide (manufactured by Wako Pure Chemical Industries, Ltd.) 86 86 g, catalyst amount of 4-dimethyl group Aminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.) was stirred under a nitrogen atmosphere for 24 hours to cause a reaction. After the completion of the reaction, the precipitate was filtered off, and the precipitate which was filtered off was washed three times with 30 ml of propylene glycol monomethyl ether acetate. All the filtrates were placed in a 300 ml eggplant-shaped flask and concentrated by a rotary evaporator to obtain a polymer compound 2 propylene glycol monoterpene ether acetate solution. The concentration of the solid component in the solution was 18.3% by weight. The polymer compound 2 has the following repeating unit. The number next to the bracket indicates the molar fraction of the repeating unit. 323900 57 201239046

高分子化合物2 ΤΙPolymer compound 2 ΤΙ

所得之高分子化合物2之由標準聚苯乙稀所求得之重 量平均分子量為112000(島津製GPC，Tskgel super ημ_η 一根+ Tskgel super Η2000 — 根’移動相=thf)。 合成例3 (化合物3的合成） 於置入有水阱（water trap)、攪拌子之5〇〇ml茄形燒 瓶中，置入1-環己烯-1,2-二羧酸酐（東京化成製）25g、3-胺基丙醇12g、甲苯200ml，於油浴中以14〇。(：反應4小時。 反應結束後，將反應混合物以旋轉蒸發器濃縮，加入二乙 醚（和光純藥製）l〇〇ml。將所得之二***溶液移置分液漏 斗，以破酸納水溶液洗淨後，將水層水洗至中性為止’進 行分液。將有機層以無水硫酸鎂乾燥後，將固體成分過滤 取出，將濾液以旋轉蒸發器濃縮，製得黃褐色之黏_狀液 體之化合物3。The obtained polymer compound 2 had a weight average molecular weight of 112,000 as determined by standard polystyrene (GPC, Tskgel super ημ_η + Tskgel super Η 2000 - root moving phase = thf). Synthesis Example 3 (Synthesis of Compound 3) In a 5 〇〇ml eggplant-shaped flask in which a water trap and a stir bar were placed, 1-cyclohexene-1,2-dicarboxylic anhydride was placed (Tokyo Chemical Co., Ltd.) 25 g, 3-aminopropanol 12 g, toluene 200 ml, 14 liters in an oil bath. (: The reaction was carried out for 4 hours. After the reaction was completed, the reaction mixture was concentrated on a rotary evaporator, and diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the obtained diethyl ether solution was transferred to a separatory funnel to dissolve the aqueous sodium chloride solution. After washing, the aqueous layer was washed with water until neutral. The organic layer was dried over anhydrous magnesium sulfate, and then the solid component was filtered, and the filtrate was concentrated on a rotary evaporator to obtain a yellow-brown viscous liquid. Compound 3.

化合物3 323900 58 201239046 (化合物4的合成） 於安裝有三通旋塞之1L的三口燒瓶中，置入2618g 化合物3、甲基丙稀酸11.31g、N，N，-二環己基碳二醯亞 胺（和光純藥製）27. l〇g、觸媒量之4-二曱基胺基处咬（和 光純藥製）、1，4-二嗜烷400ml，於氮環境下擾掉^ 口 使其反應。 μ# 反應結束後，將析出物過濾取出，將渡液以 器濃縮’加入二乙越（和光純藥製）10〇m 1。將所棋少_ 、 又一^乙喊 至中性為止，進行分液。 溶液移置分液漏斗，以碳酸鈉水溶液洗淨後，將水_ &先 將有機層以無水硫酸鎂乾燥後，將固體成分過歲 出，將濾液以旋轉蒸發器濃縮，製得黃褐色之點祠狀$ 之化合物4。Compound 3 323900 58 201239046 (Synthesis of Compound 4) In a 1-L three-necked flask equipped with a three-way cock, 2618 g of compound 3, methyl propylene diacid 11.31 g, N,N,-dicyclohexylcarbodiimide were placed. (made by Wako Pure Chemical Industries) 27. l〇g, the amount of catalyst 4-bittylamine group bite (made by Wako Pure Chemical Industries), 1,4-dioxane 400ml, disturbed in the nitrogen environment Its reaction. After the completion of the reaction, the precipitate was filtered and taken out, and the liquid was concentrated by the apparatus to be added to DM 2 (manufactured by Wako Pure Chemical Industries, Ltd.) at 10 〇m 1 . Put the less _, and the other ^ y to the neutral, and dispense. The solution was transferred to a separatory funnel, washed with an aqueous solution of sodium carbonate, and then the organic layer was dried over anhydrous magnesium sulfate, and then the solid portion was passed over the mixture, and the filtrate was concentrated on a rotary evaporator to obtain a tan. Point the compound 4 of $.

SsX〇 〇 化合物4 (高分子化合物5之合成） 於50ml耐壓容器（Ace製）中置入2, 3, 4,5, 6〜五氣苯 乙烯（Aldrich製）2. 00g、胺基苯乙烯（東京化成製） (K82g、2-(0-[Γ -曱基亞丙基胺基]羧基胺基）乙基〜甲基 丙烯酸酯（昭和電工製，商品名「KarenzMOI-BM」）i. 65g、 2.86g化合物4、2,2，-偶氮雙（2-曱基丙腈）0.〇4g、丙二 醇單曱醚乙酸酯（和光純藥製）Π· ng ’以氬氣起泡後，密 323900 59 201239046 栓。於60 C之油浴中聚合20小時，製得溶解有高分子化 合物5之黏稠之丙二醇單曱醚乙酸酯溶液。高分子化合物 5具有下述重複單元。括弧旁之數字表示重複單元之莫耳 分率。00克,胺苯苯。 The SsX 〇〇 compound 4 (the synthesis of the polymer compound 5) in a 50ml pressure vessel (made from Ace) placed 2, 3, 4, 5, 6 ~ five gas styrene (made by Aldrich) 2. 00g, aminobenzene Ethylene (manufactured by Tokyo Chemical Industry Co., Ltd.) (K82g, 2-(0-[Γ-mercaptopropylamino)carboxyamino)ethyl-methacrylate (manufactured by Showa Denko, trade name "KarenzMOI-BM") i 65g, 2.86g of compound 4, 2, 2, - azobis(2-mercaptopropionitrile) 0. 〇 4g, propylene glycol monoterpene ether acetate (made by Wako Pure Chemical Industries, Ltd.) Π · ng 'from argon After foaming, 323900 59 201239046 plug was polymerized in an oil bath of 60 C for 20 hours to obtain a viscous propylene glycol monoterpene ether acetate solution in which the polymer compound 5 was dissolved. The polymer compound 5 had the following repeating unit. The number next to the brackets indicates the molar fraction of the repeating unit.

高分子化合物5 所得之高分子化合物5之由標準聚苯乙烯所求得之重 量平均分子量為50000(島津製GPC，Tskgel super HM-H 一根+ Tskgel super H2000 — 根，移動相=THF)。 合成例4 (高分子化合物6的合成） 於含有2，1，3-苯并噻二唑-4, 7-二（伸乙基硼酸酯） 1. 88g、及 2, 6-二溴-(4, 4-雙-十六醯基-4H-環五[2, Ι-b ; 3, 4-b’ ]-二噻吩3. 81g之曱笨（80mL)中，於氮氣下，加入 肆（三苯膦）鈀〇.75g、曱基三辛基鋁氣化物（Aldrich製， 商品名「Aliquat 336」（註冊商標））1. 〇g、及2M之碳酸納 水溶液24mL。將該混合物劇烈地攪拌，並加熱回流24小 時。將黏稍之反應混合物注入丙酮50 OniL中，使纖維狀之 323900 60 201239046 黃色之聚合物沉澱。藉由過濾收集兮取 於真空烘箱中以6 (TC乾燥-晚。將;;：：物’以㈣洗淨， 子化合物6。高分子化合物6具有下、^之聚合物稱為高分 複單元之數目。 處重複單心表示重The polymer compound 5 obtained from the polymer compound 5 had a weight average molecular weight of 50,000 (standard GPC, Tskgel super HM-H + Tskgel super H2000 - root, mobile phase = THF). Synthesis Example 4 (Synthesis of Polymer Compound 6) Containing 2,1,3-benzothiadiazole-4,7-di(ethylethyl borate) 1.88 g, and 2,6-dibromo- (4,4-bis-hexadecanoyl-4H-cyclopenta[2, Ι-b; 3, 4-b']-dithiophene 3. 81g of scorpion (80mL), added under argon (triphenylphosphine) palladium rhodium. 75 g, decyl trioctyl aluminum vapor (manufactured by Aldrich, trade name "Aliquat 336" (registered trademark)) 1. 〇g, and 2M aqueous sodium carbonate solution 24 mL. Stir and heat under reflux for 24 hours. Inject the viscous reaction mixture into acetone 50 OniL to precipitate the fibrous 323900 60 201239046 yellow polymer. Collect it by vacuum and extract it in a vacuum oven to 6 (TC dry - Late; will;;:: the object 'washed with (4), sub-compound 6. The polymer compound 6 has the number of polymers, which are called high-resolution complex units.

所得之高分子化合物6之由標準聚苯乙烯所求得之重 量平均分子量為32000(島津製GPC，Tskgei super HM-H 一根+ Tskgel super H2000 — 根，移動相=THF)。 實施例1 (有機薄膜電晶體絕緣層材料及電場效應型有機薄膜電晶 體之製造） 於10ml之樣品瓶中置入〇.20g合成例1所得之高分 子化合物1、合成例2所得之活性氳化合物之高分子化合 物2之丙二醇單曱醚乙酸酯溶液〇.73g、IRGACURE 907C昭 和電工製）0. 033g、丙二醇單甲醚乙酸酯2. 00g， 一邊攪拌一邊使其溶解，調製成含有有機薄膜電晶體絕緣 層材料之均勻的塗佈溶液1。The weight average molecular weight of the obtained polymer compound 6 obtained from standard polystyrene was 32,000 (GPC by Shimadzu, Tskgei super HM-H + Tskgel super H2000 - root, mobile phase = THF). Example 1 (Production of organic thin film transistor insulating layer material and electric field effect type organic thin film transistor) Into a 10 ml sample bottle, 20 g of the polymer compound obtained in Synthesis Example 1 and the active hydrazine obtained in Synthesis Example 2 were placed. The propylene glycol monoterpene ether acetate solution of the polymer compound 2 of the compound 73. 73 g, IRGACURE 907C, manufactured by Showa Denko, 0. 033 g, propylene glycol monomethyl ether acetate, 2.00 g, dissolved while stirring, and prepared to contain A uniform coating solution 1 of an organic thin film transistor insulating layer material.

IRGACURE 907 323900 61 201239046 將所得之塗佈溶液1使用孔徑0. 2//m之膜過據器進 行過濾，旋塗於鉻電極所附有之玻璃基板上後，於加熱板 上以100C乾综1分知。之後，使.用對準器（Canon製； PLA-521)照射1600mJ/cm之UV光（波長365nm)後’於氮氣 中，於加熱板上以200°C燒成30分鐘製得閘極絕緣層。 接著，以溶劑之一甲本溶解高分子化合物6，製作成 濃度為0_ 5重量％之溶液（有機半導體組成物），將其以膜過 濾器過濾調製成塗佈液。 將所得之塗佈液，以旋塗法塗佈於上述閘極絕緣層 上，形成具有約30nm厚度之活性層，接著，以使用金屬遮 罩之真空蒸鍍法，於活性層上，形成通道長2〇#m、通道 寬2mm之源極電極及汲極電極（具有由活性層侧起以氧化 鉬、金之順序之積層結構），藉此製作成電場效應型有機薄 膜電晶體1。 實施例2 (有機薄膜電晶體絕緣層材料及電場效應型有機薄膜電晶 體之製造） 於l〇ml之樣品瓶中置入〇. 5〇g合成例丨所得之高分 子化合物1、合成例2所得之活性氫化合物之高分子化合 物2之丙二醇單甲醚乙酸酯溶液L 82g、合成例3所得之 高分子化合物5之丙二醇單曱醚乙酸酯溶液〇 83g、丙二 醇單甲謎乙_ 5. 48g…邊麟-邊使其溶解，調製成 含有有機薄膜電晶體絕緣層材料之均勻的塗佈溶液2。 將所知之塗佈溶液2使用孔徑〇 · 2以m之膜過滤器進 323900 62 201239046 行過渡，旋塗於鉻電極所附有之玻璃基板上後，於加熱板 上以100。(：乾燥1分鐘。之後，使用對準器（canon製； PLA-521)照射i6〇〇mj/cm2之UV光（波長365nm)後，於氮氣 中’於加熱板上以2〇〇。(：燒成30分鐘製得閘極絕緣層。 接著，與實施例1同樣地形成活性層、源極電極及汲 極電極而製作成電場效應型有機薄膜電晶體2。 &lt;電晶體特性之評價&gt; 對如此所製作之電場效應型有機薄膜電晶體1及電場 效應型有機薄膜電晶體2,以使閘極電壓Vg於20至-40V、 源極/汲極間電壓Vsd於0至-40V變化的條件，使用真空 探測器（BCT2 2MDC-5-HT-SCU;Nagase Electronic Equipments Service Co.，LTD製）測定其電晶體特性。將結果示於表1。 電場效應型有機薄膜電晶體之磁滯係以源極/汲極間 電壓Vsd在-40V，使閘極電壓Vg由20V—-40V變化時之臨 限電壓Vthl與閘極電壓Vg由-40V—20V變化時之臨限電 壓Vth2之電壓差來表示。 比較例1 (電場效應型有機薄膜電晶體之製造） 於10ml之樣品瓶中置入聚乙烯酚-共-聚曱基丙烯酸曱 酯（Aldrich 製，Mn=6700)1.00g、N，N，N，，N，，N”，N” -六曱氧基曱基矽烷（住友化學製）0. 163g、熱酸產生劑（綠化 學（股）製，商品名：TAZ-108)0. 113g、2-庚酮7. 00g，攪 拌溶解以調製成均勻之塗佈溶液3。 使用塗佈溶液3取代塗佈溶液1，於閘極絕緣層之形 323900 63 201239046 成時不進行UV照射，除此之外，與實施例1同樣地製作電 場效應型有機薄膜電晶體3，測定電晶體特性，評價的閘 極電壓Vg在20V-^-40V之區域，電晶體未動作。 [表1] 磁滯 Vthl 實施例1 1. IV 0. 9V 實施例2 0. 0V 9. 8V 比較例1 未動作 【圖式簡單說明】 第1圖係顯示本發明之一實施形態之下閘極上接觸型 有機薄膜電晶體之構造的模式截面圖。 第2圖係顯示本發明之其他實施形態之下閘極下接觸 型有機薄膜電晶體之構造的模式截面圖。 【主要元件符號說明】 1 基板 2 閘極電極 3 閘極絕緣層 4 有機半導體層 5 源極電極 6 汲極電極 7 保護層 323900 64IRGACURE 907 323900 61 201239046 The obtained coating solution 1 was filtered using a membrane filter having a pore diameter of 0.2/m, spin-coated on a glass substrate attached to a chromium electrode, and dried on a hot plate at 100 C. 1 point know. Thereafter, an aligner (manufactured by Canon; PLA-521) was used to irradiate 1600 mJ/cm of UV light (wavelength 365 nm), and then burned at 200 ° C for 30 minutes on a hot plate in a nitrogen atmosphere to obtain a gate insulation. Floor. Then, the polymer compound 6 was dissolved in one of the solvents to prepare a solution (organic semiconductor composition) having a concentration of 0 to 5% by weight, which was filtered into a coating liquid by a membrane filter. The obtained coating liquid is applied onto the gate insulating layer by spin coating to form an active layer having a thickness of about 30 nm, and then a channel is formed on the active layer by vacuum evaporation using a metal mask. The electric field effect type organic thin film transistor 1 was fabricated by a source electrode having a length of 2 m and a source electrode having a channel width of 2 mm and a gate electrode having a laminated structure in the order of molybdenum oxide and gold from the active layer side. Example 2 (Production of organic thin film transistor insulating layer material and electric field effect type organic thin film transistor) 高分子. 5 〇g of the polymer compound obtained in the synthesis example, Synthesis Example 2 Propylene glycol monomethyl ether acetate solution L 82g of the polymer compound 2 of the obtained active hydrogen compound, propylene glycol monoterpene ether acetate solution of the polymer compound 5 obtained in Synthesis Example 3, 83 g, propylene glycol monomethyl _ 5 48 g...Blank-Lin was dissolved to prepare a uniform coating solution 2 containing an organic thin film transistor insulating layer material. The known coating solution 2 was transferred using a membrane filter of pore size 〇 2 in m, 323900 62 201239046, spin-coated on a glass substrate attached to the chromium electrode, and then placed on the heating plate at 100. (: Drying for 1 minute. Thereafter, an aligner (manufactured by Canon Co.; PLA-521) was used to irradiate i6 〇〇mj/cm2 of UV light (wavelength 365 nm), and then, under nitrogen, was placed on a hot plate at 2 Torr. The gate insulating layer was obtained by firing for 30 minutes. Next, an active layer, a source electrode, and a gate electrode were formed in the same manner as in Example 1 to prepare an electric field effect type organic thin film transistor 2. <Evaluation of Transistor Characteristics &gt; The electric field effect type organic thin film transistor 1 and the electric field effect type organic thin film transistor 2 thus produced are such that the gate voltage Vg is 20 to -40 V, and the source/drain voltage Vsd is 0 to -40 V The conditions of the change were measured using a vacuum detector (BCT2 2MDC-5-HT-SCU; manufactured by Nagase Electronic Equipments Service Co., LTD.). The results are shown in Table 1. Magnetic field effect type organic thin film transistor The hysteresis voltage Vsd at the source/drain voltage Vsd is -40V, and the threshold voltage Vth1 when the gate voltage Vg is changed from 20V to -40V and the threshold voltage Vth2 when the gate voltage Vg is changed from -40V to 20V The voltage difference is shown. Comparative Example 1 (Manufacture of electric field effect type organic thin film transistor) in 10 ml The sample vial was filled with polyvinylphenol-co-poly(decyl methacrylate) (manufactured by Aldrich, Mn=6700) 1.00 g, N,N,N,,N,,N",N"-hexamethoxy oxime Base decane (manufactured by Sumitomo Chemical Co., Ltd.) 0. 163g, hot acid generator (manufactured by Green Chemical Co., Ltd., trade name: TAZ-108) 0. 113g, 2-heptanone 7. 00g, stirred and dissolved to prepare a uniform coating The cloth solution solution 3. The electric field effect type organic thin film electric power was produced in the same manner as in the first embodiment except that the coating solution 3 was used instead of the coating solution 1 in the form of the gate insulating layer 323900 63 201239046. Crystal 3, the transistor characteristics were measured, and the evaluated gate voltage Vg was in the region of 20 V - - 40 V, and the transistor was not operated. [Table 1] Hysteresis Vthl Example 1 1. IV 0. 9V Example 2 0. 0V 9. 8V Comparative Example 1 Not Operating [Simplified Schematic Description] Fig. 1 is a schematic cross-sectional view showing the structure of a gate-contacting organic thin film transistor according to an embodiment of the present invention. Fig. 2 is a view showing the present invention. A schematic cross-sectional view of the structure of a gate-under contact type organic thin film transistor under other embodiments. ] 1 substrate 2 gate electrode 3 gate insulating layer 4, an organic semiconductor layer 5 source electrode 6 drain electrode protective layer 7 32390064

Claims (1)

201239046 七、申請專利範圍： 1. 一種有機薄膜電晶體絕緣層材料，係含有高分子化合物 (A)，該高分子化合物（A)含有式（1)所表示之官能基及 2個以上之第1官能基，201239046 VII. Patent application scope: 1. An organic thin film transistor insulating layer material containing a polymer compound (A) containing a functional group represented by formula (1) and two or more 1 functional group, [式中，R!表示氫原子或曱基] 該第1官能基係藉由電磁波或熱的作用，而生成與 活性氫反應之第2官能基之官能基。 2.如申請專利範圍第1項所述之有機薄膜電晶體絕緣層 材料，其中，上述高分子化合物（A)進一步含有式（2) 所表示之重複單元，[In the formula, R! represents a hydrogen atom or a thiol group] The first functional group is a functional group which generates a second functional group which reacts with active hydrogen by the action of electromagnetic waves or heat. 2. The organic thin film transistor insulating layer material according to claim 1, wherein the polymer compound (A) further contains a repeating unit represented by the formula (2). [式中，R2表示氫原子或曱基；R表示氫原子或碳 數1至20之一價之有機基；Rf表示氟原子或具有氟原 子之碳數1至20之一價之有機基；Raa表示連結高分子 323900 1 201239046 化合物之主鏈與側鏈之可具有氟原子之連結部分；U表 示0或1之整數，b表示1至5之整數；當R為複數個 時，該等可為相同或相異；當Rf為複數個時，該等可 為相同或相異]。 3. 如申請專利範圍第1或2項所述之有機薄膜電晶體絕緣 層材料，其中，上述第1官能基係選自以封端劑 (blocking agent)封端之異氰酸醋基及以封端劑封端 之異硫氰酸基（isothiocyanato)所構成群中之至少1 種基。 4. 如申請專利範圍第3項所述之有機薄膜電晶體絕緣層 材料，其中，上述以封端劑封端之異氰酸酯基及以封端 劑封端之異硫氰酸基，係式（3)所表示之基，Wherein R 2 represents a hydrogen atom or a fluorenyl group; R represents a hydrogen atom or an organic group having a carbon number of 1 to 20; and Rf represents a fluorine atom or an organic group having a fluorine atom having a carbon number of 1 to 20; Raa represents a linking moiety of a main chain and a side chain of a compound of the compound 323900 1 201239046 which may have a fluorine atom; U represents an integer of 0 or 1, and b represents an integer of 1 to 5; when R is plural, such They are the same or different; when Rf is plural, they may be the same or different]. 3. The organic thin film transistor insulating layer material according to claim 1 or 2, wherein the first functional group is selected from the group consisting of isocyanate groups blocked with a blocking agent and At least one group of the group consisting of isothiocyanato blocked by a blocking agent. 4. The organic thin film transistor insulating layer material according to claim 3, wherein the isocyanate group blocked with a blocking agent and the isothiocyanate group blocked with a blocking agent are used. ) the basis of the [式中，Xa表示氧原子或硫原子，R5及R6為相同或相異， 表示氫原子或碳數1至20之一價之有機基]。 5.如申請專利範圍第3項所述之有機薄膜電晶體絕緣層 材料，其中，以封端劑封端之異氰酸酯基及以封端劑封 端之異硫氰酸基，係式（4)所表示之基， 323900 2 201239046[wherein, Xa represents an oxygen atom or a sulfur atom, and R5 and R6 are the same or different, and represent a hydrogen atom or an organic group having a carbon number of 1 to 20]. 5. The organic thin film transistor insulating layer material according to claim 3, wherein the isocyanate group blocked with a blocking agent and the isothiocyanate group blocked with a blocking agent, (4) The basis of the representation, 323900 2 201239046 (4) [式中，Xb表示氧原子或硫原子，R?至匕為相同或 相異，表示氫原子或碳數1至20之一價之有機基]。 6. 如申請專利範圍第1至5項中任一項所述之有機薄膜電 晶體絕緣層材料，其中，上述高分子化合物（A)進一步 含有2個以上之具有1個活性氫之構造單元、或具有2 個以上活性氫之構造單元。 7. 如申請專利範圍第1至6項中任一項所述之有機薄膜電 晶體絕緣層材料，進一步含有選自屬於含有2個以上活 性氫之低分子化合物之活性氫化合物、及屬於含有2 個以上活性氫之高分子化合物之活性氫化合物所構成 群中之至少1種活性氫化合物。 8. 如申請專利範圍第1至7項中任一項所述之有機薄膜電 晶體絕緣層材料，進一步含有選自含有2個以上式（6) 所表示之官能基之低分子化合物及含有含該官能基之重 複單元之高分子化合物所構成群中之至少1種化合物，(4) [wherein, Xb represents an oxygen atom or a sulfur atom, and R? to 匕 are the same or different, and represent a hydrogen atom or an organic group having a carbon number of 1 to 20]. The organic thin film transistor insulating layer material according to any one of claims 1 to 5, wherein the polymer compound (A) further contains two or more structural units having one active hydrogen, Or a structural unit with more than 2 active hydrogens. 7. The organic thin film transistor insulating layer material according to any one of claims 1 to 6, further comprising an active hydrogen compound selected from the group consisting of low molecular compounds containing two or more active hydrogens, and containing 2 At least one active hydrogen compound in the group of active hydrogen compounds of the polymer compound of the above active hydrogen. The organic thin film transistor insulating layer material according to any one of claims 1 to 7, further comprising a low molecular compound selected from two or more functional groups represented by the formula (6) and containing At least one compound of the group consisting of the polymer compound of the repeating unit of the functional group, 323900 3 201239046 [式中，R3及R4分別獨立地表示氫原子或碳數i至2〇 之一價之有機基；該一價之有機基中之氫原子可經氟原 子取代；R3中之碳原子與R4中之碳原子亦可鍵結而形 成5員環或6員環]。 9. 一種有機薄膜電晶體絕緣層之形成方法，係包含下述步 驟： 將含有申請專利範圍第1至8項中任一項所述之有 機薄膜電晶體絕緣層材料之液塗佈於基材，以於該基材 上形成塗佈層之步驟；以及 對該塗佈層照射電磁波或電子射線之步驟。 10. 一種有機薄膜電晶體絕緣層之形成方法，係包含下述步 驟： +將含有申請專利範圍第1至8項中任一項所述之有 機薄膜電晶體絕緣層材料之液塗佈於基材，以於該基材 上形成塗佈層之步驟； 對該塗佈層照射電磁波或電子射線之步驟；以及 對該塗佈層施加熱之步驟。 如申請專㈣圍第9或1G項所述之有機薄膜電晶體絕 緣層之形成方法，其中，上述電磁波係紫外線。 種有機薄膜電晶體，係具有使用中請專利範圍第1 至8項中任一項所述之有機薄膜電晶體絕緣層材料所 形成之有機薄臈電晶體絕緣層。 13·如申請專利範圍第12項所述之有機薄膜電晶體，其 中，上述有機薄膜電晶體絕緣層為閘極絕緣層。 323900 4 201239046 14. 一種顯示器用構件，係含有申請專利範圍第12或13 項所述之有機薄膜電晶體。 15. —種顯示器，係含有申請專利範圍第14項所述之顯示 器構件。 323900 5323900 3 201239046 [wherein R3 and R4 each independently represent a hydrogen atom or an organic group having a carbon number of i to 2 Å; a hydrogen atom in the monovalent organic group may be substituted by a fluorine atom; a carbon in R3 The atom and the carbon atom in R4 may also be bonded to form a 5-membered ring or a 6-membered ring]. A method of forming an organic thin film transistor insulating layer, comprising the steps of: applying a liquid containing the organic thin film transistor insulating layer material according to any one of claims 1 to 8 to a substrate And a step of forming a coating layer on the substrate; and irradiating the coating layer with electromagnetic waves or electron beams. A method of forming an organic thin film transistor insulating layer, comprising the steps of: coating a liquid containing the organic thin film transistor insulating layer material according to any one of claims 1 to 8; a step of forming a coating layer on the substrate; a step of irradiating the coating layer with electromagnetic waves or electron beams; and a step of applying heat to the coating layer. The method for forming an organic thin film transistor insulating layer according to Item 9 or 1G, wherein the electromagnetic wave is ultraviolet light. The organic thin film transistor is an organic thin germanium transistor insulating layer formed by using the organic thin film transistor insulating layer material according to any one of claims 1 to 8. The organic thin film transistor according to claim 12, wherein the organic thin film transistor insulating layer is a gate insulating layer. 323900 4 201239046 14. A member for display comprising the organic thin film transistor of claim 12 or 13. 15. A display comprising the display member of claim 14 of the patent application. 323900 5
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