TW201031687A - Underlayer film for forming image - Google Patents

Underlayer film for forming image Download PDF

Info

Publication number
TW201031687A
TW201031687A TW098135951A TW98135951A TW201031687A TW 201031687 A TW201031687 A TW 201031687A TW 098135951 A TW098135951 A TW 098135951A TW 98135951 A TW98135951 A TW 98135951A TW 201031687 A TW201031687 A TW 201031687A
Authority
TW
Taiwan
Prior art keywords
film
group
carbon atoms
formula
polyimine
Prior art date
Application number
TW098135951A
Other languages
Chinese (zh)
Other versions
TWI453235B (en
Inventor
Shinichi Maeda
Go Ono
Satoshi Minami
Original Assignee
Nissan Chemical Ind Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Ind Ltd filed Critical Nissan Chemical Ind Ltd
Publication of TW201031687A publication Critical patent/TW201031687A/en
Application granted granted Critical
Publication of TWI453235B publication Critical patent/TWI453235B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40Organic transistors
    • H10K10/46Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462Insulated gate field-effect transistors [IGFETs]
    • H10K10/468Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/471Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10Substrates, e.g. flexible substrates
    • H10K77/111Flexible substrates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78606Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
    • H01L29/78618Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device characterised by the drain or the source properties, e.g. the doping structure, the composition, the sectional shape or the contact structure
    • H01L29/78621Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device characterised by the drain or the source properties, e.g. the doping structure, the composition, the sectional shape or the contact structure with LDD structure or an extension or an offset region or characterised by the doping profile
    • H01L2029/7863Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device characterised by the drain or the source properties, e.g. the doping structure, the composition, the sectional shape or the contact structure with LDD structure or an extension or an offset region or characterised by the doping profile with an LDD consisting of more than one lightly doped zone or having a non-homogeneous dopant distribution, e.g. graded LDD
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Ceramic Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Thin Film Transistor (AREA)

Abstract

An underlayer film for image formation, which is characterized by containing a polyimide precursor having a repeating structure represented by formula (1) or a polyimide obtained by dehydration ring closing of the polyimide precursor. In the formula, A represents a tetravalent organic group, and B represents a divalent organic group represented by formula (2) or (3).

Description

201031687 六、發明說明: 【發明所屬之技術領域】 本發明係關於形成畫像用下層膜, 成畫像之下層膜製作之有機電晶體。 【先前技術】 目前,電子裝置之製造步驟中,對 Φ 性薄膜之圖型主要使用遮罩蒸鏟法或利 刻方法。該等以往之方法受被指出有基 步驟繁複等之問題點。 近年來,對於該等以往之方法,已 性之差異之分開塗佈技術應用於機能性 此係於板表面上製作由液體易潤濕之領 之領域所組成之圖型化層,接著,將形 之溶液塗佈於該圖型化層之上,並經乾 φ 濕之領域上形成機能性薄膜,而製作有 )元件或有機FET (電場效型電晶體) 之方法。 該等機能性薄膜用之圖型化層已知 氧化鈦與有機聚矽氧烷所構成之含光觸 而成者(例如參照專利文獻1 )、於由 收部位之化合物與含氟聚合物所構成之 過遮罩照射紫外光而成者(例如參照專 外,亦提出透過遮罩蒸鍍氟系塗覆劑而 進而關於使用該形 於形成電極或機能 用光微影蝕刻之蝕 板之大型化困難且 提出利用液體潤濕 薄膜之圖型化中。 域與液體不易潤濕 成機能性薄膜材料 燥,僅在液體易潤 機EL (電致發光 元件等之電子裝置 有透過遮罩於由二 媒層上照射紫外線 染料等之具有光吸 層上照射雷射或透 利文獻2 )等。另 形成上述圖型化層 -5- 201031687 之方法(例如參照專利文獻3 )。 上述專利文獻等截至目前爲止提出之圖型化層僅管達 成機能性薄膜之圖型化之角色,但在元件中仍殘存。因此 ,該圖型化層對於隨後步驟之耐久性及即使處於電子裝置 中亦不會對其特性造成不良影響之信賴性成爲必要。圖型 化層之該等必要特性係隨著所製作之圖型或圖型化層之使 用部位而不同,其中,電極之圖型化層之電絕緣性爲重要 之必要特性。 ^ 又,迄今爲止提出之方法僅將重點放在圖型化層之特 性上。因此,例如將有機FET元件之源極電極及汲極電 極圖型化時,必須在圖型化層之下方另外準備閘極絕緣膜 〇 另一方面,聚醯亞胺之耐熱性或機械強度、電絕緣性 、耐藥品性等優異而已使用於各式各樣之電子裝置中。使 用聚醯亞胺作爲圖型化層之例已揭示有使用具有脂環構造 之四羧酸酐者(例如參照專利文獻4)。然而’於該等之 ❹ 例由於紫外線之照射量極大,故不得不進行長時間的曝光 處理。 專利文獻1 :特開2000-223270號公報 專利文獻2 :特開20〇4-146478號公報 專利文獻3 :特開2〇〇4·273 8 5 1號公報 專利文獻4 ··特開2006- 1 85898號公報 【發明內容】 -6- 201031687 本發明係有鑑於該情況而完成者,本發明係提供一種 即使以少量的紫外線照射量,仍可容易地改變所形成之形 成畫像用下層膜之膜表面的親疏水性之形成畫像用下層膜 [用以解決課題之手段] 本發明者爲達成上述目的而重複積極檢討之結果,發 現藉由於聚醯亞胺前驅物或由該聚醯亞胺前驅物獲得之聚 醯亞胺之側鏈中含有硫醇酯構造,於由該聚醯亞胺前驅物 及聚醯亞胺獲得之硬化膜之表面上,可以少量之曝光量使 水接觸角變大,因而完成本發明。 亦即,本發明之第一觀點係關於一種形成畫像用下層 膜,其特徵爲含有以下述式(η表示之重複構造之聚醯 亞胺前驅物或使該聚醯亞胺前驅物脫水閉環所得之聚醯亞201031687 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an organic transistor produced by forming a lower layer film for an image and forming a film under the image. [Prior Art] At present, in the manufacturing steps of an electronic device, a masking method or a scribing method is mainly used for the pattern of the Φ film. These prior methods have been pointed out to have problems such as complex steps. In recent years, for these prior methods, the difference coating technique has been applied to the functional layer which is formed on the surface of the board to form a patterned layer composed of a field which is easily wetted by liquid, and then, A solution of the shape is applied to the patterned layer, and a functional film is formed on the dry φ wet field to produce a device or an organic FET (electric field effect transistor). The patterned layer for the functional film is known to contain a photo-contact with titanium oxide and an organic polyoxyalkylene (see, for example, Patent Document 1), a compound at a receiving portion, and a fluoropolymer. In the case where the mask is irradiated with ultraviolet light (for example, referring to the special purpose, it is also proposed to deposit a fluorine-based coating agent through the mask, and further to use a large-sized etching plate for forming an electrode or function photolithography. Difficulty and suggesting the use of a liquid wetting film in the patterning. The domain and the liquid are not easily wetted into a functional film material, only in the liquid emollient machine EL (electroluminescent device and other electronic devices have a transparent mask A method of irradiating a laser or a transparent article on a light-absorbing layer, such as a UV-ray dye, etc. 2), etc., and forming the above-described patterning layer-5-201031687 (for example, refer to Patent Document 3). The patterned layer proposed so far only fulfills the role of the patterning of the functional film, but remains in the component. Therefore, the patterned layer is durable to the subsequent steps and even in the electronic device. It is also necessary that the reliability of the characteristic is not adversely affected. The necessary characteristics of the patterned layer differ depending on the pattern used or the location of the patterned layer, wherein the patterning of the electrodes The electrical insulation of the layer is an important characteristic. ^ Also, the method proposed so far only focuses on the characteristics of the patterned layer. Therefore, for example, the source electrode and the drain electrode of the organic FET device are patterned. In addition, it is necessary to separately prepare a gate insulating film under the patterned layer. On the other hand, polyimine is excellent in heat resistance, mechanical strength, electrical insulating property, chemical resistance, etc., and has been used in various kinds of electrons. In the apparatus, the use of polyimine as a patterning layer has been disclosed using a tetracarboxylic anhydride having an alicyclic structure (for example, refer to Patent Document 4). However, in such cases, the amount of ultraviolet rays is extremely large. For this reason, it is necessary to carry out a long-term exposure process. Patent Document 1: JP-A-2000-223270 Patent Document 2: JP-A-2000-146478 Patent Document 3: Special Opening 2〇〇4·273 8 5 1 Bulletin patent document The present invention has been made in view of the above circumstances, and the present invention provides a method which can be easily changed even with a small amount of ultraviolet irradiation. The lower layer film for forming an image of the surface of the film on the surface of the underlayer film is formed. [The means for solving the problem] The present inventors have repeatedly reviewed the results of the above-mentioned objects and found that the polyimide precursor or The side chain of the polyimine obtained from the polyimine precursor contains a thiol ester structure, and can be exposed to a small amount on the surface of the cured film obtained from the polyimide precursor and the polyimide. The present invention has been completed in such a manner that the water contact angle becomes large, that is, the first aspect of the present invention relates to an underlayer film for forming an image, which is characterized by containing a polyimine precursor having a repetitive structure represented by the following formula (η) a polyphthalate obtained by dehydrating a ring of the polyimine precursor

[化1] R1OOC、/COOR2 -N 一 C 一A一C 一N一B I II II I Η Ο Ο ΗR1OOC, /COOR2 -N - C - A - C - N - B I II II I Η Ο Ο Η

(式中,Α表示4價有機基,Β表示以下述式(2)或(3 )表示之2價構造,R1、R2分別獨立表示氫原子或1價 有機基,η表示自然數); 201031687 [化2](wherein Α represents a tetravalent organic group, Β represents a divalent structure represented by the following formula (2) or (3), R1 and R2 each independently represent a hydrogen atom or a monovalent organic group, and η represents a natural number); 201031687 [Chemical 2]

(2) Ο S-C-X-Y-2(2) Ο S-C-X-Y-2

(式中’X表不單鍵或碳原子數6至20之2價芳香族基 ,Y 表示單鍵、-0-、-COO-、-oco-、-CONH-、_ch2o-、-ch2coo-或-ch2ch2coo-,Z表示可經氟原子取代之(wherein 'X is not a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y is a single bond, -0-, -COO-, -oco-, -CONH-, _ch2o-, -ch2coo- or -ch2ch2coo-, Z indicates that it can be replaced by a fluorine atom

碳原子數3至26之脂肪族烴基,R各獨立表示氟原子、 碳原子數1至3之烷氧基或碳原子數1至3之烷基,t表 示〇至3之整數)。 本發明之第二觀點係關於一種形成畫像用下層膜,其The aliphatic hydrocarbon group having 3 to 26 carbon atoms, R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 〇 to 3. A second aspect of the present invention relates to an underlayer film for forming an image,

特徵爲包含使含有以下述式(6)表示之四羧酸二酐之四 羧酸二酐成分與含有以式(7)表示之二胺之二胺成分反 應所得之聚醯亞胺前驅物,或使該聚醯亞胺前驅物脫水閉 環所得之聚醯亞胺: [化3] 0 〇The present invention is characterized in that it comprises a polyfluorene imine precursor obtained by reacting a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) with a diamine component containing a diamine represented by the formula (7). Or the polyimine obtained by dehydrating and ring-closing the polyimine precursor: [Chemical 3] 0 〇

(6) H2N—B—NH2 ( 7) [式中,A表示4價有機基’ B表示以式(2)或式(3) 表示之2價構造: 201031687 [化4] ο(6) H2N-B-NH2 (7) [wherein A represents a tetravalent organic group] B represents a divalent structure represented by the formula (2) or the formula (3): 201031687 [Chemical 4]

Z (R)t S-C-X—Υ—Ζ (R)t (式中,X表示單鍵或碳原子數6至20之2價芳香族基 ,Y 表示單鍵、-0-、-COO-、-OCO-、-CONH-、-CH20-' -ch2coo-或-ch2ch2coo-,z表示可經氟原子取代之 碳原子數3至26之脂肪族烴基’R各獨立表示氟原子、 碳原子數1至3之烷氧基或碳原子數1至3之烷基,t表 示〇至3之整數)]。 第三觀點係關於第一或第二觀點所述之形成畫像用下 層膜,其中式(2)或式(3)之Z表示任意氫原子經氟原 子取代之碳原子數3至26之脂肪族烴基。 第四觀點係關於第一觀點至第三觀點所述之形成畫像 用下層膜,其中 A表示具有脂肪族環或僅由脂肪族所構 成之4價有機基。 第五觀點係關於第一觀點至第四觀點任一項中所述之 形成畫像用下層膜,其中B表示以式(2)表示之2價構 造。 第六觀點係關於第一觀點至第五觀點中任一項所述之 形成畫像用下層膜,其中X及Y表示單鍵。 第七觀點係關於一種有機電晶體,其特徵爲含有第一 觀點至第六觀點中任一項所述之形成畫像下層膜。 第八觀點係關於一種以下述式(14)或下述式(15) -9 - 201031687 表示之二胺化合物, [化5]Z (R)t SCX—Υ—Ζ(R)t (wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, —0-, —COO—, - OCO-, -CONH-, -CH20-'-ch2coo- or -ch2ch2coo-, z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and each independently represents a fluorine atom and a carbon number of 1 to An alkoxy group of 3 or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 〇 to 3)]. The third aspect relates to the underlayer film for forming an image according to the first or second aspect, wherein Z of the formula (2) or the formula (3) represents an aliphatic group having 3 to 26 carbon atoms substituted by a fluorine atom of any hydrogen atom. Hydrocarbyl group. The fourth viewpoint is an underlayer film formed by the first to third aspects, wherein A represents a tetravalent organic group having an aliphatic ring or only an aliphatic group. The fifth aspect relates to an underlayer film for forming an image described in any one of the first to fourth aspects, wherein B represents a bivalent structure represented by the formula (2). The sixth aspect relates to the underlayer film for forming an image according to any one of the first to fifth aspects, wherein X and Y represent a single bond. The seventh aspect relates to an organic transistor characterized by comprising the image forming underlayer film according to any one of the first aspect to the sixth aspect. The eighth aspect relates to a diamine compound represented by the following formula (14) or the following formula (15) -9 - 201031687, [Chem. 5]

(式中,X表示單鍵或碳原子數6至20之2價芳香族基 ,Y 表示單鍵、-〇-、-COO-、-OCO-、-CONH-、-CH20-、-ch2coo -或- CH2CH2COO-,Z表示任意的氫原子經氟 原子取代之碳原子數3至26之脂肪族烴基’ R各獨立表 示氟原子、碳原子數1至3之烷氧基或碳原子數1至3之 烷基,t表示0至3之整數)。 第九觀點係關於一種聚醯亞胺,其含有以下述式(1 )表示之重複單位之聚醯亞胺前驅物或使該聚醯亞胺前驅 物脫水閉環所得,(wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -〇-, -COO-, -OCO-, -CONH-, -CH20-, -ch2coo - Or -CH2CH2COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted with a fluorine atom by any fluorine atom, and each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon number of 1 to An alkyl group of 3, t represents an integer of 0 to 3). The ninth aspect relates to a polyimine which contains a polyimine precursor of a repeating unit represented by the following formula (1) or which is obtained by dehydrating and ring-closing the polyimine precursor.

[化6][Chemical 6]

R1OOC /COOR2R1OOC /COOR2

-N-C-A-C-N-B I II II I HO OH (式中,A表示4價有機基,B表示以下述式(2a)或( 3a)表示之2價構造,R1、R2分別獨立表示氫原子或1 價有機基,η表示自然數); -10- 201031687 [化7]-NCACNB I II II I HO OH (wherein A represents a tetravalent organic group, and B represents a divalent structure represented by the following formula (2a) or (3a), and R1 and R2 each independently represent a hydrogen atom or a monovalent organic group; , η represents a natural number); -10- 201031687 [Chem. 7]

(式中,X表示單鍵或碳原子數6至20之2價芳香族基 ,Y 表示單鍵、-0·、-COO-、-OCO-、-CONH-、-CH20_(wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -0·, -COO-, -OCO-, -CONH-, -CH20_

、-ch2coo-或-ch2ch2coo-,Z表示任意的氫原子經氟 原子取代之碳原子數3至26之脂肪族烴基,R各獨立表 示氟原子、碳原子數1至3之烷氧基或碳原子數1至3之 烷基,t表示0至3之整數)。 第十觀點係關於一種形成畫像下層膜塗佈液,其特徵 爲包含使含有以下述式(6)表示之四羧酸二酐之四羧酸 二酐成分與含有以式(7)表示之二胺之二胺成分反應所 得之聚醯亞胺前驅物或使該聚醯亞胺前驅物脫水閉環所得 之聚醯亞胺: [化8], -ch2coo- or -ch2ch2coo-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or carbon. An alkyl group having 1 to 3 atoms, and t represents an integer of 0 to 3. The tenth aspect relates to a method for forming an image forming film of a lower layer, comprising a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and containing the formula (7). The polyimine precursor obtained by reacting the amine diamine component or the polyimine obtained by dehydrating and ring-closing the polyimine precursor: [Chem. 8]

(6) H2N-B-NH2 (7) (式中,A表示4價有機基,B表示以式(2)或式(3) 表不之2價構造: -11 - 201031687 [化9](6) H2N-B-NH2 (7) (wherein A represents a tetravalent organic group, and B represents a divalent structure represented by formula (2) or formula (3): -11 - 201031687 [Chemical 9]

R1、R2分別獨立表示氫原子或1價有機基’ X表示單 鍵或碳原子數6至20之2價芳香族基,Y表示單鍵、-〇_ 、-COO-、-OCO-、-CONH-、-CH2〇·、-CH2COO-或R1 and R2 each independently represent a hydrogen atom or a monovalent organic group 'X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -〇_, -COO-, -OCO-, - CONH-, -CH2〇·, -CH2COO- or

-CH2CH2COO_,Z表示可經氟原子取代之碳原子數3至26 之脂肪族烴基,R獨立表示氟原子、碳原子數1至3之院 氧基或碳原子數1至3之烷基,t表示〇至3之整數)。 第十一觀點係關於第十觀點所述之形成畫像用下層膜 塗佈液,其中式(2)或式(3)之Z表示任意氫原子經氟 原子取代之碳原子數3至26之脂肪族烴基。-CH2CH2COO_, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, t Represents an integer up to 3). The eleventh aspect is the lower layer film coating liquid for forming an image according to the tenth aspect, wherein the Z of the formula (2) or the formula (3) represents a fat having 3 to 26 carbon atoms in which any hydrogen atom is replaced by a fluorine atom. A hydrocarbon group.

第十二觀點係關於第十觀點或第十一觀點所述之形成 畫像下層膜塗佈液,其中進一步含有醯亞胺化率爲80% 以上之可溶性聚醯亞胺。 第十三觀點係關於一種形成畫像之下層膜,其特徵爲 使第十觀點是第十二觀點所述之形成畫像下層膜塗佈液燒 成而得。 第十四觀點係關於一種有機電晶體’其特徵爲具有使 第十觀點至第十三觀點所述之形成畫像下層膜塗佈液燒成 而得之膜。 [發明效果] -12- 201031687 本發明之形成畫像用下層膜爲可以少量之紫外線照射 量’將膜之表面由疏水性改變成親水性,據此,可利用該 特性形成電極等之機能性材料等之畫像。因此,可大幅縮 短電子裝置製造中之步驟時間,成爲就生產性而言相當有 效之材料。 【實施方式】 本發明係關於含有由側鏈上具有硫醇酯鍵之聚醯亞胺 前驅物或該聚醯亞胺前驅物獲得之聚醯亞胺的新穎形成畫 像之下層膜。進而,本發明係關於使用前述形成畫像之膜 之有機電晶體。 [聚醯亞胺前驅物]本發明爲一種形成畫像用下層膜 ,其特徵爲含有以下述式(1)表示之重複構造之聚醯亞 胺前驅物或使該聚醯亞胺前驅物脫水閉環所得之聚醯亞胺 [化 10]The twelfth aspect is the image forming underlayer film coating liquid according to the tenth aspect or the eleventh aspect, which further comprises a soluble polyimine having a ruthenium iodide ratio of 80% or more. The thirteenth aspect relates to a layer film for forming an image, which is characterized in that the tenth aspect is the formation of the image forming underlayer film coating liquid described in the twelfth aspect. The fourteenth aspect relates to an organic transistor which is characterized by having a film obtained by firing the formed underlayer film coating liquid described in the tenth to thirteenth aspects. [Effect of the Invention] -12-201031687 The lower layer film for forming an image of the present invention has a small amount of ultraviolet irradiation amount, and the surface of the film is changed from hydrophobic to hydrophilic, whereby a functional material such as an electrode can be formed by using the characteristic. Waiting for the portrait. Therefore, the step time in the manufacture of the electronic device can be greatly shortened, and it becomes a material which is quite effective in terms of productivity. [Embodiment] The present invention relates to a novel formed image underlayer film containing a polyimine imine obtained from a polythioimine precursor having a thiol ester bond in a side chain or the polyimine precursor. Further, the present invention relates to an organic transistor using the above-described film forming an image. [Polyimine precursor] The present invention is an underlayer film for forming an image, which is characterized in that it contains a polyimine precursor having a repetitive structure represented by the following formula (1) or dehydration of the polyimine precursor. Polyimine obtained [Chemical 10]

R1OOC COOR2 (1)R1OOC COOR2 (1)

•N—C 一A—C—N一B. I II II I• N—C—A—C—N—B. I II II I

Η Ο OH (式中,A表示4價有機基’ B表示以下述式(2)或(3 )表示之2價構造’R^R2分別獨立表示氫原子或1價 有機基,η表示自然數)。 上述式(1 )中’ R1、R2分別表示氫原子或1價有機 基,1價有機基之具體例列舉爲例如碳原子數1至4之烷 基。 -13- 201031687 碳原子數1至4之烷基可列舉爲甲基、乙基、丙基、 異丙基、丁基、異丁基、第三丁基。 其中,R1及R2較好爲氫原子。 上述式(1)中’以A表示之有機基之構造只要是4 價有機基則無特別限制。又,聚醯亞胺前驅物亦可具有一 種或複數種以式(1)表示之構造。因此,聚醯亞胺前驅 物中,以A表示之有機基之構造可爲一種,亦可混合複 數種。其中A較好爲具有脂肪族環或僅由脂肪族所構成 之4價有機基。更好爲具有脂肪族環之4價有機基。 以A表示之有機基之較佳具體例可列舉爲下述式A-1 至A-46之有機基。 -14 - 201031687 [表1] [表-1式A-l至式A-24] A-1 Α-2 h3c ch3 A-3 A-4 h3c ch3 .— — h3c ch3 A-5 介 A-6 A-7 女 A-8 XX A-9 xc A-10 Α-Π A-12 3CWX A-13 :φχ A-14 :二 tuc A-15 A-16 A-17 A-18 ch3 A-19 A-20 、ch3 A-21 V ch3 A-22 A-23 A-24 IK>^Η OH OH (wherein A represents a tetravalent organic group 'B represents a divalent structure represented by the following formula (2) or (3) 'R^R2 independently represents a hydrogen atom or a monovalent organic group, and η represents a natural number ). In the above formula (1), R1 and R2 each independently represent a hydrogen atom or a monovalent organic group, and specific examples of the monovalent organic group are, for example, an alkyl group having 1 to 4 carbon atoms. -13- 201031687 The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-butyl group. Among them, R1 and R2 are preferably a hydrogen atom. The structure of the organic group represented by A in the above formula (1) is not particularly limited as long as it is a tetravalent organic group. Further, the polyimine precursor may have one or a plurality of structures represented by the formula (1). Therefore, in the polyimine precursor, the organic group represented by A may be one type or a plurality of kinds. Wherein A is preferably a tetravalent organic group having an aliphatic ring or only an aliphatic group. More preferably, it is a tetravalent organic group having an aliphatic ring. Preferred examples of the organic group represented by A are exemplified by the organic groups of the following formulae A-1 to A-46. -14 - 201031687 [Table 1] [Table-1 Formula Al to Formula A-24] A-1 Α-2 h3c ch3 A-3 A-4 h3c ch3 .— — h3c ch3 A-5 介 A-6 A- 7 Female A-8 XX A-9 xc A-10 Α-Π A-12 3CWX A-13 : φχ A-14 : Two tuc A-15 A-16 A-17 A-18 ch3 A-19 A-20 ,ch3 A-21 V ch3 A-22 A-23 A-24 IK>^

[*2] [表-1 式 A-25] A-25 -15- 201031687 [表3] [表-3 式A-25至A-36] A-26 Α-27 Α-28 A-29 Α-30 Α-31 A-32 Α-33 Α-34 χΛχ A-35 Α-36 :0½ [表4] [表-4 式 A-37 至 A-46] Α-37 38 00C 39 00C Α-40 A-41 Α-42 D%tC h3c A-43 CH3 h3c Α-44 ch3 h3c A-45 Α-46 -16- 201031687 上述式A-1至A-46作爲形成畫像用下層膜時,可依 據所要求之特性適當選擇。 例如,上述式A-1至A-46中’作爲提高曝光感度( 本說明書中,所謂曝光感度表示每曝光量(紫外線照射量 )之自疏水性變換成親水性之程度)之4價有機基列舉爲 式A-1至A-25之具有脂肪族環或僅由脂肪族所構成之4 φ 價有機基,效果最高之有機基列舉爲A-1、A-6、A-16或 A-19。 又,式A-1至A-25之4價有機基就提高絕緣性效果 之觀點而言亦較佳。 前述式(1)中,以A表示之有機基中,混合式A-1 至A-25以外之基時,式A-1至A-25之比例較好爲10莫 耳%以上,更好爲50莫耳%以上,最好爲80莫耳%以上 〇 φ 上述式(1)中,B表示如以下述式(2)或式(3) 表示之側鏈上具有硫醇酯鍵之2價構造。 藉由於含有以式(1)表示之重複構造之聚醯亞胺前 驅物(或由此獲得之聚醯亞胺)之側鏈上含有硫醇鍵,於 硫醇酯基經光分解時,透過硫醇酯基鍵結之側鏈將從聚合 物主鏈切斷。因此’藉由調整透過硫醇鍵鍵結之側鏈的親 疏水性’可期待利用紫外線等之光照射而使親疏水性產生 變化者。 201031687 [化 11] ο[*2] [Table-1 Formula A-25] A-25 -15- 201031687 [Table 3] [Table-3 Formula A-25 to A-36] A-26 Α-27 Α-28 A-29 Α -30 Α-31 A-32 Α-33 Α-34 χΛχ A-35 Α-36 :01⁄2 [Table 4] [Table-4 Equations A-37 to A-46] Α-37 38 00C 39 00C Α-40 A-41 Α-42 D%tC h3c A-43 CH3 h3c Α-44 ch3 h3c A-45 Α-46 -16- 201031687 The above formulas A-1 to A-46 can be used as the underlayer film for forming an image. The characteristics required are appropriately selected. For example, in the above formulae A-1 to A-46, 'as a tetravalent organic group for improving the exposure sensitivity (in the present specification, the exposure sensitivity means the degree of self-hydrophobicity per unit of exposure amount (ultraviolet irradiation amount)) Listed as the 4 φ valent organic group having an aliphatic ring or only an aliphatic group of the formulae A-1 to A-25, the most effective organic group is exemplified as A-1, A-6, A-16 or A- 19. Further, the tetravalent organic group of the formulae A-1 to A-25 is also preferable from the viewpoint of improving the insulating effect. In the above formula (1), in the organic group represented by A, when the group other than the formula A-1 to A-25 is mixed, the ratio of the formulae A-1 to A-25 is preferably 10 mol% or more, more preferably 50 mol% or more, preferably 80 mol% or more 〇φ In the above formula (1), B represents a thiol ester bond having a side chain represented by the following formula (2) or formula (3) Price structure. By the thiol bond on the side chain of the polyimine precursor containing the repetitive structure represented by the formula (1) (or the polyimine thus obtained), when the thiol ester group is photodecomposed, The side chain of the thiol ester linkage will be cleaved from the polymer backbone. Therefore, by adjusting the hydrophilicity of the side chain bonded through the thiol bond, it is expected that the hydrophilicity and the like are changed by irradiation with light such as ultraviolet rays. 201031687 [化11] ο

IIII

s-c-χ-γ-ζS-c-χ-γ-ζ

上述式(2)或(3)中,X表示單鍵或碳原子數6至 20之2價芳香族基。 Y 表示單鍵、-0-、-COO-、-OCO-、-CONH-、-CH20-、-CH2CO〇-或-CH2CH2COO-。 z表示碳原子數3至26之脂肪族烴基,且任意之氫 原子可經氟原子取代。 R各獨立表示氟原子、碳原子數1至3之院氧基或碳 原子數1至3之烷基,t表示0至3之整數。 以上述式(2)或(3)表示之B之構造,就提高紫外 線之吸收效率之觀點而言,側鏈構造中亦可包含芳香族之 碳環。 因此,上述式(2)或(3)中,X表示碳原子數6至 20之2價芳香族基時,較佳之芳香族基列舉爲伸苯基、 聯苯基、三聯苯基、伸萘基、伸蒽基等。 上述Z中之碳原子數3至26之脂肪族烴基列舉爲例 如丙基、異丙基、丁基、異丁基、第三丁基、戊基、己基 、辛基、2-乙基己基、壬基、第二壬基、異壬基、癸基、 十二烷基、十四烷基、十六烷基、十八烷基等之直鏈狀或 分支狀烷基;烯丙基、己烯基等之烯基;具有環丁烷、環 戊烷、環己烷、環癸烷、類固醇骨架、金剛烷等之脂環式 -18- 201031687 烴基;甲酸乙酯、乙酸甲酯、乙酸乙酯、丙酸甲酯、雙乙 醯酮(diacetyl )、異丁酸甲酯、異丁酸乙酯、丁酸乙酯 、丁酸丙酯、乙酸異丁酯、異丁酸異丁酯、丁酸異丁酯、 異戊酸異丁酯、乙酸異戊酯、丙酸異戊酯、丙酸戊指、異 丁酸戊酯、丁酸戊酯、異戊酸戊酯、己酸烯丙酯、乙醯基 乙酸乙酯、庚酸乙酯、乙酸庚酯、辛酸乙酯、乙酸硬脂酯 、乙酸壬酯、乙酸冰片酯、苯二甲酸二乙酯之酯基等,最 _ 好爲碳原子數12至26之直鏈狀烷基。 上述之脂肪族烴基之任意氫原子亦可經氟原子取代, 較好任意氫原子經氟原子取代之碳原子數3至26之脂肪 族烴基,最好爲碳數4至7之直鏈狀氟烷基。 以上述式(2)或(3)表示之B構造之較佳具體例列 舉爲下述[B-1]至[B-1 7]所示之構造。該等2價之構造中, 就疏水性容易提高之觀點而言,最好爲以[B-13]至 表示之2價構造,又更好爲以[B-15]至[B-17]表示之2價 構造。 -19- 201031687 [化 12] o:c ,S(CH2)k-CH3 \_(CH2)k-CH3In the above formula (2) or (3), X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms. Y represents a single bond, -0-, -COO-, -OCO-, -CONH-, -CH20-, -CH2CO〇- or -CH2CH2COO-. z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms, and any hydrogen atom may be substituted with a fluorine atom. R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3. The structure of B represented by the above formula (2) or (3) may contain an aromatic carbocyclic ring in the side chain structure from the viewpoint of improving the absorption efficiency of ultraviolet rays. Therefore, in the above formula (2) or (3), when X represents a divalent aromatic group having 6 to 20 carbon atoms, preferred aromatic groups are phenyl, biphenyl, terphenyl, and naphthene. Base, stretch base, etc. The aliphatic hydrocarbon group having 3 to 26 carbon atoms in the above Z is exemplified by propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, a linear or branched alkyl group of a fluorenyl group, a second fluorenyl group, an isodecyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group or the like; an allyl group Alkenyl group such as alkenyl group; alicyclic -18-201031687 hydrocarbon group having cyclobutane, cyclopentane, cyclohexane, cyclodecane, steroid skeleton, adamantane, etc.; ethyl formate, methyl acetate, ethyl acetate Ester, methyl propionate, diacetyl, methyl isobutyrate, ethyl isobutyrate, ethyl butyrate, propyl butyrate, isobutyl acetate, isobutyl isobutyrate, butyl Isobutyl phthalate, isobutyl isovalerate, isoamyl acetate, isoamyl propionate, pentyl propionate, amyl isobutyrate, amyl butyrate, amyl isovalerate, allyl hexanoate Ethyl acetate, ethyl heptanoate, heptyl acetate, ethyl octanoate, stearyl acetate, decyl acetate, borneol acetate, ester of diethyl phthalate, etc. atom A linear alkyl group of 12 to 26 is used. Any hydrogen atom of the above aliphatic hydrocarbon group may be substituted by a fluorine atom, preferably an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom, preferably a linear fluorine having 4 to 7 carbon atoms. alkyl. Preferred examples of the B structure represented by the above formula (2) or (3) are as shown in the following [B-1] to [B-1 7]. Among these two-valent structures, from the viewpoint that the hydrophobicity is easily improved, it is preferably a structure of [B-13] to a two-valent structure, and more preferably a [B-15] to [B-17]. Indicates the two-valent structure. -19- 201031687 o:c ,S(CH2)k-CH3 \_(CH2)k-CH3

=11-17 S k=11-17 [B-1] -0- [B-2]=11-17 S k=11-17 [B-1] -0- [B-2]

Jh3c ch3[叫 CH3 h3c ch3Jh3c ch3[called CH3 h3c ch3

[B-5] o:c -0- s^〇-(CH2)k-CH3 〇:C ° k=11-17 _irV- [S'6] [化 13][B-5] o:c -0- s^〇-(CH2)k-CH3 〇:C ° k=11-17 _irV- [S'6] [Chem. 13]

-20- 201031687 [化 14] 〇V〇^0^(CH2)k-CH3 s>〇-(CH2)k-CH3 ^ “η, l k=11-17 k=11-i7 [B-12]-20- 201031687 〇V〇^0^(CH2)k-CH3 s>〇-(CH2)k-CH3 ^ “η, l k=11-17 k=11-i7 [B-12]

.^CF3 S [化 15].^CF3 S [化15]

[B-14] ^/(CF2)j-CF3 j=3-17[B-14] ^/(CF2)j-CF3 j=3-17

(CF2)j-CF3 1=3-17(CF2)j-CF3 1=3-17

FF FF FF ?O~(CF2)卜 CF3 [B-15] -6- [B-16 ] j=3-17 [B-17] 又’考慮到其他特性,例如絕緣性、溶劑溶解性、成 膜性、進而膜之密著性等亦爲重要特性時,本發明之形成 畫像用下層膜中所用之聚醯亞胺前驅物(及由其獲得之聚 醯亞胺)亦可爲除了以前述式(1)表示之構造以外,亦 含有前述式(1)中之2價有機基B置換成側鏈上不具有 硫醇酯鍵之其他2價有機基D之以下述式(4)表示之構 造之聚醯亞胺前驅物(及由其獲得之聚醯亞胺)。 此時,含有於側鏈上具有硫醇酯鍵之2價有機基B之 以上述式(〇表示之構造與含有於側鏈上不具有硫醇酯 鍵之其他2價有機基之式(4)之構造之鍵結可爲嵌段鍵 -21 - 201031687 結及/或無規鍵結之任一種。 [化 16] (R1OOC COOR2 \ —N—C—C—N—D*4— (4} I II II I / HO 〇 H /m 式中,A、R1及R2與上述式(1)中之定義相同,m 表示自然數,D表示側鏈上不具有硫醇酯鍵之其他2價之 構造。 本發明之形成畫像用下層膜中所用之聚醯亞胺前驅物 (及由其獲得之聚醯亞胺)中,式(4)中,D爲側鏈上 具有長鏈烷基時,若過度提高以式(4)表示之構造(側 鏈上不具有硫醇酯鍵之構造)之含有比例將使對於紫外線 之感度下降。據此,含有以式(4)表示之構造時,以式 (1 )表示之構造(側鏈上具有硫醇酯鍵之構造)之比例 較好爲30莫耳%以上。 又’爲了進一步提高曝光感度,縮短紫外線之照射時 間’有必要進一步提高以式(1 )表示之構造之含有比例 ,此時之含有比例較好爲50莫耳%以上。 又式(4)中’ D於側鏈上不具有長鏈烷基時,由於 膜之疏水性主要受以式(1)表示之構造之比例影響,故 考慮畫像形成液之表面張力或與上層構件之密著性等,而 決定以式(1 )表示之構造之比例即可。 又’以上述式(2)或式(3)表示之構造中,z之脂 肪族烴基之一部份經氟原子取代時,以式(n表示之構 造之比例即使爲10莫耳%以下亦可獲得高的疏水性與感 -22- 201031687 度。亦即,認爲膜之親疏水性之變化係導因於側鏈構造之 分解•分離’於式(1)之比例爲10莫耳%以下時,曝光 感度亦未必會降低。 上述式(4)中,不具有硫醇酯鍵之其他2價構造D 較好爲具有絕緣性高之構造者,具體而言,可列舉爲下述 [D-1]至[D-57]之構造。 下述[D-1]至[D-57]中,就提高絕緣性容易性之觀點而 φ 言較好爲[D-1]至[D-5]之構造。 又’溶劑溶解性提高效果較高之構造列舉爲[D_2J、 [D-5] 、 [D-7] 、 [D-8] 、 [D-12] 、 [D-22] 、 [D-24]至[D-27] 、[D-29]。 又’側鏈上具有長鏈烷基之疏水性構造之具體例可列 舉爲[D-55]至[D-27]之構造,但作爲有機電晶體之特性, 可期待絕緣性之提高,可在不降低感度之範圍內使用,該 等使用時需注意其使用比例等。 ❹ -23- 201031687 [化 17]FF FF FF ?O~(CF2) Bu CF3 [B-15] -6- [B-16 ] j=3-17 [B-17] Also 'considering other characteristics such as insulation, solvent solubility, When the film property and the adhesion of the film are also important characteristics, the polyimide precursor (and the polyimide obtained therefrom) used in the underlayer film for forming an image of the present invention may be in addition to the foregoing. In addition to the structure represented by the formula (1), the divalent organic group B in the above formula (1) is substituted with another divalent organic group D having no thiol ester bond in the side chain, and is represented by the following formula (4). Constructed polyimine precursor (and polyimine obtained therefrom). In this case, the divalent organic group B having a thiol ester bond in the side chain is represented by the above formula (the structure represented by 〇 and the other divalent organic group having no thiol ester bond on the side chain) (4) The bond of the structure may be any one of the block bond - 21,031,687 knot and/or random bond. [Chem. 16] (R1OOC COOR2 \ -N - C - C - N - D * 4 - (4 } I II II I / HO 〇H /m where A, R1 and R2 are the same as defined in the above formula (1), m represents a natural number, and D represents another 2 valence having no thiol ester bond in the side chain The polyimine precursor (and the polyimine obtained therefrom) used in the underlayer film for forming an image of the present invention, wherein D is a long-chain alkyl group in a side chain in the formula (4) When the ratio of the structure represented by the formula (4) (the structure having no thiol ester bond in the side chain) is excessively increased, the sensitivity to ultraviolet rays is lowered. Accordingly, when the structure represented by the formula (4) is included, The ratio of the structure represented by the formula (1) (the structure having a thiol ester bond in the side chain) is preferably 30 mol% or more. Further, in order to further improve the exposure sensitivity, the ultraviolet rays are shortened. It is necessary to further increase the content ratio of the structure represented by the formula (1), and the content ratio at this time is preferably 50 mol% or more. In the formula (4), 'D does not have a long-chain alkane in the side chain. In the case of the base, since the hydrophobicity of the film is mainly affected by the ratio of the structure represented by the formula (1), the structure represented by the formula (1) is determined in consideration of the surface tension of the image forming liquid or the adhesion to the upper member. In the structure represented by the above formula (2) or (3), when one part of the aliphatic hydrocarbon group of z is substituted by a fluorine atom, the ratio of the structure represented by the formula (n is 10) A high degree of hydrophobicity and sensibility can be obtained below 5% - 201031687 degrees. That is, it is considered that the change in the hydrophilicity of the membrane is caused by the decomposition/separation of the side chain structure in the ratio of the formula (1). When the molar concentration is 10 mol% or less, the exposure sensitivity does not necessarily decrease. In the above formula (4), the other divalent structure D having no thiol ester bond is preferably a structure having high insulating properties, and specifically, It is the structure of [D-1] to [D-57] described below. In the following [D-1] to [D-57], it is improved. From the viewpoint of the ease of insulation, φ is preferably a structure of [D-1] to [D-5]. Further, the structure having a high solvent solubility improving effect is listed as [D_2J, [D-5], [D]. -7], [D-8], [D-12], [D-22], [D-24] to [D-27], [D-29]. Also with a long chain alkyl group on the side chain Specific examples of the hydrophobic structure include the structures of [D-55] to [D-27]. However, as the characteristics of the organic transistor, improvement in insulation can be expected, and it can be used without reducing the sensitivity. When using, pay attention to the proportion of use. ❹ -23- 201031687 [Chem. 17]

众 [D-1 ] [ D-2 ]Public [D-1 ] [ D-2 ]

普众-bPuzhong-b

[D-10] [D-11 ] [D-12] [D-13] [D-14] ,ch3 H3Q PH,hQ-Q- [D-15] [D-16][D-10] [D-11] [D-12] [D-13] [D-14] , ch3 H3Q PH, hQ-Q- [D-15] [D-16]

-24- 201031687 [化 18]-24- 201031687 [Chem. 18]

ΟΟ

ΜΜ

[D-19] F3CvCF:3 [D-22 ] [D-25 ] [ D-26 ][D-19] F3CvCF: 3 [D-22 ] [D-25 ] [ D-26 ]

[D-27 ][D-27 ]

-25- 201031687 [化 19]-25- 201031687 [Chem. 19]

φΦ

[D-41 ] [ D-42 ] [化 20] -(CH2)ni一(n1 = 2 — 12) [D-43 ] ch3 ch3 -CH2-CH_(CH2)2—CH—(CH2)2 [D-45 ] CH3 -(CH2)2_CH 一 (CH2)5 [D-47] (CH2)3—〇_(CH2)2—(CH2)3_ ch3 -(CH2)2—C—(CH2)2— [D-44] CH3 ch3 -(CH2)4—C—(CH2)3-[D-41 ] [ D-42 ] [Chem. 20] -(CH2)ni-(n1 = 2 - 12) [D-43 ] ch3 ch3 -CH2-CH_(CH2)2—CH—(CH2)2 [ D-45 ] CH3 -(CH2)2_CH-(CH2)5 [D-47] (CH2)3—〇_(CH2)2—(CH2)3_ ch3 -(CH2)2—C—(CH2)2— [D-44] CH3 ch3 -(CH2)4—C—(CH2)3-

[D-46 ] CH3 ch3 —(CH2)4- CH_(CH2)5— [D-48 ] [D-49 ] -26- 201031687 [化 21][D-46 ] CH3 ch3 —(CH2)4- CH_(CH2)5— [D-48 ] [D-49 ] -26- 201031687 [Chem. 21]

(CH2)n2 (η2 = 3 — 7) [D-51 ](CH2)n2 (η2 = 3 — 7) [D-51 ]

CH3 [D-53 ] (π5 = 11 / 17) 〇-(CH2)n5CH3 [D-55 ] (n6 = 4 — 6) ^^-〇-(CH2)n6CH3 [D-56]CH3 [D-53 ] (π5 = 11 / 17) 〇-(CH2)n5CH3 [D-55 ] (n6 = 4 — 6) ^^-〇-(CH2)n6CH3 [D-56]

[D-57 ] 前述聚醯亞胺前驅物係藉由例如使四羧酸二酐及其衍 生物與二胺聚合而製造。尤其,就以四羧酸酐成分與二胺 成分作爲原料進行反應比較簡便之理由,較好爲以下述式 (5)表示之聚醯亞胺前驅物(聚醯胺酸)。 [化 22][D-57] The above polyimine precursor is produced by, for example, polymerizing a tetracarboxylic dianhydride and a derivative thereof with a diamine. In particular, the polyimine precursor (polyglycine) represented by the following formula (5) is preferred because the reaction of the tetracarboxylic anhydride component and the diamine component as a raw material is relatively simple. [化22]

/ HOOC COOH (5)/ HOOC COOH (5)

N—CN-C

I II Η Ο (式中’A、Β及η與式(1)中之定義相同) 《四殘酸二酐及其衍生物》 酐及其衍生物並無特別限制,但 -27- 201031687 較好使用以下述式(6)表示之四羧酸二酐。式中之A與 上述式(1)之定義相同,其具體例列舉爲上述之式A-1 至A-46所示者。 [化 23] Ο 〇I II Η Ο (wherein 'A, Β and η are the same as defined in formula (1)) "Quaternary acid dianhydride and its derivatives" Anhydride and its derivatives are not particularly limited, but -27-201031687 The tetracarboxylic dianhydride represented by the following formula (6) is preferably used. A in the formula is the same as defined in the above formula (1), and specific examples thereof are as shown in the above formulas A-1 to A-46. [化 23] Ο 〇

Ο 〇Ο 〇

(式中,A與式(1)中之定義相同)。(wherein A is the same as defined in the formula (1)).

如截至目前所述,聚醯亞胺前驅物中,以A表示之 有機基之構造可爲一種,亦可混合存在複數種。其中 A 較好爲具有脂肪族環或僅由脂肪族所構成之4價有機基, 更好爲具有脂肪族環之4價有機基。據此,四羧酸二酐成 分中較好含有較多之A爲具有脂肪族環或僅由脂肪族所 構成之4價有機基之式(6)化合物。更好,以含有較多 之A爲具有脂肪族環之4價有機基之式(6)化合物較佳 此於僅使用芳香族酸二酐製造聚醯亞胺前驅物等,作 爲形成畫像用下層膜時,有若對該形成畫像用下層膜施加 高電場時絕緣性顯著降低之傾向。相反地,使用脂肪族酸 一酐時,於筒電場之絕緣性優異。 例如’有機電晶體之作動電壓亦有成爲IMV/cm左右 之時’於該用途之情況,就絕緣性之觀點而言,尤其以使 用脂肪酸二酐作爲聚醯亞胺前驅物之原料較適宜。 -28- 201031687 《二胺》 本發明中,二胺成分中所用之二胺爲以下述式(7) 表示,B爲以下述式(2)或下述式(3)表示之構造’亦 即爲於側鏈上具有硫醇酯鍵之2價構造° B之具體例列舉 爲以上述之[B-1]至[B-17]所示之構造。 [化 24] H2N-B-NH2 (7) ❹ [化 25]As described so far, in the polyimine precursor, the organic group represented by A may be one type or a plurality of kinds may be mixed. Wherein A is preferably a tetravalent organic group having an aliphatic ring or only an aliphatic group, more preferably a tetravalent organic group having an aliphatic ring. Accordingly, the tetracarboxylic dianhydride component preferably contains a large amount of the compound of the formula (6) wherein A is a tetravalent organic group having an aliphatic ring or only an aliphatic group. More preferably, the compound of the formula (6) containing a large amount of A is a tetravalent organic group having an aliphatic ring, and preferably a polyiminoimine precursor is produced by using only an aromatic acid dianhydride, and the like is used as a lower layer for forming an image. In the case of a film, the insulating property tends to be remarkably lowered when a high electric field is applied to the underlayer film for forming an image. On the contrary, when an aliphatic acid monoanhydride is used, it is excellent in insulation properties in a cylindrical electric field. For example, in the case where the operating voltage of the organic transistor is about 1 MV/cm, it is preferable to use a fatty acid dianhydride as a raw material of the polyimide precursor in view of the insulating property. -28-201031687 "Diamine" In the present invention, the diamine used in the diamine component is represented by the following formula (7), and B is a structure represented by the following formula (2) or the following formula (3), that is, Specific examples of the divalent structure ° B having a thiol ester bond in the side chain are as shown in the above [B-1] to [B-17]. [Chemical 24] H2N-B-NH2 (7) ❹ [Chem. 25]

(R)t(R)t

〇 II S-C-X-Y-Z〇 II S-C-X-Y-Z

(式中,X表示單鍵或碳原子數6至20之2價芳香族基 ,Y 表示單鍵、-〇-、-coo-、-OCO-、-CONH-、-CH20-、-ch2coo -或-ch2ch2coo-,Z表示可經氟原子取代之 碳原子數3至26之脂肪族烴基,R各獨立表示氟原子、 碳原子數1至3之烷氧基或碳原子數1至3之烷基,t表 示〇至3之整數)。 又’在展現本發明效果之範圍內,除了以式(7)表 示之二胺以外’亦可倂用以式(q丨)表示之式(7 )以外 之二胺。 [化 26] H2N-D-NH2 (Q1 ) 式(Q1)中’D與上述式(4)中之定義相同。據此 ’以式(Q1)表示之二胺之具體例列舉爲D之構造具有 -29 - 201031687 上述[D-1]至[D-57]所示之2價構造之二胺。 [二胺化合物之合成方法](wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -〇-, -coo-, -OCO-, -CONH-, -CH20-, -ch2coo - Or -ch2ch2coo-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. Base, t means 〇 to an integer of 3). Further, in addition to the diamine represented by the formula (7), a diamine other than the formula (7) represented by the formula (q丨) may be used in the range in which the effects of the present invention are exhibited. H2N-D-NH2 (Q1) 'D in the formula (Q1) is the same as defined in the above formula (4). Here, a specific example of the diamine represented by the formula (Q1) is a diamine having a divalent structure represented by the above-mentioned [D-1] to [D-57] in the structure of D. [Synthesis method of diamine compound]

以上述式(7)表示之二胺中,獲得b爲式(2)構造 之一 fee之方法並無特別限制。若以一例顯示,則合成對應 之以下述通式(8)表示之二硝基化合物,且將硝基還原 轉換成胺基而獲得。還原二硝基化合物之方法並無特別限 制’通常使用鈀-碳、氧化舶、阮尼鎳、鐵、氯化錫、鉑 黑、铑-氧化鋁等作爲觸媒,使用乙酸乙酯、甲苯、四氫 呋喃、二噁烷、醇系等溶劑,氫氣、聯胺、氯化氫、氯化 銨等反應進行之方法。本發明中,二硝基化合物之骨架中 具有硫原子等之化合物由於偶爾會成爲觸媒毒,有時會使 觸媒失活’故更好使用利用阮尼鎳、鐵 '氯化錫等之化學 還原法。 [化 27] o2n 〇:c-s-x_y-z<^-n〇2 (8)In the diamine represented by the above formula (7), the method of obtaining b as one of the structures of the formula (2) is not particularly limited. When an example is shown, a dinitro compound represented by the following formula (8) is synthesized, and a nitro group is converted into an amine group. The method for reducing the dinitro compound is not particularly limited. Usually, palladium-carbon, oxidized, nickel, iron, tin chloride, platinum black, lanthanum-alumina or the like is used as a catalyst, and ethyl acetate, toluene, and the like are used. A method in which a solvent such as tetrahydrofuran, dioxane or an alcohol is reacted with hydrogen, hydrazine, hydrogen chloride or ammonium chloride. In the present invention, a compound having a sulfur atom or the like in the skeleton of the dinitro compound may occasionally become catalytically toxic, and may inactivate the catalyst. Therefore, it is more preferable to use nickel hydride, iron, tin chloride or the like. Chemical reduction method. [2] 2:c-s-x_y-z<^-n〇2 (8)

(R)t (式中’X、Y、Z、R及t與上述式(2)中之定義相同) 上述式(8)之二硝基化合物可藉由使下述所示之二 硝基苯甲酿氯(9)與含有硫醇基之化合物(1〇)之反應 等而獲得。 -30- 201031687 [化 28] o2n o=c -^-N02 ( 9 ) (R)t HS-X-Y-Z (10) (式中,X、Y、Z、R及t與上述式(2)中之定義相同)(R)t (wherein 'X, Y, Z, R and t are the same as defined in the above formula (2)) The dinitro compound of the above formula (8) can be obtained by the following dinitro group It is obtained by reacting benzoyl chloride (9) with a compound containing a thiol group (1 〇). -30- 201031687 [2] o2n o=c -^-N02 ( 9 ) (R)t HS-XYZ (10) (wherein X, Y, Z, R and t are in the above formula (2) Same definition)

以上述式(7)表示之二胺中,獲得b爲式(3)構造 之二胺之方法並無特別限制。例如,可合成對應之以下述 式(11)表示之二硝基化合物,隨後與如上述二硝基化合 物(8 )之情況同樣地使硝基還原轉換成胺基而獲得。 [化 29] 〇2N<^r Ο .C-X-Y-Z 〇 N〇2 (11) (R)tAmong the diamines represented by the above formula (7), a method of obtaining a diamine having a structure of the formula (3) is not particularly limited. For example, a dinitro compound represented by the following formula (11) can be synthesized, and then obtained by subjecting a nitro group to an amine group in the same manner as in the case of the above dinitro compound (8).化2N<^r Ο .C-X-Y-Z 〇 N〇2 (11) (R)t

(式中’ X、Y、Z、R及t與上述式(3)中之定義相同) 上述式(11)之二硝基化合物可藉由下述所示之含有 硫醇基之二硝基化合物(12)與具有亦可含有氟原子之脂 肪族烴之醯氯(1 3 )反應等而獲得。 [化 30] SH 〇2Ν&quot;ή&quot;Ν〇2 (12&gt; CI-E-X-Y-Z (13)(R)t -31 - 201031687 (式中’ X、Y、Z、R及t與上述式(3)中之定義相同) 《聚醯亞胺前驅物之製造方法》 獲得具有以式(1)表示之重複構造之聚醯亞胺前驅 物而言’使包含以上述式(6)表示之四羧酸二酐之四羧 酸二酐成分與包含以上述式(7)表示之二胺以及依據需 要之以上述式(Q1)表示之二胺成分之二胺成分於有機 溶劑中混合並反應之方法爲簡便之方法。 使四羧酸二酐成分與二胺成分於有機溶劑中混合之方 法,列舉爲使二胺成分分散或溶解於有機溶劑中之溶液予 以攪拌,並直接添加四羧酸二酐直接或者將其分散或溶解 於有機溶劑中添加之方法;相反地將二胺成分添加於將四 羧酸二酐成分分散或溶解於有機溶劑之溶液中之方法;交 互添加四羧酸二酐成分與二胺成分之方法等。 又’四羧酸二酐成分與二胺成分以複數種存在之化合 物之情況,可以事先混合該等複數種成分之狀態進行聚合 反應,亦可個別依序進行聚合反應。 本發明所用之上述聚醯亞胺前驅物聚合之際,四羧酸 二酐成分與二胺成分之調配比,亦即〈四羧酸二gf成分之 總莫耳數〉:〈二胺成分之總莫耳數〉較好爲1 : 0.5至1 :1.5。與通常聚合反應相同,其莫耳比越接近1:丨所生 成之聚酿亞女目U驅物之聚合度越大,分子量增加。 前述聚醯亞胺前驅物之製造方法中,使四狻酸二酐成 -32- 201031687 分與二胺成分在有機溶劑中反應時之溫度通常爲_20至 1 5 0 °C ’較好爲0至8 0 °C。 將反應溫度設定成高溫時聚合反應迅速進行並完成, 但過高時會有無法獲得高分子量之聚醯亞胺前驅物之情況 〇 又,在有機溶劑中進行聚合反應時,溶劑中之兩成分 (四羧酸酐成分及二胺成分之合計質量)之固體成分濃度 φ 並無特別限制,但濃度太低時難以獲得高分子量之聚醯亞 胺前驅物,濃度太高時反應液體之黏度過高而難以均勻攪 拌,故較好爲1至50質量%,更好爲5至30質量%。亦 可爲聚合反應初期以高濃度進行,隨後與聚合物(聚醯亞 胺前驅物)純化同時追加有機溶劑。 上述聚合反應中所用之有機溶劑只要是可溶解生成之 聚醯亞胺前驅物者即無特別限制,但若要列舉其具體例, 則可列舉爲Ν,Ν-二甲基甲醯胺、N,N-二甲基乙醯胺、N-Φ 甲基-2-吡咯啶酮、N -甲基己內醯胺、二甲基亞楓、四甲 基脲、吡啶、二甲基楓、六甲基亞颯、r-丁內酯等。該 等可單獨使用,亦可混合兩種以上使用。另外,即使爲無 法溶解聚醯亞胺前驅物之溶劑,只要在不使生成之聚醯亞 胺前驅物析出之範圍內,亦可混合於上述溶劑中。 如此獲得之含有聚醯亞胺前驅物之溶液可直接使用於 調製後述之形成畫像之下層膜塗佈液中。又,亦可在水、 甲醇、乙醇等弱溶劑中使聚醯亞胺前驅物沉澱單離並回收 後使用。 -33- 201031687 [聚醯亞胺] 可使具有以前述式(1)及(4)(以及前述式(5) )表示之構造之聚醯亞胺前驅物藉由脫水閉環成爲聚醯亞 胺。該醯亞胺化反應之方法並無特別限制,但使用鹼性觸 媒與酸酐之觸媒醯亞胺化,由於在醯亞胺化反應時不易引 起醯亞胺分子量降低,且醯亞胺化率之控制較容易故而較 佳。 觸媒醯亞胺化可藉由使前述聚醯亞胺前驅物在有機溶 劑中,於鹼性觸媒及酸酐存在下攪拌1至1 〇〇小時。 又其中,聚醯亞胺前驅物亦可直接(未經單離)使用 包含由前述四羧酸酐成分及二胺成分之聚合獲得之聚醯亞 胺前驅物之溶液。 鹼性觸媒可列舉爲吡啶、三乙基胺、三甲基胺、三丁 基胺、三辛基胺等。其中,吡啶由於進行反應時帶有適度 之鹼性故而較佳。 作爲酸酐可列舉爲乙酸酐、偏苯三酸酐、均苯四酸酐 等。其中乙酸酐由於醯亞胺化結束後所得之聚醯亞胺之純 化較容易故而較佳。 作爲有機溶劑可使用前述聚醯亞胺前驅物聚合反應時 所用之溶劑。 觸媒醯亞胺化時之反應溫度較好爲-20至250t,更 好爲0至180 °C。反應溫度設定在高溫時醯亞胺化會迅速 進行,但過高時有聚醯亞胺之分子量降低之情況。 -34- 201031687 鹼性觸媒之量相對於前述聚醯亞胺前驅物中之酸醯胺 基較好爲0.5至30莫耳倍,更好爲2至20莫耳倍。又, 酸酐之量相對於前述聚醯亞胺前驅物中之酸醯胺基爲1至 50莫耳倍,更好爲3至30莫耳倍。 調整上述反應溫度及觸媒量,可控制所得聚醯亞胺之 醯亞胺化率。 如上述獲得之溶劑可溶性聚醯亞胺之反應溶液,雖可 φ 直接使用於後述之閘極絕緣膜之製作,但由於反應液中含 有醯亞胺化觸媒,故較好使用聚醯亞胺經純化•回收•洗 淨者。 聚醯亞胺之回收之簡便方法爲在攪拌下將反應液倒入 弱溶劑中使聚醯亞胺沉澱,並將其過濾之方法。 此時使用之弱溶劑並無特別限制,但可例示爲甲醇、 己烷、庚烷、乙醇、甲苯、水等。過濾回收沉澱物後,較 好以上述弱溶劑洗淨。 Φ 回收之聚醯亞胺可在常壓或減壓下,於常溫或加熱乾 燥成爲聚醯亞胺粉末。 使該聚醯亞胺粉末進一步溶解於良溶劑中,於弱溶劑 中再沉澱重複操作2至1〇次,亦可進一步減少聚合物中 之雜質。 此時使用之良溶劑只要是可溶解聚醯亞胺前驅物或聚 醯亞胺則無特別限制,但其例列舉爲例如N,N_二甲基甲 醯胺、N,N-二甲基乙醯胺、2_吡咯啶酮、N_甲基-2-吡咯 陡酮、N-乙基-2-吡咯啶酮、N_乙烯基-2_吡咯啶酮、N-甲 -35- 201031687 基己內醯胺、二甲基亞楓、四甲基脲、吡啶、r-丁內酯 等。 又,使用例如醇類、酮類、烴等三種類以上之弱溶劑 作爲再沉殿所用之弱溶劑時,可進一步提高純化效率。 [形成畫像之下層膜塗佈液] ❺ 本發明之形成畫像用下層膜可使用形成畫像之下層膜 塗佈液而形成。該形成畫像之下層膜塗佈液可爲含有前述 之聚醯亞胺前驅物、前述之聚醯亞胺、以及溶劑,及依據 需要可進一步含有後述之偶合劑或界面活性劑之塗佈液, 較好爲包含使含有以下述式(6)表示之四羧酸二酐之四 羧酸二酐成分及含有以式(7)表示之二胺之二胺成分反 應獲得之聚醯亞胺前驅物,或使該聚醯亞胺前驅物經脫水 閉環獲得之聚醯亞胺之塗佈液。 [化 31] Ο 〇(wherein X, Y, Z, R and t are the same as defined in the above formula (3)) The dinitro compound of the above formula (11) can be represented by the dinitro group having a thiol group shown below The compound (12) is obtained by reacting with ruthenium chloride (1 3 ) having an aliphatic hydrocarbon which may also contain a fluorine atom. [化30] SH 〇2Ν&quot;ή&quot;Ν〇2 (12&gt; CI-EXYZ (13)(R)t -31 - 201031687 (wherein X, Y, Z, R and t are in the above formula (3) The definition of the same is as follows: "Method for producing polyimine precursor" A polyphthalimide precursor having a repeating structure represented by the formula (1) is obtained, and the tetracarboxylic acid represented by the above formula (6) is contained. The method of mixing and reacting the tetracarboxylic dianhydride component of the anhydride with the diamine component containing the diamine represented by the above formula (7) and, if necessary, the diamine component represented by the above formula (Q1) in an organic solvent is simple. A method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent is exemplified by stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and directly adding a tetracarboxylic dianhydride directly or a method of dispersing or dissolving it in an organic solvent; conversely adding a diamine component to a solution of dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent; and mutually adding a tetracarboxylic dianhydride component and two Amine component method, etc. Further 'tetracarboxylic dianhydride component and diamine In the case where a plurality of compounds are present, the polymerization may be carried out by mixing the plurality of components in advance, or the polymerization may be carried out individually. The polymerization of the above polyimine precursor used in the present invention, tetracarboxylic acid The ratio of the acid dianhydride component to the diamine component, that is, the total mole number of the dicarboxylic acid di-gf component: <the total mole number of the diamine component> is preferably 1:0.5 to 1:1.5. Generally, the polymerization reaction is the same, and the molar ratio of the molar ratio is closer to 1: the greater the degree of polymerization of the U-branched U-batter produced by hydrazine, the greater the molecular weight. In the method for producing the polyimine precursor, the tetradecanoic acid is used. The dianhydride is -32-201031687. The temperature at which the diamine component is reacted in an organic solvent is usually from -20 to 150 ° C. Preferably, it is from 0 to 80 ° C. The polymerization temperature is set to a high temperature. It is carried out quickly and completely, but when it is too high, there is a case where a high molecular weight polyimine precursor cannot be obtained. Further, when the polymerization is carried out in an organic solvent, the two components in the solvent (tetracarboxylic anhydride component and diamine component) Solid mass concentration There is no particular limitation, but when the concentration is too low, it is difficult to obtain a high molecular weight polyimine precursor. When the concentration is too high, the viscosity of the reaction liquid is too high to be uniformly stirred, so it is preferably from 1 to 50% by mass, more preferably 5 to 30% by mass. It may be carried out at a high concentration in the initial stage of the polymerization, and then an organic solvent may be added together with the purification of the polymer (polyimine precursor). The organic solvent used in the above polymerization reaction is a polymer which can be dissolved. The quinone imine precursor is not particularly limited, but specific examples thereof include hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, and N-Φ methyl group. -2-pyrrolidone, N-methyl caprolactam, dimethyl sulfite, tetramethyl urea, pyridine, dimethyl maple, hexamethylarylene, r-butyrolactone and the like. These may be used singly or in combination of two or more. Further, even a solvent which cannot dissolve the polyimide precursor can be mixed in the solvent as long as it does not precipitate the formed polyimide precursor. The solution containing the polyimine precursor thus obtained can be used as it is in the formation of a film coating liquid which is formed below the image. Further, the polyimine precursor precipitate may be isolated and recovered in a weak solvent such as water, methanol or ethanol. -33- 201031687 [Polyimide] A polyimine precursor having a structure represented by the above formulas (1) and (4) (and the above formula (5)) can be made into a polyimine by dehydration ring closure . The method for the ruthenium imidization reaction is not particularly limited, but the imidization of a catalyzed ruthenium using a basic catalyst and an acid anhydride is less likely to cause a decrease in the molecular weight of the quinone imine during the ruthenium imidization reaction, and the ruthenium imidization The control of the rate is easier and better. The catalyst imidization can be carried out by stirring the aforementioned polyimine precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride for 1 to 1 hour. Further, the polyimine precursor may be used as it is (without isolation) a solution comprising a polyimide precursor obtained by polymerization of the above tetracarboxylic anhydride component and a diamine component. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity in carrying out the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferred because it is easier to purify the polyimine obtained after the quinone imidization. As the organic solvent, a solvent used in the polymerization of the above polyimine precursor can be used. The reaction temperature in the imidization of the catalyst oxime is preferably from -20 to 250 t, more preferably from 0 to 180 °C. When the reaction temperature is set to a high temperature, the imidization is rapidly progressed, but when the reaction temperature is too high, the molecular weight of the polyimine is lowered. The amount of the basic catalyst is preferably from 0.5 to 30 moles, more preferably from 2 to 20 moles, relative to the acid amide group in the aforementioned polyimide intermediate. Further, the amount of the acid anhydride is from 1 to 50 moles, more preferably from 3 to 30 moles, relative to the acid amide group in the aforementioned polyimide intermediate. By adjusting the above reaction temperature and the amount of the catalyst, the yield of the obtained ruthenium imine can be controlled. The reaction solution of the solvent-soluble polyimine obtained as described above can be directly used for the production of the gate insulating film described later, but since the reaction solution contains a ruthenium-based catalyst, it is preferred to use a polyimide. Purified • Recycled • Washed. A convenient method for recovering polyimine is to pour the reaction solution into a weak solvent under stirring to precipitate the polyimine and filter it. The weak solvent to be used at this time is not particularly limited, and may, for example, be methanol, hexane, heptane, ethanol, toluene, water or the like. After the precipitate is recovered by filtration, it is preferably washed with the above weak solvent. Φ The recovered polyimine can be dried at room temperature or under reduced pressure to become a polyimide pigment at normal temperature or under heat. The polyimine powder is further dissolved in a good solvent, and reprecipitation is repeated in a weak solvent for 2 to 1 time, and impurities in the polymer can be further reduced. The good solvent to be used at this time is not particularly limited as long as it is a soluble polyimide precursor or a polyimine, but examples thereof are, for example, N,N-dimethylformamide, N,N-dimethyl Acetamide, 2_pyrrolidone, N-methyl-2-pyrrole, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methyl-35- 201031687 Base hexamethyleneamine, dimethyl sulfoxide, tetramethyl urea, pyridine, r-butyrolactone and the like. Further, when three or more kinds of weak solvents such as alcohols, ketones, and hydrocarbons are used as the weak solvent for the re-sinking chamber, the purification efficiency can be further improved. [Formation film coating liquid under the image formation] 下 The underlayer film for forming an image of the present invention can be formed by forming a film coating liquid under the image. The film coating liquid under the formation of the image may be a coating liquid containing the above-mentioned polyimide precursor, the above-mentioned polyimine, and a solvent, and if necessary, a coupling agent or a surfactant which will be further described, It is preferred to contain a polyfluorene imine precursor obtained by reacting a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and a diamine component containing a diamine represented by the formula (7). Or a coating liquid of the polyimine obtained by subjecting the polyimine precursor to dehydration ring closure. [化31] Ο 〇

H2N-B-NH2 (7}H2N-B-NH2 (7}

(式中,A表示4價有機基,B表示以式(2)或(3)表 示之2價構造, -36 - 201031687 [化 32](wherein A represents a tetravalent organic group, and B represents a divalent structure represented by the formula (2) or (3), -36 - 201031687 [Chem. 32]

(3) Ο ιι S-C-X-Y-2 R1、R2分別獨立表示氫原子或1價有機基, 鍵或碳原子數6至20之2價芳香族基,Y表示 ' -COO- ' -OCO- ' -CONH- ' -CH2〇- ' -CH2COO -CH2CH2COO-,Z表示可經氟原子取代之碳原子 之脂肪族烴基,R各獨立表示氟原子、碳原子數 烷氧基或碳原子數1至3之烷基,t表示0至3 最好爲前述式(2)或(3)之Z表示任意 原子取代之碳原子數3至26之脂肪族烴基之 下層膜塗佈液。 前述之形成畫像之下層膜塗佈液中所用之 ❷ 胺前驅物及/或聚醯亞胺之分子量,就操作之 形成時之耐溶劑性等安定性之觀點而言,宜使用 (或聚環氧乙烷)換算之重量平均分子量(以 之結果)爲2,000至200,000,更好爲5,000至 〇 使用前述之形成畫像之下層膜塗佈液製作坨 下層膜,且照射紫外線時,關於親疏水性之變佔 聚醯亞胺前驅物與聚醯亞胺之間並無太大差異, 成畫像用下層膜以該點爲重點時,醯亞胺化率並 X表示單 單鍵、-Οι 數3至26 1至3之 之整數) ,原子經氟 :成畫像之 ’述聚醯亞 7易性、膜 聚乙二醇 GPC測定 50,000 者 '成畫像用 ,量由於在 故所得形 .無特別限 -37- 201031687 制。 然而,藉由使用聚醯亞胺,可獲得在塑膠基板可對應 之低溫燒成(1 8 0 °C以下)之信賴性高之膜的觀點而言, 由於聚醯亞胺比聚醯亞胺前驅物之極性低,可獲得提高紫 外線照射前之水接觸角(可提高疏水性)方面等之優點, 故以使用聚醯亞胺更佳。 另一方面,於重點爲絕緣性之形成畫像用下層膜(例 如閘極絕緣膜)中使用前述形成畫像之下層膜塗佈液時, 該塗佈液之醯亞胺化率較好爲90%以上。但,在不損及 溶劑溶解性之情況下亦可降低醯亞胺化率,但該情況下, 形成膜時,藉由使用後述之摻合手法使最下層成爲高醯亞 胺化(高絕緣性),可保有作爲下層膜之高絕緣性而爲有 用。 前述之形成畫像之下層膜塗佈液中使用之溶劑只要是 可溶解聚醯亞胺前驅物或聚醯亞胺者即無特別限制,其例 列舉爲Ν,Ν-二甲基甲醯胺、N,N-二甲基乙醯胺、2-吡咯 啶酮、N -甲基-2-吡咯啶酮、N -乙基-2-吡咯啶酮、N -乙稀 基-2-吡咯啶嗣、N-甲基己內醯胺、二甲基亞楓、四甲基 脲、吡啶、r-丁內酯等良溶劑。該等可單獨使用一種, 亦可混合使用,再者,亦可將醇類、酮類、烴等弱溶劑與 前述良溶劑混合使用。 前述形成畫像之下層膜塗佈液中之固體成分比例,只 要使亦包含後述之偶合劑等之各成分均勻溶解於溶劑中即 無特別的限制,例如爲1至3 0質量%,又例如爲5至2〇 -38- 201031687 質量%。其中,所謂固體成分係指自形成畫像之下層膜塗 佈液之全部成分去除溶劑者。 前述形成畫像之下層膜塗佈液之調製方法並無特別限 制,但亦可直接使用包含由前述之四羧酸酐成分及二胺成 分之聚合所得之聚醯亞胺前驅物之溶液’或者使用該溶液 所得之聚醯亞胺之反應溶液。 又,於前述之形成畫像之下層膜塗佈液中’爲提高該 Φ 塗佈液與基板之密著性,只要不損及本發明之效果’亦可 進而含有偶合劑。 上述偶合劑可列舉爲含有官能性矽烷之化合物或含有 環氧基之化合物,具體而言可列舉爲3-胺基丙基三甲氧 基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基 矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺 基丙基三甲氧基矽烷、N- (2-胺基乙基)-3-胺基丙基甲 基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基 φ 三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷 、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三甲氧基 矽烷基丙基三伸乙基三胺、N -三乙氧基砂烷基丙基三伸乙 基三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙 氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二 氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸 酯、N -苄基-3-胺基丙基三甲氧基矽烷、N_苄基_3_胺基丙 基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N_ 苯基-3-胺基丙基三乙氧基矽烷、N —雙(氧基伸乙基)-3_ -39- 201031687 胺基丙基三甲氧基矽烷、N-雙(氧基伸乙基)-3-胺基丙 基三乙氧基矽烷、乙二醇二縮水甘油醚、聚乙二醇二縮水 甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、 聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己 二醇二縮水甘油醚、丙三醇二縮水甘油醚、2,2-二溴新戊 二醇二縮水甘油醚、6-四縮水甘油基-2,4-己二醇、 N,N,N’,N’-四縮水甘油基-間-二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N’,N’-四縮水甘油 基-4,4’-二胺基二苯基甲烷等化合物。 該等可單獨使用一種,亦可組合兩種以上使用。 使用該偶合劑時,其含量相對於形成畫像之下層膜塗 佈液1〇〇質量份,較好以0.1至30質量份添加,更好爲1 至20質量份。 再者前述形成畫像之下層膜塗佈液中,爲提高該塗佈 液之塗佈性、自該塗佈液獲得之膜之膜厚均勻性或表面平 化性,亦可含有界面活性劑。 前述界面活性劑並無特別限制,列舉爲例如氟系界面 活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等。 該種界面活性劑列舉爲例如F TOP EF301、EF303、EF352 (Jam co (股)製造)、MEGAFACE F171、F173、R-30 ( 大曰本油墨化學(股)製造)、FLORARD FC430、FC431 (住友3M化學工業(股)製造)、ASAHIGUARD AG7 10 、SURFLON S-3 82、SC 1 0 1、SC 1 02、SC 1 03、SC 1 04、 SC105、SC106(旭硝子(股)製造)等。 201031687 使用該界面活性劑時’其含量相對於形成畫像之下層 膜塗佈液中所含之聚合物成分100質量份,較好爲0.01 至2質量份,更好爲0.01至1質量份。 [有關聚合物慘合物] 前述之形成畫像之下層膜塗佈液,除前述之聚醯亞胺 前驅物或聚醯亞胺以外,亦可混合可形成膜之其他聚合物 φ (例如高絕緣性聚合物),成爲所謂聚合物摻合物之形態 〇 該聚合物摻合物中,藉由適當調整含有之聚合物(前 述之聚醯亞胺前驅物、聚醯亞胺及其他聚合物)之構造等 ,可於形成畫像用下層膜形成時可於膜內厚度方向產生聚 合物之濃度梯度,故可利用作爲有用之手段。 例如,爲了主要在膜表面引起親疏水性之變化,就該 觀點而言,只要僅在形成畫像用下層膜之上層(表面層) φ 上存在有前述之於側鏈具有硫醇酯鍵之聚醯亞胺前驅物及 /或聚醯亞胺即可。 因此,使前述形成畫像之下層膜塗佈液設爲聚合物摻 合物之形態(以下將該形態之塗佈液稱爲摻合物塗佈液) 時,前述聚醯亞胺前驅物或聚醯亞胺之調配比例在該摻合 物塗佈液之固體成分中爲1質量%至100質量%。若爲1 質量%以下時,於膜上形成該摻合物塗佈液時難以完全覆 蓋膜之最表面,而有形成畫像之能力劣化之虞。 上述聚合物摻合物成爲有用者可列舉爲例如要求特別 -41 - 201031687 高絕緣性之閘極絕緣膜用途中使用前述形成畫像之下層膜 塗佈液之情況。 用於閘極絕緣膜用途時,該塗佈液被要求有對應於 1 80 °C以下之燒成溫度、可藉由塗佈成膜、對於有機半導 體塗佈液之耐溶劑性(二甲苯、三甲基苯等極性溶劑)、 低吸水率等之各種特性,但關於絕緣性之要求性能特別高 。爲達成此高絕緣性,前述之形成畫像之下層膜塗佈液之 醯亞胺化率至少爲80%以上,依據情況有時亦要求90% 以上,但相反地,醯亞胺化率超過90 %以上時會喪失溶 劑溶解性。此時,藉由僅使高絕緣性之層位在該絕緣膜之 最下層,由前述之形成畫像之下層膜塗佈液所構成之層爲 在上層,可保有該絕緣膜之高絕緣性,且亦可消除溶解性 問題。 如上述,爲了使形成畫像用下層膜之下層成爲高絕緣 層,上層爲親疏水性變換層,亦可將該等層依序層合製作 ,但操作相當繁雜。 此時,將高絕緣層之材料與親疏水性變換層之材料( 亦即前述之聚醯亞胺前驅物及/或聚醯亞胺)混合,此時 ,若使上層材料之極性或分子量比下層者小,則將混合物 塗佈於基板上並經乾燥使溶劑蒸發之過程中,由於顯示上 層材料移行至表面而形成層之舉動,故可輕易地控制上述 濃度梯度(此處稱爲層分離)。 可形成前述下層之高絕緣性膜之形成材料最佳者爲可 溶性聚醯亞胺。使用可溶性聚醯亞胺作爲下層材料時,就 -42- 201031687 絕緣性之觀點而言,以溶液中之聚醯亞胺之醯亞胺化率高 者較佳,至少爲50%以上,較好爲80%以上,最好爲90 %以上。 可作爲下層材料使用之其他材料列舉爲環氧樹脂、丙 烯酸樹脂、聚丙烯、聚乙烯醇、聚乙烯酚、聚異丁烯、聚 甲基丙烯酸甲酯等之一般有機聚合物。 至於較佳之可溶性聚醯亞胺列舉爲由選自由式(1 6 ) 0 之構造所構成群組之一種或複數種之構造所構成之可溶性 聚醯亞胺。 [化 33](3) Ο ιι SCXY-2 R1 and R2 each independently represent a hydrogen atom or a monovalent organic group, a bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents '-COO- ' -OCO- ' -CONH - '-CH2〇- '-CH2COO -CH2CH2COO-, Z represents an aliphatic hydrocarbon group of a carbon atom which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, a carbon atom alkoxy group or an alkyl group having 1 to 3 carbon atoms The base, t represents 0 to 3, and preferably Z of the above formula (2) or (3) represents an aliphatic hydrocarbon group underlayer coating liquid having 3 to 26 carbon atoms substituted by any atom. The molecular weight of the guanamine precursor and/or polyimine used in the film coating liquid formed under the above-mentioned image formation is preferably used in view of stability such as solvent resistance at the time of formation of the operation (or poly ring). The weight average molecular weight (as a result of oxyethylene) is 2,000 to 200,000, more preferably 5,000 to 〇. The underlayer film is formed by using the above-mentioned layer film coating liquid under the image formation, and when irradiated with ultraviolet rays, regarding the hydrophilicity and hydrophobicity There is not much difference between the polyimine precursor and the polyimine. When the lower layer of the image is focused on this point, the imidization ratio and X represent the single bond, -Οι 3 to 26 The integer of 1 to 3), the atomic fluorine: the image of the 'representation of the polyether, the film polyethylene glycol GPC determination of 50,000 'for the portrait, the amount due to the resulting shape. No special limit -37 - 201031687 system. However, by using polyimine, it is possible to obtain a highly reliable film which can be fired at a low temperature (less than 180 ° C), which is a polyimine. Since the polarity of the precursor is low, the advantage of improving the water contact angle (which can improve the hydrophobicity) before the ultraviolet irradiation can be obtained, and therefore it is more preferable to use the polyimide. On the other hand, when the underlayer film coating liquid is formed in the underlayer film (for example, a gate insulating film) which is mainly used for forming an insulating layer, the coating solution has a yttrium imidation ratio of preferably 90%. the above. However, the ruthenium imidization ratio can be lowered without impairing the solvent solubility. However, in this case, when the film is formed, the lowermost layer is made into a high-yield imidization by using a blending method described later (high insulation). It is useful to retain high insulation as a lower film. The solvent to be used in the film coating liquid for forming the image layer described above is not particularly limited as long as it is a soluble polyimide precursor or a polyimide, and examples thereof include hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-ethlyl-2-pyrrolidinium , N-methyl caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, r-butyrolactone and other good solvents. These may be used singly or in combination, and a weak solvent such as an alcohol, a ketone or a hydrocarbon may be used in combination with the above-mentioned good solvent. The ratio of the solid content in the layer coating liquid to be formed in the image formation layer is not particularly limited as long as the components including the coupling agent to be described later are uniformly dissolved in the solvent, and are, for example, 1 to 30% by mass, for example, 5 to 2〇-38- 201031687% by mass. Here, the solid content means that the solvent is removed from all the components of the layer coating liquid under the formation image. The method for preparing the layer coating liquid under the formation of the image is not particularly limited, but a solution containing a polyimine precursor obtained by polymerization of the tetracarboxylic anhydride component and the diamine component described above may be used as it is or used. The reaction solution of the polyimine obtained by the solution. Further, in the layer coating liquid under the image formation described above, the coupling agent may be further contained in order to improve the adhesion between the Φ coating liquid and the substrate without impairing the effects of the present invention. The coupling agent may, for example, be a compound containing a functional decane or a compound containing an epoxy group, and specific examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 2 -Aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-amine Benzyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyl φ triethoxy decane, N-ethoxycarbonyl- 3-Aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-trimethoxydecylpropyltriethylamine, N-triethyl Oxyalkylalkylpropyltriethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-tri Azadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N- Benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-I-propylpropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxy Baseline, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl)-3_-39- 201031687 Aminopropyltrimethoxydecane, N-bis (oxyethyl) 3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 6-tetrahydration Glyceryl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino) a compound such as cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane. These may be used alone or in combination of two or more. When the coupling agent is used, the content thereof is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per part by mass of the film coating liquid under the formation of the image. Further, in the layer coating liquid for forming the image, the surfactant may be contained in order to improve the coating property of the coating liquid, the film thickness uniformity or the surface flatness of the film obtained from the coating liquid. The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. Such surfactants are listed, for example, as F TOP EF301, EF303, EF352 (manufactured by Jam Co), MEGAFACE F171, F173, R-30 (manufactured by Otsuka Ink Chemicals Co., Ltd.), FLORARD FC430, FC431 (Sumitomo 3M Chemical Industry Co., Ltd., ASAHIGUARD AG7 10, SURFLON S-3 82, SC 1 0 1 , SC 1 02, SC 1 03, SC 1 04, SC105, SC106 (made by Asahi Glass Co., Ltd.). In the case of using the surfactant, the content is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component contained in the film coating liquid under the formation of the image. [Related Polymer Phenomenon] The above-mentioned layered film coating liquid can be mixed with other polymer φ (for example, high insulation) which can form a film in addition to the above-mentioned polyimine precursor or polyimine. a polymer), in the form of a so-called polymer blend, by appropriately adjusting the polymer (the aforementioned polyimine precursor, polyimine and other polymers) The structure or the like can form a concentration gradient of the polymer in the thickness direction of the film when the underlayer film for image formation is formed, and thus can be utilized as a useful means. For example, in order to cause a change in the hydrophobicity of the film mainly on the surface of the film, as far as this is concerned, the above-mentioned layer having a thiol bond in the side chain exists only on the layer (surface layer) φ of the underlayer film for forming an image. The imine precursor and/or polyimine can be used. Therefore, when the film formation liquid under the formation of the image forming film is in the form of a polymer blend (hereinafter, the coating liquid of the form is referred to as a blend coating liquid), the polyimine precursor or the poly The blending ratio of the quinone imine is 1% by mass to 100% by mass in the solid content of the blend coating liquid. When it is 1% by mass or less, it is difficult to completely cover the outermost surface of the film when the blend coating liquid is formed on the film, and the ability to form an image is deteriorated. The above-mentioned polymer blend is useful, for example, in the case where a gate insulating film for forming an image is used in the use of a gate insulating film which is required to have a high insulating property of -41 - 201031687. When it is used for a gate insulating film, the coating liquid is required to have a firing temperature corresponding to 1 80 ° C or lower, a film formation by coating, and a solvent resistance to an organic semiconductor coating liquid (xylene, Various properties such as a low solvent such as trimethylbenzene and a low water absorption rate, but the performance required for insulation is particularly high. In order to achieve such high insulation properties, the imidization ratio of the film coating liquid formed under the above-described image formation layer is at least 80% or more, and may be required to be 90% or more depending on the case, but conversely, the sulfhydrylation ratio exceeds 90%. Solubility is lost when it is above %. In this case, by providing only a layer having a high insulating property in the lowermost layer of the insulating film, the layer formed by the layer coating liquid under the image formation described above is in the upper layer, and the insulating property of the insulating film can be maintained. It also eliminates solubility problems. As described above, in order to form the lower layer of the lower layer film for forming an image as a high insulating layer, and the upper layer is a hydrophilic/hydrophobic conversion layer, the layers may be laminated in this order, but the operation is rather complicated. At this time, the material of the high insulating layer is mixed with the material of the hydrophilic-hydrophobic conversion layer (that is, the aforementioned polyimine precursor and/or polyimine), and at this time, if the polarity or molecular weight of the upper material is lower than the lower layer If the mixture is coated on a substrate and dried to evaporate the solvent, the above-mentioned concentration gradient (herein referred to as layer separation) can be easily controlled by the action of forming the layer by moving the upper layer material to the surface. . The material for forming the high insulating film of the lower layer described above is preferably a soluble polyimide. When a soluble polyimine is used as the underlayer material, from the viewpoint of the insulating property of -42 to 201031687, it is preferred that the sulfhydryl imidization ratio of the polyimine in the solution is high, at least 50% or more. It is 80% or more, preferably 90% or more. Other materials which can be used as the underlayer material are exemplified by general organic polymers such as epoxy resin, acrylic resin, polypropylene, polyvinyl alcohol, polyvinyl phenol, polyisobutylene, and polymethyl methacrylate. The preferred soluble polyimine is exemplified by a soluble polyimine consisting of one or a plurality of structures selected from the group consisting of the structures of the formula (1 6 ) 0 . [化33]

(式中A表示脂肪族環或僅由脂肪族所構成之4價有機 基,D表示2價有機基)。 前述可溶性聚醯亞胺之分子量宜使用聚乙二醇(或聚 環氧乙烷)換算之重量平均分子量(以GPC測定之結果 )較好爲2,000至200,000,更好爲5,000至50,000者° 式(16 )中,A之具體例列舉爲選自A-1至A-25之 4價有機基,D之具體例列舉爲D-1至D-57。其中’就使 可溶性聚醯亞胺具有高溶解性之觀點而言’最好A之構 造爲 A-5、 A-6、 A-16、 A-18、 A-19、 A-20、 A-21、 A-22 、A-25之4價有機基’ D之構造爲D-7、D-8、D-9、D-12 、D-19 、 D-20 、 D-22 、 D-29 、 D-39 、 D-41 、 D-42 之 2 價 -43- 201031687 有機基。 該等可溶性聚醯 〇 又,上述聚合物 左右之有機電晶體用 所必要之前述聚醯亞 摻合物中之含有比例 像用之下層膜表面物 5質量%以上。 [塗膜及形成畫像用1 以浸漬法、旋轉 墨法、噴佈法、刷毛 塗佈液塗佈於聚丙烯 乙二酯、聚醚碾、聚 用之塑膠基板或玻璃 等預乾燥,藉此形成 理,形成可作爲形成 像用下層膜。 上述加熱處理方 板或烘箱,在適當氛 體、真空等中進行之 燒成溫度就促進 言,較好爲1 8 0 °C至 亞胺可單獨使用亦可組合複數種使用 ^摻合物使用於例如要求膜厚40〇nm 途時’設置上層(親疏水性變換層) 胺前驅物及/或聚醯亞胺在該聚合物 爲1質量%以上即可。過少時形成畫 性之面內有偏差較大之情況。較好爲 '層膜之製造方法] 塗佈法、轉印印刷法、輥塗佈法、噴 塗佈等,將前述之形成畫像之下層膜 、聚乙烯、聚碳酸酯、聚對苯二甲酸 萘二甲酸乙二酯、聚醯亞胺等廣泛使 基板等之上,隨後,以加熱板或烘箱 塗膜。隨後藉由使該塗膜進行加熱處 畫像用下層膜或絕緣膜使用之形成畫 法並無特別限制,可例示爲使用加熱 圍氣體中,亦即大氣、氮氣等惰性氣 方法。 聚醯亞胺前驅物之熱醯亞胺之觀點而 250°C,由在塑膠基板上成膜之觀點 -44- 201031687 而言更好爲180°C以下。 燒成亦可使用兩階段以上之溫度變化。階段性燒成可 更提高所得膜之均勻性。 又製作形成畫像用下層膜時,形成畫像之下層膜塗佈 液由於爲包含聚醯亞胺前驅物及/或聚醯亞胺及上述溶劑 之形態,故可直接用於基板之塗佈,但爲了調整濃度,或 確保塗膜之平坦性,或提高塗佈液對基板之潤濕性、塗佈 φ 液之表面張力、極性、沸點之調整等之目的,亦可添加上 述溶劑、額外之其他各種溶劑作爲塗佈液使用。 該等溶劑之具體例,除上述說明書第29頁第一段所 述之溶劑以外,可列舉有乙基溶纖素、丁基溶纖素、乙基 卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇等,1 -甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙 二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯 φ 、二丙二醇、2-(2 -甲氧基丙氧基)丙醇、2_(2_乙氧基 丙氧基)丙醇及2- ( 2-丁氧基丙氧基)丙醇等丙二醇衍生 物’乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸正丁酯、乳 酸異戊酯等乳酸衍生物等。該等可單獨使用亦可倂用。 又’就提高塗佈液之保存性、塗膜之膜厚均勻性之觀 點,較好全部溶劑量之20至80質量%係選自N,N-二甲 基甲醯胺、N,N-二甲基乙醯胺、N_甲基-2-吡咯啶酮、r -丁內酯、二甲基亞颯之至少一種溶劑。 塗佈液之濃度並無特別限制,但聚醯亞胺前驅物及聚 -45- 201031687 醯亞胺之固成分濃度較好爲0·1至30質量%,更好爲1 至10質量%。該等可藉由塗佈裝置之規格或所得膜厚任 意設定。 如上述製作之本發明之形成畫像用下層膜使用作爲形 成畫像用下層膜時,若膜厚太薄則經紫外線照射後之圖型 化性降低,又若太厚則將損及表面均勻性。據此,其膜厚 較好爲5nm至lOOOnm,更好爲10nm至300nm,最好爲 20nm 至 1 OOnm 〇 另外’本發明之形成畫像用下層膜在絕緣性充分高之 情況下亦可作爲絕緣膜發揮機能。該情況下,該形成畫像 用下層膜在例如有機FET元件中,係直接配置在閘極電 極上作爲閘極絕緣膜使用。此時,該形成畫像用下層膜之 膜厚爲了確保絕緣性’較好比作爲上述形成畫像用下層膜 使用時更厚。其膜厚較好爲20nm至lOOOnm,更好爲 50nm 至 800 nm,最好爲 l〇〇nm 至 500nm° [形成畫像用電極之製造方法] 對本發明之形成畫像用下層膜以圖型狀照射紫外線, 接著’藉由塗佈後述之畫像形成液,可製造形成畫像用電 極。 本發明中’對上述形成畫像用下層膜以圖型狀照射紫 外線之方法並無特別限制,列舉爲例如透過描繪有電極圖 型之遮罩進行照射之方法’使用雷射光描繪電極圖型之方 法等。 -46- 201031687 上述遮罩之材質或形狀並無特別限制,只要使電極必 要之區域透過紫外線,其以外之區域不透過紫外線即可。 此時’所用紫外線之波長通常爲200nm至5〇Onm之 範圍,較好選擇符合使用之形成畫像用下層膜之種類之適 宜紫外線波長。具體而言列舉爲248nm、254nm、3 03nm 、313nm、365nm 等波長。最好爲 248nm、254nm。 本發明之形成畫像用下層膜係藉由紫外線照射使其表 φ 面能量緩慢上升’成爲充分照射量同時飽和。該表面能量 之上升導致畫像形成液之接觸角降低,結果提高紫外線照 射部之畫像形成液之潤濕性。 據此’在經紫外線照射後之本發明形成畫像用下層膜 上塗佈畫像形成液時,沿著於形成畫像用下層膜上以表面 能量差所描繪之圖型形狀,畫像形成液形成自我組織之圖 型,可獲得任意圖型形狀之電極。 據此,對形成畫像用下層膜之紫外線照射量有必要照 魯 射使畫像形成液之接觸角充分變化之量,但就能量效率與 縮短製造步驟之時間等方面而言,較好爲20J/Cm2以下, 更好爲l〇J/cm2以下,最好爲5J/cm2以下。 又,形成畫像用下層膜之紫外線照射部與未照射部之 畫像形成液之接觸角差異愈大愈容易圖型化,使電極加工 成複雜之圖型或細微之圖型成爲可能。因此,由紫外線照 射引起之接觸角變化量較好爲5°以上,更好爲10°以上, 最好爲20°以上。 基於同樣理由,較好畫像形成液之接觸角在紫外線未 -47- 201031687 照射部爲30°以上,在紫外線照射部爲20°以下。 又目前,由於畫像形成液之溶劑大多使用水,故對下 層膜之性能評價,亦可簡易地以水之接觸角變化量代替前 述畫像形成液接觸角之變化量進行評價。 本發明中所謂的畫像形成液爲塗佈於基板上之後,藉 由蒸發掉其中所含之溶劑,而可作爲機能性薄膜使用之塗 佈液,列舉爲例如使電荷輸送性物質溶解或均勻分散於至 少一種溶劑中而成者。此處,所謂電荷輸送性係與導電性 同義,意指電洞輸送性、電子輸送性、電洞及電子之二電 荷輸送性之任一種。 上述電荷輸送性物質只要具有可輸送電洞或電子之導 電性即無特別限制。其實例列舉爲例如金、銀、銅、鋁等 金屬微粒子或碳黑、富勒烯類、碳奈米管等無機材料,或 聚噻吩、聚苯胺、聚吡咯、聚莽及該等之衍生物等有機π 共軛聚合物等。 又,爲了提高電荷輸送物質之電荷輸送能,亦可於畫 像形成液中進一步添加鹵素、路易士酸、質子酸、過渡金 屬化合物(具體例爲 Br2、I2、Cl2、FeCl3、MoC15、BF3 、asf5、so3、hno3、H2S04、聚苯乙烯磺酸等)等之電 荷接受性物質’或者鹼金屬、烷基敍離子(具體例爲Li 、Na、K、Cs、四伸乙基銨、四丁基銨等)等電荷供給物 質作爲摻雜物。 畫像形成液之溶劑只要是可使上述電荷輸送性物質或 摻雜物溶解或均勻分散者即無限制。但,就獲得正確之電 -48 · 201031687 極圖型之觀點而言,較好對於形成畫像用下層膜之紫外線 未照射部顯示足夠大之接觸角,且就對於本發明之形成畫 像用下層膜之損害較少而言,較好爲水或各種醇類。 又’ N,N-二甲基甲醯胺、N,N_二甲基乙醯胺、2_吡略 D定酮、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-乙烯 基-2-吡咯啶酮、N_甲基己內醯胺、二甲基亞碾、四甲基 脲等極性溶劑對有機系電荷輸送性物質之溶解性亦優異 φ 就對於形成畫像用下層膜之紫外線未照射部顯示足夠大之 接觸角之觀點而言較佳,但該等較好在對本發明之形成畫 像用下層膜之損壞最少之範圍內使用。 畫像形成液中之電荷輸送性物質之濃度較好爲〇 . 〇 i 至30質量% ’更好爲〇.〗至10質量%,最好爲1至5質 量%。 本發明之畫像形成液之具體例列舉爲Baytron (註冊 商標)P (聚伸乙基二氧基噻吩,Bayer公司製造)等。 φ 本發明之電極係將上述畫像形成液塗佈於本發明之形 成畫像用下層膜上,形成圖型後,使溶劑蒸發而製作。溶 劑之蒸發方法並無特別限制,但可使用加熱板或烘箱,在 適當氛圍氣體中,亦即大氣、氮氣等惰性氣體、真空中等 進行蒸發,獲得均勻之成膜面。 蒸發溶劑之溫度並無特別限制,較好在40至2 5 0 t: 進行。就達成圖型形狀之維持及膜厚均勻性等之觀點而言 ,亦可利用兩階段以上之溫度變化。 由該畫像形成液作成之電極不僅可利用使用作爲連接 -49- 201031687 電子裝置彼此之配線,亦可利用作爲電場效電晶體、雙極 電晶體、各種二極體、各種感應器等電子裝置之電極等。 本發明之電子裝置爲具有上述本發明之電極者。 以下顯示於有機FET元件中使用本發明之形成畫像 用下層膜之例,但本發明並不限於該等。 首先準備高摻雜型η型矽基板。較好基板預先以洗劑 、醇、純水等進行液體洗淨而淨化,在使用之前進行臭氧 處理,氧-電漿處理等表面處理。以熱氧化、濺鍍、CVD _ 、蒸鍍等方法將Si02、Ta205、Α12〇3等成膜於基板上, 形成閘極絕緣膜。閘極絕緣膜之膜厚隨有機FET之用途 而不同,但就兼顧驅動電壓與電絕緣性而言,較好爲 30nm至lOOOnm之範圍。 接著,於絕緣膜上依前述順序形成含有具有以前述通 式(1)表示之重複構造之聚醯亞胺前驅物及/或聚醯亞 胺之層。層之膜厚較好爲20nm至lOOnm。隨後,使用欲 獲得期望電極形狀之遮罩等照射紫外線。 @ 接著,將使用水等極性溶劑之畫像形成液塗佈於形成 畫像用下層膜表面上。經塗佈之畫像形成液排斥疏水性部 (紫外線未照射部)並加速擴展至親水性部(紫外線照射 部)而安定化,使之乾燥,形成圖型化之源極及汲極電極 。畫像形成液之塗佈法不特別限定於旋轉塗佈法、澆鑄法 等,但較好爲易控制液量之噴墨印刷法或噴佈塗佈法。 最後,使有機FET之活性層的并五苯、聚烯烴等之 有機半導體材料成膜而完成。有機半導體材料之成膜方法 -50- 201031687 並未特別限制,但舉例有例如真空蒸鍍或使溶液旋轉塗佈 法'澆鑄法、噴墨印刷法或噴佈塗佈法等。 如此’所製作之有機FET可大幅削減製造步驟,再 者可製作比遮罩蒸鍍法更短通道之有機FET,故於使用低 移動度之有機半導體材料作爲活性層時,亦可能取出大電 流。又,由本發明方法所得之形成畫像用下層膜亦具有優 異之電絕緣性,故亦可使用作爲閘極絕緣層,製造步驟可 φ 更簡略化。 [實施例] 以下以實施例更詳細說明本發明,但本發明並不受該 等之限制。 [數平均分子量及重量平均分子量之測定] 依循以下合成例獲得之聚酿亞胺前驅物之數平均分子 • 量(以下稱爲Μη)及重量平均分子量(以下稱爲Mw) 係以GPC (常溫凝膠滲透層析儀)’以下述裝置及測定條 件測定,且以聚乙二醇(或聚環氧乙烷)換算値算出。 GPC裝置:昭和電工(股)製造之shodex(註冊商 標)(GPC-101 ) 管柱:昭和電工(股)製造之Sh〇dex (註冊商標) (KD803、KD805 串聯)(In the formula, A represents an aliphatic ring or a tetravalent organic group composed only of an aliphatic group, and D represents a divalent organic group). The molecular weight of the above-mentioned soluble polyimine is preferably a weight average molecular weight (as a result of GPC) in terms of polyethylene glycol (or polyethylene oxide), preferably from 2,000 to 200,000, more preferably from 5,000 to 50,000. In (16), specific examples of A are exemplified by a tetravalent organic group selected from A-1 to A-25, and specific examples of D are exemplified as D-1 to D-57. Among them, 'the best A's structure is A-5, A-6, A-16, A-18, A-19, A-20, A- from the viewpoint of high solubility of soluble polyimine. 21. The structure of the 4-valent organic group 'D of A-22 and A-25 is D-7, D-8, D-9, D-12, D-19, D-20, D-22, D-29 2, D-39, D-41, D-42 2 -43- 201031687 organic base. The soluble polyfluorene 〇 〇 , 〇 有机 有机 有机 有机 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [Application film 1 and the use of a dipping method, a rotary ink method, a spray method, and a brush coating liquid are applied to a polyethylene substrate, a polyether mill, a plastic substrate for polysilicon, or glass for pre-drying. The formation is formed to form an underlayer film for forming an image. In the above-mentioned heat-treated square plate or oven, the firing temperature in a suitable atmosphere, vacuum or the like is promoted, preferably from 180 ° C to imine, which may be used alone or in combination of plural kinds of use. For example, when the film thickness is required to be 40 〇 nm, the upper layer (hydrophobic hydrophobic conversion layer) of the amine precursor and/or the polyimine may be used in an amount of 1% by mass or more. When there is too little, there is a case where there is a large deviation in the form of the image. Preferably, the method for producing a film is a coating method, a transfer printing method, a roll coating method, a spray coating, or the like, and the above-mentioned underlayer film, polyethylene, polycarbonate, and polyterephthalic acid are formed. Ethylene naphthalate, polyimine, and the like are widely used on a substrate or the like, and then coated on a hot plate or an oven. The patterning method for forming the image by the underlayer film or the insulating film by heating the coating film is not particularly limited, and may be exemplified by using an inert gas such as air or nitrogen gas in the heating surrounding gas. The viewpoint of the thermal imine imine of the polyimide precursor is 250 ° C, and it is preferably 180 ° C or less from the viewpoint of film formation on a plastic substrate -44 - 201031687. It is also possible to use a temperature change of two or more stages for firing. The staged firing can further improve the uniformity of the resulting film. When the underlayer film for forming an image is formed, the film coating liquid under the image formation can be directly used for coating the substrate because it is in the form of a polyimide precursor and/or a polyimide and the solvent. In order to adjust the concentration, or to ensure the flatness of the coating film, or to improve the wettability of the coating liquid to the substrate, the surface tension of the coating φ liquid, the polarity, the boiling point adjustment, etc., the above solvent may be added, and the others may be added. Various solvents are used as the coating liquid. Specific examples of such solvents include, in addition to the solvent described in the first paragraph of the above-mentioned specification, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl card. Alcohol acetate, ethylene glycol, etc., 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate φ, dipropylene glycol , propylene glycol derivatives such as 2-(2-methoxypropoxy)propanol, 2-(2-ethoxypropoxy)propanol and 2-(2-butoxypropoxy)propanol A lactic acid derivative such as methyl ester, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate. These can be used alone or in combination. Further, from the viewpoint of improving the preservability of the coating liquid and the uniformity of the film thickness of the coating film, preferably 20 to 80% by mass of the total amount of the solvent is selected from N,N-dimethylformamide, N,N- At least one solvent of dimethylacetamide, N-methyl-2-pyrrolidone, r-butyrolactone, dimethylhydrazine. The concentration of the coating liquid is not particularly limited, but the solid concentration of the polyimine precursor and the poly-45-201031687 quinone is preferably from 0.1 to 30% by mass, more preferably from 1 to 10% by mass. These can be arbitrarily set by the specification of the coating device or the resulting film thickness. When the underlayer film for forming an image of the present invention produced as described above is used as the underlayer film for forming an image, if the film thickness is too thin, the pattern property after ultraviolet irradiation is lowered, and if it is too thick, the surface uniformity is impaired. Accordingly, the film thickness is preferably from 5 nm to 100 nm, more preferably from 10 nm to 300 nm, most preferably from 20 nm to 100 nm. Further, the underlayer film for forming an image of the present invention can also be used as an insulating layer in the case where the insulating property is sufficiently high. The membrane functions. In this case, the underlayer film for forming an image is used as a gate insulating film directly on the gate electrode, for example, in an organic FET device. In this case, the film thickness of the underlayer film for forming an image is preferably thicker than that of the underlayer film for forming the image. The film thickness is preferably from 20 nm to 100 nm, more preferably from 50 nm to 800 nm, and most preferably from 10 nm to 500 nm. [Method for Producing Electrode for Forming Image] The underlayer film for forming an image of the present invention is irradiated in a pattern Ultraviolet rays, then, by applying an image forming liquid described later, an electrode for forming an image can be produced. In the present invention, the method of irradiating ultraviolet rays in the form of the lower layer film for forming the image is not particularly limited, and is, for example, a method of irradiating with a mask having an electrode pattern, and a method of drawing an electrode pattern using laser light. Wait. -46- 201031687 The material or shape of the above mask is not particularly limited as long as the necessary area of the electrode is transmitted through the ultraviolet ray, and the area other than the ultraviolet ray is not transmitted. At this time, the wavelength of the ultraviolet light used is usually in the range of 200 nm to 5 Å Onm, and it is preferable to select an appropriate ultraviolet wavelength which is suitable for the type of the underlayer film for forming an image to be used. Specifically, wavelengths of 248 nm, 254 nm, 303 nm, 313 nm, and 365 nm are listed. It is preferably 248 nm or 254 nm. In the formation of the image of the present invention, the surface of the lower layer film is slowly increased by ultraviolet irradiation, and the surface is saturated with sufficient irradiation amount. This increase in surface energy causes a decrease in the contact angle of the image forming liquid, and as a result, the wettability of the image forming liquid in the ultraviolet ray irradiation portion is improved. According to this, when the image forming liquid is applied to the underlayer film for forming an image of the present invention after ultraviolet irradiation, the image forming liquid forms a self-organized shape along the pattern shape drawn by the surface energy difference on the underlying film for forming the image. With the pattern, an electrode of any shape can be obtained. According to this, it is necessary to sufficiently change the contact angle of the image forming liquid to the ultraviolet irradiation amount of the underlayer film for forming an image. However, in terms of energy efficiency and time for shortening the manufacturing step, it is preferably 20 J/ Below Cm2, it is more preferably l〇J/cm2 or less, and most preferably 5 J/cm2 or less. Further, the larger the difference in the contact angle between the ultraviolet ray irradiated portion forming the lower layer film for the image and the image forming liquid in the unirradiated portion, the easier the patterning is, and the electrode can be processed into a complicated pattern or a fine pattern. Therefore, the amount of change in contact angle caused by ultraviolet irradiation is preferably 5 or more, more preferably 10 or more, and most preferably 20 or more. For the same reason, the contact angle of the preferred image forming liquid is 30° or more in the ultraviolet ray-free period from -47 to 201031687, and is 20° or less in the ultraviolet ray irradiation unit. Further, since water is often used as the solvent for the image forming liquid, the performance evaluation of the underlayer film can be easily evaluated by changing the contact angle of the image forming liquid in accordance with the amount of change in the contact angle of water. The image forming liquid in the present invention is a coating liquid which can be used as a functional film by evaporating the solvent contained therein after being applied onto a substrate, and is, for example, dissolved or uniformly dispersed in a charge transporting substance. It is made up of at least one solvent. Here, the charge transport property is synonymous with conductivity, and means any one of hole transportability, electron transport property, and electron and electron transport properties. The charge transporting substance is not particularly limited as long as it has conductivity capable of transporting holes or electrons. Examples thereof are metal fine particles such as gold, silver, copper, aluminum, or inorganic materials such as carbon black, fullerenes, and carbon nanotubes, or polythiophenes, polyanilines, polypyrroles, polyfluorenes, and derivatives thereof. Such as organic π conjugated polymers and the like. Further, in order to increase the charge transporting ability of the charge transporting substance, a halogen, a Lewis acid, a protonic acid, or a transition metal compound may be further added to the image forming liquid (specific examples are Br2, I2, Cl2, FeCl3, MoC15, BF3, and asf5). , charge accepting substance such as so3, hno3, H2S04, polystyrenesulfonic acid, etc.' or an alkali metal or an alkyl group (specific examples are Li, Na, K, Cs, tetraethylammonium, tetrabutyl) A charge supply substance such as ammonium or the like is used as a dopant. The solvent of the image forming liquid is not limited as long as it can dissolve or uniformly disperse the above-mentioned charge transporting substance or dopant. However, from the viewpoint of obtaining a correct electro-type pattern, it is preferable to display a sufficiently large contact angle with respect to the ultraviolet non-irradiated portion forming the underlayer film for image formation, and to form an underlayer film for the image forming of the present invention. In terms of less damage, it is preferably water or various alcohols. Also 'N,N-dimethylformamide, N,N-dimethylacetamide, 2-pyrrolidine, N-methyl-2-pyrrolidone, N-ethyl-2- Polar solvents such as pyrrolidone, N-vinyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sub-milling, and tetramethyl urea are also excellent in solubility in organic charge transporting substances. It is preferable from the viewpoint of exhibiting a sufficiently large contact angle with respect to the ultraviolet non-irradiated portion of the underlayer film for image formation, but these are preferably used in the range which minimizes damage to the underlayer film for forming an image of the present invention. The concentration of the charge transporting substance in the image forming liquid is preferably 〇. 〇 i to 30% by mass ‘more preferably 〇 to 10% by mass, preferably 1 to 5% by mass. Specific examples of the image forming liquid of the present invention include Baytron (registered trademark) P (polyethylidene dioxythiophene, manufactured by Bayer Co., Ltd.). φ The electrode of the present invention is produced by applying the above-mentioned image forming liquid to the underlayer film for forming an image of the present invention, forming a pattern, and evaporating the solvent. The evaporation method of the solvent is not particularly limited, but it can be evaporated by using a hot plate or an oven in an appropriate atmosphere, that is, an inert gas such as air or nitrogen, or a vacuum to obtain a uniform film formation surface. The temperature of the solvent to be evaporated is not particularly limited, and is preferably carried out at 40 to 250 t:. From the viewpoint of maintaining the shape of the pattern and uniformity of the film thickness, it is also possible to use a temperature change of two or more stages. The electrode formed of the image forming liquid can be used not only as a wiring for connecting electronic devices of the connection -49-201031687, but also as an electronic device such as an electric field effect transistor, a bipolar transistor, various diodes, or various inductors. Electrodes, etc. The electronic device of the present invention is the electrode having the above-described present invention. The following is an example in which the underlayer film for forming an image of the present invention is used in an organic FET device, but the present invention is not limited to these. First, a highly doped n-type germanium substrate is prepared. Preferably, the substrate is preliminarily cleaned by washing with a lotion, alcohol, pure water or the like, and subjected to surface treatment such as ozone treatment or oxygen-plasma treatment before use. SiO 2 , Ta 205 , Α 12 〇 3 or the like is formed on the substrate by thermal oxidation, sputtering, CVD _ , vapor deposition, or the like to form a gate insulating film. The film thickness of the gate insulating film varies depending on the use of the organic FET, but it is preferably in the range of 30 nm to 100 nm in terms of driving voltage and electrical insulating properties. Next, a layer containing a polyimide precursor having a repeating structure represented by the above formula (1) and/or a polyimide is formed on the insulating film in the above-described order. The film thickness of the layer is preferably from 20 nm to 100 nm. Subsequently, ultraviolet rays are irradiated using a mask or the like for obtaining a desired electrode shape. @ Next, an image forming liquid using a polar solvent such as water is applied onto the surface of the underlayer film for forming an image. The applied image forming liquid repels the hydrophobic portion (ultraviolet-irradiated portion) and accelerates to the hydrophilic portion (ultraviolet irradiation portion) to be stabilized and dried to form a patterned source and a drain electrode. The coating method of the image forming liquid is not particularly limited to a spin coating method or a casting method, but is preferably an ink jet printing method or a spray coating method which is easy to control the amount of liquid. Finally, the organic semiconductor material such as pentacene or polyolefin of the active layer of the organic FET is formed into a film. The film formation method of the organic semiconductor material is not particularly limited, and examples thereof include vacuum deposition or spin coating of a solution, a casting method, an inkjet printing method, or a spray coating method. Such an organic FET can be greatly reduced in manufacturing steps, and an organic FET having a shorter channel than the mask evaporation method can be fabricated. Therefore, when a low mobility organic semiconductor material is used as an active layer, a large current may be taken out. . Further, since the underlayer film for forming an image obtained by the method of the present invention also has excellent electrical insulating properties, it can also be used as a gate insulating layer, and the manufacturing step can be simplified. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. [Measurement of Number Average Molecular Weight and Weight Average Molecular Weight] The number average molecular weight (hereinafter referred to as Μη) and the weight average molecular weight (hereinafter referred to as Mw) of the chitosan precursor obtained by the following synthesis examples are GPC (normal temperature). The gel permeation chromatograph "is measured by the following apparatus and measurement conditions, and calculated by polyethylene glycol (or polyethylene oxide). GPC device: shodex (registered trademark) (GPC-101) manufactured by Showa Denko Electric Co., Ltd. Pipe column: Sh〇dex (registered trademark) manufactured by Showa Denko (share) (KD803, KD805 series)

管柱溫度:50°C 溶離液:N,N-二甲基甲醯胺 -51 - 201031687 (作爲添加劑:溴化鋰-水合物(LiBr · H20 ) 30mmol/L ,磷酸•無水結晶(〇-磷酸)30mmol/L,四氫呋喃(THF )1 0ml/L ) 流速:1.0ml/分鐘 檢量線作成用標準樣品: TOSOH (股)製造之TSK標準聚環氧乙烷(分子量 :約 900,000、1 50,000 ' 100,000 &gt; 30,000 )Column temperature: 50 ° C Dissolution: N,N-dimethylformamide-51 - 201031687 (as additive: lithium bromide-hydrate (LiBr · H20) 30mmol / L, phosphoric acid • anhydrous crystals (〇-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) 10 ml/L) Flow rate: 1.0 ml/min. Measured wire for standard sample: TSK standard polyethylene oxide manufactured by TOSOH (molecular weight): molecular weight: about 900,000, 1 50,000 '100,000 &gt; 30,000 )

Polymer · Laboratory公司製造之聚乙二醇(分子量 ^ :約 1 2,000、4,000、1,000 ) [膜厚測定] 聚醯亞胺膜之膜厚係以切割刀剝離膜之一部份,且使 用全自動細微形狀測定機(ΕΊΜΟΟΟΑ,小坂硏究所(股) 製造),測定力爲1 〇 V Ν,掃描速度爲0 · 〇 5 mm/秒測定其 段差而求得。 ❿ [紫外線照射] 紫外線係透過使以高壓水銀燈作爲光源之波長254nm 之光通過帶通濾波器照射在聚醯亞胺膜上。 又’於聚醯亞胺膜上曝光量之計算,係於照度計( OAI公司製造,MODEL306 )上安裝於波長253.7nm具有 高峰値感度之Deep UV用探針測定紫外線之照度。 所得照度爲45〜50mW/cm2。所得照度乘以曝光時間 作爲曝光量(J/cm2 )。 -52- 201031687 [接觸角之測定] 接觸角之測定係在®溫恒濕環境(2 5 C ί 2 C,5 0 % RH±5%)中,使用全自動接觸角計CA-W(協和介面化學 公司製造)測定。 水之接觸角係由液量3 # L ’著液後靜止5秒後測定 〇 丙二醇單甲基醚(PGME)之接觸角係由液量3.0〜3.5 β L,著液後靜止5秒後測定。 〈合成例〉 [合成例1:二胺化合物(〇人-1:3,5-二胺基硫代苯甲酸十 八烷酯)之合成] [化 34]Polyethylene glycol manufactured by Polymer Laboratory (molecular weight ^: about 1 2,000, 4,000, 1,000) [Measurement of film thickness] The film thickness of the polyimide film is a part of the film peeled off by a cutter, and it is fully automatic. The fine shape measuring machine (manufactured by 坂硏 坂硏 坂硏 ( ( , , , , , , , , , , 测定 测定 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 ❿ [Ultraviolet Irradiation] Ultraviolet light is transmitted through a band-pass filter on a polyimide film at a wavelength of 254 nm using a high-pressure mercury lamp as a light source. Further, the amount of exposure on the polyimide film was measured by an illuminometer (manufactured by OAI Corporation, MODEL 306), and was attached to a Deep UV probe having a peak sensitivity of 253.7 nm to measure the illuminance of ultraviolet rays. The obtained illuminance was 45 to 50 mW/cm2. The obtained illuminance is multiplied by the exposure time as the exposure amount (J/cm2). -52- 201031687 [Measurement of contact angle] The contact angle is measured in a constant temperature and humidity environment (2 5 C ί 2 C, 50% RH ± 5%) using a fully automatic contact angle meter CA-W (Concord Measured by Interface Chemical Company). The contact angle of water is determined by the liquid amount 3 # L ' after standing for 5 seconds, and the contact angle of propylene glycol monomethyl ether (PGME) is determined by the liquid amount of 3.0~3.5 β L, and after standing for 5 seconds, the liquid is measured. . <Synthesis Example> [Synthesis Example 1: Synthesis of diamine compound (deuterated-1:3,5-diaminothiobenzoic acid octadecyl ester)] [Chem. 34]

[Hi][Hi]

於氮氣氛圍下’使含化合物[丨丨](20.0(^,6 9.79111111〇1 )、三乙胺(8.07g,79.76mmol)之四氣呋喃(I55g)溶 液冷卻至1 0 °C ,且邊注意發熱邊滴加含化合物[i]( 15_3 3g ’ 66.47mxn〇l )之四氫呋喃(70g )溶液。滴加結束 -53- 201031687 後’使反應溫度上升至23°C,再進行反應。以HPLC (高 速液體層析)確認反應結束後,將反應液排空倒入蒸餾水 (1.8L)中,過濾析出之固體,水洗後,以甲醇(i92g) 分散洗淨’獲得化合物[iii](產量:26.4g,產率:83% )。 'H-NMR ( 400MHz &gt; CDC13 &gt; δ ppm ) : 9.21-9.20 ( 1H &gt; m ),9.07-9.06 ( 2H,m ) ,3 .1 8 ( 1 2 H,t ) ,1 · 7 3 - 1.6 7 ( 2H,m ) &gt; 1.48 - 1.3 7 ( 2H &gt; m ) ,1.23 ( 28H,s) ,0.86 (3H,t )。 在氮氣氛圍下,將化合物[iii] ( 19.95g,41.5mmol) 、鐵粉(還原鐵,13.91g,249.0mmol )、乙酸乙酯( 1 8 0 g )之混合物加熱至 7 0 °C後,滴加氯化銨(6.6 6 g, 124.5mmol)之1 0 %水溶液。以Η P L C確認反應結束後, 以矽藻土過濾過濾固體。以乙酸乙酯及蒸餾水各200mL 洗淨後,去除水層,以蒸餾水(300mL)洗淨有機層3次 。隨後,有機層以無水硫酸鎂乾燥,過濾後,餾除溶劑。 以甲醇(l〇4g )使所得化合物(DA-1 )之粗產物再結晶 ,獲得化合物(DA-1 )(產量:1 1 .7g,產率:67% )。 1 Η-NMR ( 400MHz ’ CDC13,6 ppm ) : 6_69 ( 2H,dd) ’ 6.18 ( 1H,t) ,3.69 ( 4H,brs ) ,3.00 ( 2H,t ),Cooling the solution of the compound [丨丨] (20.0 (^, 6 9.79111111〇1), triethylamine (8.07 g, 79.76 mmol) in tetrahydrofuran (I55g) to 10 ° C under a nitrogen atmosphere, and Note that a solution of the compound [i] (15_3 3g '66.47mxn〇l) in tetrahydrofuran (70g) was added dropwise while the mixture was added. After the end of the addition -53- 201031687, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. (High-speed liquid chromatography) After confirming the completion of the reaction, the reaction liquid was drained and poured into distilled water (1.8 L), and the precipitated solid was filtered, washed with water, and then washed with methanol (i92 g) to obtain a compound [iii] (yield: 26.4 g, yield: 83%). 'H-NMR (400 MHz &gt; CDC13 &gt; δ ppm ) : 9.21-9.20 (1H &gt; m ), 9.07-9.06 ( 2H, m ) , 3 .1 8 ( 1 2 H,t ) ,1 · 7 3 - 1.6 7 ( 2H,m ) &gt; 1.48 - 1.3 7 ( 2H &gt; m ) , 1.23 ( 28H, s) , 0.86 (3H, t ). Under a nitrogen atmosphere, After heating a mixture of compound [iii] (19.95 g, 41.5 mmol), iron powder (reduced iron, 13.91 g, 249.0 mmol) and ethyl acetate (180 g) to 70 ° C, ammonium chloride was added dropwise. 10% of (6.6 6 g, 124.5 mmol) After confirming the completion of the reaction by ΗPLC, the solid was filtered through celite, washed with 200 mL of ethyl acetate and distilled water, and then the aqueous layer was removed, and the organic layer was washed three times with distilled water (300 mL). After drying over anhydrous magnesium sulfate, the solvent was evaporated, and the crude product was crystallized from methanol (1 g 4 g) to give compound (DA-1) (yield: 11.7 g, yield Rate: 67%). 1 Η-NMR (400MHz ' CDC13,6 ppm ) : 6_69 ( 2H,dd) ' 6.18 ( 1H,t) , 3.69 ( 4H,brs ) ,3.00 ( 2H,t ),

1 .66- 1 .56 ( 2H,m ) ,1 · 4 2 -1 · 2 5 ( 3 0 H,m ) ,0.88 ( 3H ,t ) 0 -54- 201031687 [合成例2 :聚醯亞胺前驅物(PI-1 )之合成] 於氮氣流下,在50mL之四頸燒瓶中置入合成例1中 調製之3,5-二胺基氧代苯甲酸十八烷酯(DA-1 ) 1.2621 g (0.003mol ),溶解於10.42g之N-甲基-2-吡咯啶酮(爾 後稱爲 NMP )後,添加 0.5766g ( 〇.〇〇3mol )之 1,2,3,4-環丁烷四羧酸酐(爾後稱爲CB DA),使之在23 °C攪拌 10小時進行聚合反應,再以NMP稀釋,獲得聚醯亞胺前 驅物(PI-1)之8質量%溶液。 所得聚醯亞胺前驅物(PI-1)之數平均分子量(Μη) 與重量平均分子量(Mw)分別爲Mn=ll,650’ Mw = 28,380 [合成例3 :聚醯亞胺前驅物(PI-2 )之合成] 於氮氣流下,在 50mL之四頸燒瓶中置入 DA-1 0.8 835g ( 0.002 1 mol )、對-苯二胺(p-PDA ) 0.0973g ( 0.0009mol),溶解於 8_83g 之 NMP 後,添加 0.5766g( 0.00294mmol)之CBDA,使之在23°C下攪拌10小時進行 聚合反應,再以NMP稀釋,獲得聚醯亞胺前驅物(P1-2 )之6質量%溶液。 所得聚醯亞胺前驅物(PI-2)之數平均分子量(Μη) 與重量平均分子量(Mw)分別爲Mn = 34,670,Mw = 97,560 [合成例4 :聚醯亞胺前驅物(PI-3 )之合成] -55- 201031687 於氮氣流下,在200mL之四頸燒瓶中置入1 5.065g ( 0.040mol)之1-十八烷氧基-2,4-二胺基苯(APC18), 溶解於 127.6g 之 NMP 後,添加 7.45g( 0.038mol)之 CBDA,使之在23。(:攪拌12小時進行聚合反應,再以 NMP稀釋,獲得聚醯亞胺前驅物(PI-3 )之6重量%溶液 〇 所得聚醯亞胺前驅物(PI-3 )之數平均分子量(Mn) 與重量平均分子量(Mw)分別爲Mn=16,000’ Mw = 48,000 [合成例5 :二胺化合物(DA-2)] DA-2之合成 [化 35]1.66- 1 .56 ( 2H,m ) , 1 · 4 2 -1 · 2 5 ( 3 0 H,m ) , 0.88 ( 3H ,t ) 0 -54- 201031687 [Synthesis Example 2: Polyimine Synthesis of Precursor (PI-1) The octadecyl 3,5-diaminooxybenzoate (DA-1) prepared in Synthesis Example 1 was placed in a 50 mL four-necked flask under a nitrogen stream. g (0.003 mol), after dissolving in 10.42 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP), adding 0.5766 g (〇.〇〇3 mol) of 1,2,3,4-cyclobutane The alkanetetracarboxylic anhydride (hereinafter referred to as CB DA) was stirred at 23 ° C for 10 hours to carry out a polymerization reaction, and then diluted with NMP to obtain an 8 mass% solution of the polyimine precursor (PI-1). The number average molecular weight (?η) and the weight average molecular weight (Mw) of the obtained polyimine precursor (PI-1) were Mn = ll, 650' Mw = 28, 380, respectively [Synthesis Example 3: Polyimine precursor (PI) -2) Synthesis] Under a nitrogen flow, DA-1 0.8 835 g (0.002 1 mol) and p-phenylenediamine (p-PDA) 0.0973 g (0.0009 mol) were placed in a 50 mL four-necked flask and dissolved in 8_83 g. After NMP, 0.5766 g (0.00294 mmol) of CBDA was added, and the mixture was stirred at 23 ° C for 10 hours to carry out polymerization, and then diluted with NMP to obtain a 6 mass % solution of the polyimine precursor (P1-2). . The number average molecular weight (?η) and weight average molecular weight (Mw) of the obtained polyimine precursor (PI-2) were Mn = 34,670, Mw = 97,560, respectively [Synthesis Example 4: Polyimine precursor (PI-3) Synthesis] -55- 201031687 1 5.065 g (0.040 mol) of 1-octadecyloxy-2,4-diaminobenzene (APC18) was dissolved in a 200 mL four-necked flask under a nitrogen stream. After 127.6 g of NMP, 7.45 g (0.038 mol) of CBDA was added to make it at 23. (: stirring for 12 hours to carry out polymerization, and then diluted with NMP to obtain a 6 wt% solution of the polyimine precursor (PI-3), the number average molecular weight of the polyimine precursor (PI-3) obtained (Mn) And weight average molecular weight (Mw) are Mn=16,000' Mw = 48,000, respectively [Synthesis Example 5: Diamine compound (DA-2)] Synthesis of DA-2 [Chem. 35]

6^136^13

於氮氣氛圍下,在120t攪拌含化合物[iv]( 42.63g &gt; 209.9mmol )、化合物[v] ( 1 0 2.9 7 g ’ 2 3 0 · 9 mm 01 )、銅 粉(29.3 5g,46 1 · 8mmol ) 、2,2 ’ -聯吡陡(3 ·2 8 g ’ -56- 201031687 20.99mmol )、二甲基亞颯(341g)之混合物。以HPLC 確認反應結束後,將反應液加於蒸餾水(273 0g )中,過 濾且以蒸餾水(2L)、乙酸乙酯(1.5L)洗淨過濾物。接 著,於過濾液中添加己烷(5 00g ),以飽和食鹽水(1L) 洗淨有機層三次,以無水硫酸鎂乾燥。隨後,過濾、餾除 溶劑,獲得化合物[vi](產量:75.33g,產率:81%)。 W-NMR ( 400MHz,CDC13,δ ppm ) : 7.48 ( 2Η,d), ❹ 7.32 ( 2H,d),2.52 ( 3H,s)。 在氮氣氛圍下,於含化合物[vi]( 52.00g,117.6mmol )之乙腈(347g ) /純水(17g)溶液中添加N-氟- Ν’-(氯 甲基)三乙二胺雙(四氟硼酸酯)(43.63g,123.2mmol ),在23 °C進行反應。以HPLC確認反應結束後,餾除 溶劑。接著,添加二氯甲烷(1.2 L ),以少量添加飽和碳 酸氫鈉水溶液(7〇〇mL )。去除水層後,以飽和食鹽水( φ 700mL)洗淨有機層三次,有機層以無水硫酸鎂乾燥。隨 後,過濾進行溶劑餾除,獲得化合物[vii](產量:48.05 g ,產率:89% )。 'H-NMR ( 400MHz * CDC13 » δ ppm ) : 7.81 ( 2H ’ d), 7·78 ( 2H,d ) ,2·71 ( 3H,s )。 在氮氣氛圍下’於化合物[vii] ( 26.03g,56.8mmol) 中添加乙酸酐(46.39g ’ 454.4mmol ),於加熱回流下進 行反應。以HPLC確認反應結束後’餾除溶劑’獲得化合 -57- 201031687 物[Viii]之粗製產物。所得粗製產物以管柱層析儀(Si02 ,己烷/乙酸乙酯)純化’獲得化合物[viii](產量: 24.1 lg ·產率:85% )。 *H-NMR ( 400MHz « CDC13 5 δ ppm) : 7.54 ( 4H,s), 5.50 ( 2H,s ) ,2.14 ( 3H,s )。 在氮氣氛圍下,於含化合物[viii] ( 3 7.67g, 75.3mmol )之甲醇(15 0g)溶液中添加28%之氨水溶液 (13.73g),在23°C進行攪拌。以HPLC確認反應結束後 ,以35%鹽酸將pH調整成6後,餾除溶劑。隨後,使粗 產物溶解於二氯甲烷(1L)後,以飽和食鹽水(50 0mL) 洗淨三次,以無水硫酸鎂進行乾燥。隨後,過濾、餾除溶 劑,獲得化合物[ix](產量:31.28g,產率:97% )。 iH-NMR ( 400MHz,CDC13,(5 ppm ) : 7.44 ( 2H,d), 7.37(2H,d) ,3.61(lH,s)。 於氮氣氛圍下,使含化合物[ix] ( 3 1.00g,72.4mmol )、三乙胺(7.33g,72.4mm〇l )之四氫呋喃(139g )溶 液冷卻至1 0°C以下,且邊注意發熱邊滴加含化合物[i]( 15_90g’ 68.95mmol)之四氫呋喃(l〇〇g)溶液。滴力□結 束後,反應溫度上升至23 °C,再進行反應。以HPLC確 認反應結束後,將反應液倒入蒸餾水(1 .9 L )中,過濾析 出之固體,水洗後,自2 -丙醇(2 5 7 g )再結晶,獲得化. 合物[X](產量:27.01g’產率:63%)。 -58- 201031687 •H-NMR ( 400MHz &gt; CDC13 &gt; δ ppm) : 9.30 ( lH,t), 9. 1 5 ( 2H,d ) &gt; 7.74 ( 4H &gt; q )。 在氮氣氛圍下,於氫存在下,於23 °C攪拌含化合物 [X] ( 14.00g’ 22_5mmol) 、3% 鉑-碳(擔持 0.3% 鐵,含 水’ 2.8g’ 20wt%)、甲醇(21〇g)之混合物。以HPLC 確認反應結束後,以矽藻土過濾反應混合物,以甲醇(5 0 φ mL )洗淨矽藻土,且進行溶劑餾除。以2-丙醇(60g )分 散洗淨所得化合物(D A - 2 )之粗產物,進行過濾、乾燥 ,獲得化合物(DA-2)(產量:9.13g,產率:72%)。 'H-NMR ( 400MHz · CDCI3 &gt; δ ppm) : 7·65 ( 4H , s), 6.73 ( 2H,d) ,6.24 ( 1H,t) ,3.76 ( 4H,brs)。 [合成例6 :二胺化合物(DA-3 )]The compound [iv] (42.63g &gt; 209.9mmol), the compound [v] (1 0 2.9 7 g '2 3 0 · 9 mm 01 ), copper powder (29.3 5g, 46 1) were stirred at 120t under a nitrogen atmosphere. · 8mmol), 2,2 '-bipyrrole (3 · 2 8 g ' -56- 201031687 20.99mmol ), a mixture of dimethyl alum (341g). After confirming the completion of the reaction by HPLC, the reaction mixture was poured into distilled water (273 g), and filtered, and the filtrate was washed with distilled water (2 L) and ethyl acetate (1.5 L). Then, hexane (500 g) was added to the filtrate, and the organic layer was washed three times with saturated brine (1 L) and dried over anhydrous magnesium sulfate. Subsequently, the solvent was filtered and evaporated to give Compound [vi] (yield: 75.33 g, yield: 81%). W-NMR (400 MHz, CDC13, δ ppm): 7.48 (2 Η, d), ❹ 7.32 (2H, d), 2.52 (3H, s). Add N-fluoro-Ν'-(chloromethyl)triethylenediamine bis (0.1g, Tetrafluoroborate) (43.63 g, 123.2 mmol) was reacted at 23 °C. After confirming the completion of the reaction by HPLC, the solvent was distilled off. Next, dichloromethane (1.2 L) was added, and a saturated aqueous solution of sodium hydrogencarbonate (7 mL) was added in small portions. After the aqueous layer was removed, the organic layer was washed three times with saturated brine (? Subsequently, the solvent was distilled off by filtration to obtain a compound [vii] (yield: 48.05 g, yield: 89%). 'H-NMR (400 MHz * CDC13 » δ ppm ) : 7.81 ( 2H ' d ), 7·78 ( 2H, d ) , 2·71 ( 3H, s ). Acetic anhydride (46.39 g '454.4 mmol) was added to the compound [vii] (26.03 g, 56.8 mmol) under a nitrogen atmosphere, and the reaction was carried out under reflux with heating. After confirming the completion of the reaction by HPLC, the solvent was distilled off to obtain a crude product of the compound [Viii]. The obtained crude product was purified by column chromatography (SiO 2 , hexane / ethyl acetate) to yield compound [viii] (yield: 24.1 lg, yield: 85%). *H-NMR (400MHz « CDC13 5 δ ppm) : 7.54 ( 4H,s), 5.50 ( 2H,s ) , 2.14 ( 3H,s ). Under a nitrogen atmosphere, a 28% aqueous ammonia solution (13.73 g) was added to a solution of the compound [viii] (3 7.67 g, 75.3 mmol) in methanol (15 g), and stirred at 23 °C. After confirming the completion of the reaction by HPLC, the pH was adjusted to 6 with 35% hydrochloric acid, and then the solvent was evaporated. Subsequently, the crude product was dissolved in dichloromethane (1 L), washed three times with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. Subsequently, the solvent was filtered and distilled off to obtain Compound [ix] (yield: 31.28 g, yield: 97%). iH-NMR (400MHz, CDC13, (5 ppm): 7.44 (2H, d), 7.37 (2H, d), 3.61 (lH, s). Under a nitrogen atmosphere, compound [ix] (3 1.00g, 72.4 mmol), a solution of triethylamine (7.33 g, 72.4 mm 〇l) in tetrahydrofuran (139 g) was cooled to below 10 ° C, and tetrahydrofuran containing compound [i] (15_90 g '68.95 mmol) was added dropwise while paying attention to heat. (l〇〇g) solution. After the completion of the dropping force □, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (1.9 L), and the precipitate was separated by filtration. The solid was washed with water and recrystallized from 2-propanol (2 5 7 g) to give compound [X] (yield: 27.01 g yield: 63%). -58- 201031687 • H-NMR (400 MHz) &gt; CDC13 &gt; δ ppm) : 9.30 ( lH,t), 9. 1 5 ( 2H,d ) &gt; 7.74 ( 4H &gt; q ). Stir at 23 ° C in the presence of hydrogen in a nitrogen atmosphere. a mixture containing the compound [X] (14.00g' 22_5mmol), 3% platinum-carbon (supporting 0.3% iron, water '2.8g' 20wt%), and methanol (21〇g). After confirming the reaction by HPLC, The reaction mixture was filtered through diatomaceous earth to The diatomaceous earth was washed with an alcohol (5 0 φ mL ), and the solvent was distilled off. The crude product of the obtained compound (DA - 2 ) was washed with 2-propanol (60 g), filtered, and dried to obtain a compound (DA). -2) (yield: 9.13 g, yield: 72%). 'H-NMR (400 MHz · CDCI3 &gt; δ ppm) : 7·65 ( 4H , s), 6.73 ( 2H, d) , 6.24 ( 1H, t), 3.76 (4H, brs) [Synthesis Example 6: Diamine compound (DA-3)]

DA-3之合成 [化 36]Synthesis of DA-3 [Chem. 36]

CtF17l liv] lx Hi]CtF17l liv] lx Hi]

[xiv][xiv]

[x m[x m

-59 201031687 於氮氣氛圍下,在120°C攪拌含化合物[iv]( 27.05g ’ 133.2mmol )、化合物[xi]( 80.00g,146.5mmol )、銅 粉(18.62g,293.0mmol ) 、2,2 ’ -聯吡啶(2 · 0 8 g, 13.32mmol)、二甲基亞碾(216g)之混合物。以 HPLC 確認反應結束後,將反應液加於蒸餾水(1 73 0g )中,經 過濾且以蒸餾水(1L)、乙酸乙酯(1L)洗淨過濾物。 接著,於過濾液中添加己烷(500g),以飽和食鹽水(1L )洗淨有機層三次,以無水硫酸鎂乾燥。隨後,經過濾、 餾除溶劑,獲得化合物[xii](產量:65.72g,產率:91% )° »H-NMR ( 400MHz &gt; CDC13,δ ppm ) : 7.58 ( 2Η,d), 7.47 ( 2H,d ) ,2.54 ( 3H,s )。 在氮氣氛圍下,於含化合物[xii]( 50.00g,92.21 mmol)之乙腈( 333g) /純水(17g)溶液中添力卩N -氟-N’-(氯甲基)三乙二胺雙(四氟硼酸酯)(32.67g, 92.2 1 mmol ),在23 °C進行反應。以ηPLC確認反應結束 後,餾除溶劑。接著,添加二氯甲烷(800 mL ),以少量 添加飽和碳酸氫鈉水溶液(5 0 0 m L )。去除水層後,以飽 和食鹽水( 500 mL)洗淨有機層三次,有機層以無水硫酸 鎂乾燥。隨後,經過濾進行溶劑餾除,獲得化合物[xiii] (產量:47.98g,產率:93% )。 1H-NMR ( 400MHz ’ CDCI3 ’ &lt;5 ppm ) : 7.81 ( 2H,d ), 7.77 (2H,d) ,2.78(3H,s) 〇 201031687 在氮氣氛圍下,於化合物[xiii] ( 70.63g )中添加三氟乙酸酐(220.56g,1.05m〇l ), 下進行反應。以HP LC確認反應結束後,餾展 粗產物。接著,添加甲醇( 226g)及三乙胺 ,在23°C攪拌30分鐘後,進行溶劑之餾除t 酸乙酯(1L)使所得粗產物溶解後,以飽和毒 φ (1L)、飽和食鹽水(1L)洗淨兩次後,有 鎂乾燥,餾除溶劑,獲得化合物[xiv](產量 率:97% )。 'H-NMR ( 400MHz » CDC13 5 δ ppm) : 7.44 7.36 ( 2H &gt; d ) ,3.61 ( 1H,s )。 於氮氣氛圍下,使含化合物[xiv] ( 69. mmol) '二乙胺(13.22g,130.62mmol)之 φ 290g)溶液冷卻至1(TC以下,邊注意發熱邊 物[i]( 28.68g,124.40 mmol)之四氫呋喃( 。滴加結束後,反應溫度上升至23 °C,再進 HPLC確認反應結束後,將反應液倒入蒸餾7J ,過濾析出之固體,經水洗後,自2-丙醇( 晶,獲得化合物[xv](產量:7 7.99g,產率: 'H-NMR ( 400MHz &gt; CDCI3 &gt; δ ppm ) : 9.27 9.1 7 ( 2H « d ) ,7.61 ( 4H,q )。 ,1 2 6.5 mmol 於加熱回流 隹溶劑,獲得 (211.89g) 接著,以乙 又化銨水溶液 機層以硫酸 :64.7g ,產 (2H , d), 00g , 130.62 四氫呋喃( :滴加含化合 1 4 5 g )溶液 i行反應。以 ((3.5L )中 270g )再結 88% )。 (1Η,t ), -61 - 201031687 在氮氣氛圍下,於氫存在下,於23 °C攪拌含化合物 [xvii](8.00g,ll.lmmol) 、3% 鉬-碳(擔持 0.3% 鐵, 含水,1.6g,20wt%)、甲醇(120g)之混合物。以 HP LC確認反應結束後,以矽藻土過濾反應混合物,以甲 醇(30mL )洗淨矽藻土,且進行溶劑餾除。以2-丙醇( 28g)分散洗淨所得化合物(DA-3 )之粗產物,並進行過 濾、乾燥,獲得化合物(DA-3 )(產量:5.6g,產率·· 76 % )。 ]H-NMR ( 400MHz » CDC13 &gt; &lt;5 ppm) : 7.65 ( 4H,s), 6.73 ( 2H,d) ,6.24 ( 1H,t) ,3.76 ( 4H,brs)。 [合成例7:二胺化合物(DA-4)] t)A-4之合成 [化 37]-59 201031687 The compound [iv] (27.05 g '133.2 mmol), the compound [xi] (80.00 g, 146.5 mmol), copper powder (18.62 g, 293.0 mmol), 2, were stirred at 120 ° C under a nitrogen atmosphere. A mixture of 2'-bipyridyl (2 · 0 8 g, 13.32 mmol) and dimethyl submilling (216 g). After confirming the completion of the reaction by HPLC, the reaction mixture was poured into distilled water (1, 73 g), filtered, and the filtrate was washed with distilled water (1 L) and ethyl acetate (1 L). Next, hexane (500 g) was added to the filtrate, and the organic layer was washed three times with saturated brine (1 L) and dried over anhydrous magnesium sulfate. Subsequently, the solvent was filtered off and the solvent was evaporated to give compound [xii] (yield: 65.72 g, yield: 91%). &quot;H-NMR (400 MHz &gt; CDC13, δ ppm): 7.58 (2Η,d), 7.47 ( 2H,d), 2.54 ( 3H,s ). Add N-fluoro-N'-(chloromethyl)triethylenediamine to a solution of compound [xii] (50.00 g, 92.21 mmol) in acetonitrile (333 g) / purified water (17 g) under nitrogen atmosphere. Bis(tetrafluoroborate) (32.67 g, 92.2 1 mmol) was reacted at 23 °C. After confirming the completion of the reaction by ηPLC, the solvent was distilled off. Next, dichloromethane (800 mL) was added, and a saturated aqueous solution of sodium hydrogencarbonate (500 mL) was added in small portions. After removing the aqueous layer, the organic layer was washed three times with saturated brine (500 mL) and dried over anhydrous magnesium sulfate. Subsequently, solvent distillation was carried out by filtration to obtain a compound [xiii] (yield: 47.98 g, yield: 93%). 1H-NMR (400MHz ' CDCI3 ' &lt; 5 ppm ) : 7.81 ( 2H,d ), 7.77 (2H,d) ,2.78(3H,s) 〇201031687 under nitrogen atmosphere in compound [xiii] (70.63g) Trifluoroacetic anhydride (220.56 g, 1.05 m〇l) was added thereto, and the reaction was carried out. After confirming the completion of the reaction by HP LC, the crude product was distilled. Next, methanol (226 g) and triethylamine were added, and after stirring at 23 ° C for 30 minutes, the solvent was distilled off (ethyl acetate) (1 L) to dissolve the obtained crude product, followed by saturated φ (1 L) and saturated salt. After washing twice with water (1 L), magnesium was dried and the solvent was distilled off to obtain compound [xiv] (yield: 97%). 'H-NMR (400 MHz » CDC13 5 δ ppm): 7.44 7.36 ( 2H &gt; d ) , 3.61 ( 1H, s ). The solution containing the compound [xiv] (69. mmol) 'diethylamine (13.22 g, 130.62 mmol) φ 290 g) was cooled to 1 (TC or less) under a nitrogen atmosphere while paying attention to the heating edge [i] (28.68 g). , 124.40 mmol) of tetrahydrofuran (after the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and after confirming the completion of the HPLC, the reaction solution was poured into a distillation 7 J, and the precipitated solid was filtered, washed with water, from 2-propane. Alcohol (crystal, obtained compound [xv] (yield: 7 7.99 g, yield: 'H-NMR (400 MHz &gt; CDCI3 &gt; δ ppm ) : 9.27 9.1 7 ( 2H « d ) , 7.61 ( 4H,q ). 1 2 6.5 mmol of the solvent was heated under reflux to obtain (211.89 g). Next, the aqueous solution of the aqueous solution of ammonium bromide was used as sulfuric acid: 64.7 g to produce (2H, d), 00 g, 130.62 tetrahydrofuran (: dropwise addition of compound 1 4 5 g ) The solution was reacted with i. (8 g of 270 g in (3.5 L)). (1 Η, t ), -61 - 201031687 Stirring at 23 ° C in the presence of hydrogen under a nitrogen atmosphere a mixture of compound [xvii] (8.00 g, 11 mmol), 3% molybdenum-carbon (supporting 0.3% iron, water, 1.6 g, 20 wt%), methanol (120 g). After that, the reaction mixture was filtered through celite, and the celite was washed with methanol (30 mL), and the solvent was distilled off. The crude product of the obtained compound (DA-3) was washed with 2-propanol (28 g) and washed. Filtration and drying gave Compound (DA-3) (yield: 5.6 g, yield 76%). H-NMR (400 MHz » CDC13 &lt;5 ppm): 7.65 ( 4H, s), 6.73 (2H,d), 6.24 (1H,t), 3.76 (4H,brs). [Synthesis Example 7: Diamine compound (DA-4)] t) Synthesis of A-4 [Chem. 37]

[DA-4] 於氮氣氛圍下,使含化合物[xvi](21.87g, 45.54mmol )、二乙胺(4_61g,45.54mmol)之四氫咲喃 (90g)溶液冷卻至lor以下,邊注意發熱邊滴加含化合 物[i] ( lO.OOg’ 43.37mmol)之四氫呋喃(60g)溶液。滴 201031687 加結束後,反應溫度上升至23 °C,再進行反應。以HP (高速液體層析儀)確認反應結束後,將反應液倒入蒸H 水(1.2L)中,過濾析出之固體,經水洗後,以2-丙醇( 232g )分散洗淨,獲得化合物[xvii](產量:27.69g,產 率:95% )。 'H-NMR ( 400MHz &gt; DMSO-d6 &gt; δ ppm) : 9.06 ( 1Η &gt; t) ,8.86(2H,d) &gt; 3.44 ( 2H &gt; t ) ,2.79-2.66 (2H,m) 在氮氣氛圍下,將含化合物[xvii] (25.OOg, 3 7.1 mmol )、鐵粉(還原鐵,12.42g,222.5mmol)、乙 酸乙酯(22 5g )之混合物加熱至70 °C後,滴加氯化銨( 5.9 5 g &gt; 111.3mmol)之10%水溶液。以HPLC確認反應結 束後,以矽藻土過濾固體。以乙酸乙酯及蒸餾水各500mL 洗淨後,去除水層,且以蒸餾水(500 mL)洗淨有機層3 φ 次。隨後,有機層以無水硫酸鎂乾燥,經過濾後,餾除溶 劑。以己烷(60g )分散洗淨所得化合物(DA-4 )之粗產 物,進行過濾•乾燥,獲得化合物(DA-4 )(產量: 19.5g,產率:85% )。 'H-NMR ( 400MHz &gt; DMSO-d6 - &lt;5 ppm) : 6.36 ( 2H,d) ,6.06 ( 1H,t) ,5.14 ( 4H,brs) ,3.19 ( 2H,t), 2.64-2.5 1 ( 2H,m )。 [合成例8 :聚醯亞胺(PI-4 )之合成] -63- 201031687 在氮氣流中,於100 mL之四頸燒瓶中注入3.583 7g (8.73mmol)之2,2-雙(4-胺基苯氧基苯基)丙烷(爾後 稱爲 BAPP ) 、0.1518g ( 0.27mmol )之 DA-2,且溶解於 36.02g 之 NMP 之後,添加 2.6214g(8.73mmol)之 3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐(爾後稱爲 TDA) ,使之在50°C下攪拌24小時進行聚合反應。所得聚醯胺 酸之溶液以NMP稀釋成8質量%。 於3 0g之該溶液中添加1 lg作爲醯亞胺化觸媒之乙酸 酐、5.2g之吡啶,在50°C下反應3小時,獲得聚醯亞胺 溶液。將該溶液倒入大量甲醇中,濾掉所得白色沉澱物, 經乾燥、獲得白色之聚醯亞胺粉末。該聚醯亞胺粉末以 W-NMR確認爲90%以上醯亞胺化。使2.1g之該粉末溶 解於27.7g之丁內酯及5.3g之二丙二醇單甲基醚之混 合溶劑中,獲得聚醯亞胺(P 1-4 )之6質量%溶液。 所得聚醯亞胺(PI-4)之數平均分子量(Μη)與重量 平均分子量(Mw)分別爲Mn=14,300’ Mw = 38,000。 [合成例9 :聚醯亞胺(PI-5)之合成] 在氮氣流中,於l〇〇mL之四頸燒瓶中置入3.4728g (8.46mmol)之 BAPP、0 · 3 0 3 7 g ( 0 · 5 4 mm ο 1 )之 DA-2, 溶解於 36.25g 之 NMP 之後,添加 2.6214g ( 8.73mmol) 之TDA,使之在50 °C攪拌24小時進行聚合反應。所得聚 醯胺酸之溶液以NMP稀釋成8質量%。 於30g之該溶液中添加ng作爲醯亞胺化觸媒之乙酸 201031687 酐、5.2g之吡啶,在50 °C反應3小時,獲得聚醯亞胺溶 液。將該溶液倒入大量甲醇中,濾掉所得白色沉澱物,經 乾燥、獲得白色之聚醯亞胺粉末。該聚醯亞胺粉末以1H-NMR確認爲90%以上之醯亞胺化。使2. lg之該粉末溶解 於27.7g之丁內酯及5.3g之二丙二醇單甲基醚之混合 溶劑中,獲得聚醯亞胺(PI-5 )之6質量%溶液。 所得聚醯亞胺(P1-5)之數平均分子量(Μη)與重量 平均分子量(Mw)分別爲Mn=16,400,Mw = 39.400。 [合成例10 :聚醯亞胺(PI-6 )之合成] 在氮氣流中,於l〇〇mL之四頸燒瓶中置入3.6206g (8.82mmol )之 BAPP、0.1 1 9 2g ( 0.1 8 mmo 1 )之 DA-3, 且溶解於 36.05g 之 NMP 後,添加 2.6214g(8.73mmol) 之TDA,使之在5〇°C攪拌24小時進行聚合反應。所得聚 醯胺酸之溶液以NMP稀釋成8質量%。 於3 Og之該溶液中添加llg作爲醯亞胺化觸媒之乙酸 酐、5.2g之吡啶,在50°C反應3小時,獲得聚醯亞胺溶 液。將該溶液倒入大量甲醇中,濾掉所得白色沉澱物,經 乾燥,獲得白色之聚醯亞胺粉末。該聚醯亞胺粉末以]Η_ NMR確認爲90%以上之醯亞胺化。使2.lg之該粉末溶解 於27.7g2r -丁內酯及5.3g之二丙二醇單甲基醚之混合 溶劑中,獲得聚醯亞胺(PI-6 )之6質量%溶液。 所得聚醯亞胺(PI-6)之數平均分子量(Μη)與重量 平均分子量(Mw)分別爲Mn = 20,200,Mw = 51,400。 -65- 201031687 [合成例11:聚醯亞胺(PI-7)之合成] 在氮氣流中,於lOOmL之四頸燒瓶中置入3.9819g (9.7mmol)之 B AP P、0 · 1 8 4 2 g ( 0.3 mm ο 1 )之 DA-4,且 溶解於40.11g之NMP之後,添加2.9126g(9.7mmol)之 TDA,使之在50°C攪拌24小時進行聚合反應。所得聚醯 胺酸之溶液以NMP稀釋成8質量%。 於3 0g之該溶液中添加1 lg作爲醯亞胺化觸媒之乙酸 酐、5.2g之吡啶,且在50°C反應3小時,獲得聚醯亞胺 溶液。將該溶液倒入大量甲醇中,濾掉所得白色沉澱物, 經乾燥,獲得白色之聚醯亞胺粉末。該聚醯亞胺粉末以 W-NMR確認爲90%以上醯亞胺化。使2.1g之該粉末溶 解於27.7g之丁內酯及5.3g之二丙二醇單甲基醚之混 合溶劑中,獲得聚醯亞胺(PI-7 )之6質量%溶液。 所得聚醯亞胺(PI-7 )之數平均分子量(Μη)與重量 平均分子量(Mw)分別爲Mn=17,800,Mw = 45,000。 [合成例12 :聚醯亞胺前驅物(PI-8 )之合成] 在氮氣流中,於l〇〇mL之四頸燒瓶中置入3_9819g (9.7mmol)之 B A P P、0 · 1 8 4 2 g ( 0.3 m m ο 1 )之 DA-4,且 溶解於 34.39g 之 NMP 後,添加 1.9023 g ( 9.7mmol )之 CBDA,使之在23°C攪拌l〇小時進行聚合反應,再以 NMP稀釋,獲得聚醯亞胺前驅物(PI-8 )之6質量%溶液 201031687 所得聚酿亞胺前驅物(PI-8)之數平均分子量(Μη) 與重量平均分子量(Mw)分別爲Mn=14,3 00,Mw = 3 2,100 [合成例13 :掺合物用聚醯亞胺(PI-9 )之合成] 在氮氣流中,於200mL之四頸燒瓶中置入4.86g ( 0.045mol)之對-苯二胺、1.74g( 0.005mol)之 4-十六烷 ❹ 氧基-1,3-二胺基苯,溶解於 122.5g之NMP後,添加 15.01g(0.05mol)之TDA,使之在室溫攪拌10小時進行 聚合反應。所得聚醯胺酸之溶液以NMP稀釋成8質量% 〇 於50g之該溶液中添加10.8g作爲醯亞胺化觸媒之乙 酸酐、5.0g之吡啶,在50°C下反應3小時,獲得聚醯亞 胺溶液。將該溶液倒入大量甲醇中,濾掉所得白色沉澱物 ,經乾燥,獲得白色之聚醯亞胺粉末。該聚醯亞胺粉末以 φ i-NMR確認爲90%以上醯亞胺化。使4g之該粉末溶解 於52.67g之r -丁內酯及l〇g之二丙二醇單甲基醚之混合 溶劑中,獲得聚醯亞胺(PI-9 )之6質量%溶液。 所得聚醯亞胺(PI-9)之數平均分子量(Μη)與重量 平均分子量(Mw)分別爲Mn=1 8,000’ Mw = 54,000。 [合成例1 4 ··聚合物掺合物(組成物A )之調製] 混合9g之合成例13中調製之聚醯亞胺(PI-9)之 6wt%溶液與lg之合成例11中調製之聚醯亞胺(PI-7) -67- 201031687 之6wt%溶液’在室溫攪拌6小時,獲得組成物a。 [合成例15:聚合物掺合物(組成物B)之調製] 混合9g之合成例13中調製之聚醯亞胺(PI_9)之 6wt%溶液與lg之合成例12中調製之聚醯亞胺(PI-8) 之6wt%溶液,在室溫攪拌6小時,獲得組成物b。 [合成例16:聚合物掺合物(組成物C)之調製] 混合8g之合成例13中調製之聚醯亞胺(PI-9)之 6wt%溶液與2g之合成例12中調製之聚醯亞胺(PI-8) 之6 wt %溶液,在室溫攪拌6小時,獲得組成物C。 以下顯示於實施例中合成或使用之四羧酸酐以及二胺 化合物之構造式。 [於本實施例使用之四羧酸酐][DA-4] A solution of the compound [xvi] (21.87 g, 45.54 mmol) and diethylamine (4_61 g, 45.54 mmol) in tetrahydrofuran (90 g) was cooled to below lor under a nitrogen atmosphere. A solution of the compound [i] (10.Og' 43.37 mmol) in tetrahydrofuran (60 g) was added dropwise. Drop 201031687 After the addition, the reaction temperature rose to 23 °C and the reaction was carried out. After confirming the completion of the reaction by HP (High Speed Liquid Chromatography), the reaction liquid was poured into distilled H water (1.2 L), and the precipitated solid was filtered, washed with water, and washed with 2-propanol (232 g) to obtain a dispersion. Compound [xvii] (yield: 27.69 g, yield: 95%). 'H-NMR (400 MHz &gt; DMSO-d6 &gt; δ ppm): 9.06 (1Η &gt; t) , 8.86 (2H, d) &gt; 3.44 ( 2H &gt; t ) , 2.79-2.66 (2H, m) The mixture containing the compound [xvii] (25.OOg, 3 7.1 mmol), iron powder (reduced iron, 12.42 g, 222.5 mmol) and ethyl acetate (22 5 g) was heated to 70 ° C under a nitrogen atmosphere. A 10% aqueous solution of ammonium chloride (5.9 5 g &gt; 111.3 mmol) was added. After confirming the completion of the reaction by HPLC, the solid was filtered with celite. After washing with 500 mL of ethyl acetate and distilled water, the aqueous layer was removed, and the organic layer was washed 3 times with distilled water (500 mL). Subsequently, the organic layer was dried over anhydrous magnesium sulfate, and after filtration, solvent was evaporated. The crude product of the obtained compound (DA-4) was washed with hexane (60 g), and filtered and dried to give Compound (DA-4) (yield: 19.5 g, yield: 85%). 'H-NMR (400MHz &gt; DMSO-d6 - &lt; 5 ppm) : 6.36 ( 2H,d) , 6.06 ( 1H,t) , 5.14 ( 4H,brs ) , 3.19 ( 2H,t), 2.64-2.5 1 ( 2H,m ). [Synthesis Example 8: Synthesis of Polyimine (PI-4)] -63- 201031687 In a nitrogen flow, a 3.5 mL 7-neck flask was charged with 3.583 7 g (8.73 mmol) of 2,2-bis (4- Aminophenoxyphenyl)propane (hereinafter referred to as BAPP), 0.1518 g (0.27 mmol) of DA-2, and after dissolving in 36.02 g of NMP, 2.6214 g (8.73 mmol) of 3,4-dicarboxyl was added. -1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (hereinafter referred to as TDA) was stirred at 50 ° C for 24 hours to carry out a polymerization reaction. The solution of the obtained polyaminic acid was diluted to 8 mass% with NMP. To 100 g of this solution, 1 lg of acetic anhydride as a ruthenium iodide catalyst and 5.2 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be 90% or more imidized by W-NMR. 2.1 g of this powder was dissolved in a mixed solvent of 27.7 g of butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (P 1-4 ). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (PI-4) were Mn = 14,300' Mw = 38,000, respectively. [Synthesis Example 9: Synthesis of Polyimine (PI-5)] 3.4728 g (8.46 mmol) of BAPP and 0·3 0 3 7 g were placed in a four-necked flask of 10 mL in a nitrogen stream. After DA-2 of (0 · 5 4 mm ο 1 ) was dissolved in 36.25 g of NMP, 2.6214 g ( 8.73 mmol) of TDA was added, and the mixture was stirred at 50 ° C for 24 hours to carry out polymerization. The resulting solution of polyamic acid was diluted to 8 mass% with NMP. To 30 g of this solution, ng was added as a ruthenium iodide catalyst acetic acid 201031687 anhydride, 5.2 g of pyridine, and reacted at 50 ° C for 3 hours to obtain a polyimine solution. This solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be imidized by 90% or more by 1H-NMR. The powder of 2. lg was dissolved in a mixed solvent of 27.7 g of butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-5). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (P1-5) were Mn = 16,400 and Mw = 39.400, respectively. [Synthesis Example 10: Synthesis of Polyimine (PI-6)] 3.6206 g (8.82 mmol) of BAPP and 0.11 9 2 g (0.1 8) were placed in a four-necked flask of 10 mL in a nitrogen stream. After DA-3 of mmo 1 ), and dissolved in 36.05 g of NMP, 2.6214 g (8.73 mmol) of TDA was added, and the mixture was stirred at 5 ° C for 24 hours to carry out a polymerization reaction. The resulting solution of polyamic acid was diluted to 8 mass% with NMP. To the solution of 3 Og, llg of acetic anhydride as a ruthenium-imiding catalyst and 5.2 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. This solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be imidized by 90% or more by Η_NMR. This powder of 2.lg was dissolved in a mixed solvent of 27.7 g of 2r-butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-6). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (PI-6) were Mn = 20,200 and Mw = 51,400, respectively. -65-201031687 [Synthesis Example 11: Synthesis of polyimine (PI-7)] In a nitrogen flow, 3.9819 g (9.7 mmol) of B AP P, 0 · 1 8 was placed in a 100 mL four-necked flask. 4 2 g (0.3 mm ο 1 ) of DA-4, and after dissolving in 40.11 g of NMP, 2.9126 g (9.7 mmol) of TDA was added, and the mixture was stirred at 50 ° C for 24 hours to carry out a polymerization reaction. The solution of the obtained polyaminic acid was diluted to 8 mass% with NMP. To 100 g of this solution, 1 lg of acetic anhydride as a ruthenium amide catalyst and 5.2 g of pyridine were added, and reacted at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be 90% or more imidized by W-NMR. 2.1 g of this powder was dissolved in a mixed solvent of 27.7 g of butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-7). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (PI-7) were Mn = 17,800 and Mw = 45,000, respectively. Synthesis Example 12: Synthesis of Polyimine Precursor (PI-8) In a four-necked flask of 10 mL, a BAPP, 0·1 8 4 2 was placed in a nitrogen cylinder. g (0.3 mm ο 1 ) of DA-4, and after dissolving in 34.39 g of NMP, add 1.9023 g (9.7 mmol) of CBDA, stir it at 23 ° C for 1 hour to carry out polymerization, and then dilute with NMP. Obtaining a 6 mass% solution of the polyamidiamine precursor (PI-8) 201031687 The number average molecular weight (?η) and the weight average molecular weight (Mw) of the obtained chitosan precursor (PI-8) are respectively Mn=14, 3 00, Mw = 3 2,100 [Synthesis Example 13: Synthesis of polyetherimine (PI-9) for blend] In a 200 mL four-necked flask, 4.86 g (0.045 mol) of a pair was placed in a nitrogen stream. - phenylenediamine, 1.74 g (0.005 mol) of 4-hexadecaneoxy-1,3-diaminobenzene, after dissolving in 122.5 g of NMP, adding 15.01 g (0.05 mol) of TDA, The polymerization was carried out by stirring at room temperature for 10 hours. The obtained polylysine solution was diluted with NMP to 8 mass%. To 50 g of this solution, 10.8 g of acetic anhydride as a ruthenium amide catalyst and 5.0 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain Polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white pigment. The polyimine powder was confirmed to be 90% or more imidized by φ i-NMR. 4 g of this powder was dissolved in a mixed solvent of 52.67 g of r-butyrolactone and 1 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-9). The number average molecular weight (?η) and weight average molecular weight (Mw) of the obtained polyimine (PI-9) were Mn = 18,000 Å Mw = 54,000, respectively. [Synthesis Example 1 4 ································································ The 6 wt% solution of the polyimine (PI-7)-67-201031687 was stirred at room temperature for 6 hours to obtain a composition a. [Synthesis Example 15: Preparation of Polymer Blend (Composition B)] 9 g of a 6 wt% solution of the polyimine (PI_9) prepared in Synthesis Example 13 and lg of the polyamide prepared in Synthesis Example 12 were mixed. A 6 wt% solution of the amine (PI-8) was stirred at room temperature for 6 hours to obtain a composition b. [Synthesis Example 16: Preparation of Polymer Blend (Composition C)] 8 g of a 6 wt% solution of the polyimine (PI-9) prepared in Synthesis Example 13 and 2 g of the polymerization prepared in Synthesis Example 12 were mixed. A 6 wt% solution of quinone imine (PI-8) was stirred at room temperature for 6 hours to obtain a composition C. The structural formula of the tetracarboxylic anhydride and the diamine compound synthesized or used in the examples is shown below. [Tetracarboxylic anhydride used in this example]

[於本實施例使用之二胺] -68- 201031687 [化 39][Diamine used in this embodiment] -68- 201031687 [Chem. 39]

η2Ν^^ΝΗ DA-2 o=c-s-^-c6F13 Λ, 〇=c-s-^^-c8f17 o^-s-λ ώ· 17η2Ν^^ΝΗ DA-2 o=c-s-^-c6F13 Λ, 〇=c-s-^^-c8f17 o^-s-λ ώ· 17

DA-3 η2ν^^νη2 DA*4DA-3 η2ν^^νη2 DA*4

&lt;實施例1&gt;水接觸角變化 φ 於附有ΙΤΟ之玻璃基板(2.5cm邊長,厚度〇.7mm) 上,使用附有ο.2 # m孔過濾器之針筒滴加合成例2所調 製之PI-1之溶液,藉由旋轉塗佈法塗佈。隨後於大氣下 ,以8 0 °C之加熱板加熱處理5分鐘,使有機溶劑揮發, 接著於21(TC之加熱板燒成30分鐘,獲得膜厚約400ηιη 之聚醯亞胺膜。測定該聚醯亞胺膜之水接觸角0 (°)。 以同樣順序製作2片聚醯亞胺膜,以 20J/cm2或 40J/cm2之照射量照射紫外線後,測定該膜之水接觸角0 -69- 201031687 結果示於表A。 &lt;實施例2&gt;水接觸角變化 除使用合成例3調製之P1-2之溶液以外,使用與實 施例1同樣順序製作3片聚醯亞胺膜,設爲紫外線未照射 膜、照射紫外線20J/cm2之膜或照射紫外線40J/cm2之膜 ,測定各膜之水接觸角0 ( ° )。 結果示於表A。 &lt;比較例1 &gt;水接觸角變化 除使用合成例4調製之P1-3之溶液以外,使用與實 施例1同樣順序製作2片聚醯亞胺膜,各設爲紫外線未照 射膜或照射紫外線40〗/cm2之膜,測定各膜之水接觸角0 (°)。 結果示於表A。 &lt;實施例3&gt; PGME接觸角變化 使用與實施例1同樣順序製作3片聚醯亞胺膜,各設 爲紫外線未照射膜、照射紫外線2J/cra2之膜或照射紫外 線6J/cm2之膜,測定各膜之PGME之接觸角0 (。)。 結果示於表B。 &lt;比較例2&gt; PGME接觸角變化 除使用合成例4調製之PI_3之溶液以外,使用與實 -70 - 201031687 施例1同樣順序製作2片聚醯亞胺膜,各設爲紫外線未照 射膜或照射紫外線6J/cm2之膜’測定各膜之PGME接觸 角 0 ( °)。 結果示於表B。 &lt;實施例4&gt; PGME接觸角變化 於附有ITO之玻璃基板(2·5 cm邊長,厚度0.7mm) φ 上,使用附有0.2 /z m孔過濾器之針筒滴加合成例8所調 製之PI-4之溶液,藉由旋轉塗佈法塗佈。隨後於大氣下 ,以8 0 °C之加熱板加熱處理5分鐘,使有機溶劑揮發, 接著於180°C之加熱板燒成30分鐘,獲得膜厚約400nm 之聚醯亞胺膜。測定該聚醯亞胺膜之PGME溶液之接觸角 0 ( °) ° 以同樣順序製作1片聚醯亞胺膜,以1 J/cm2之照射 量照射紫外線後,測定該膜之PGME接觸角0 (。)。 結果不於表C。 &lt;實施例5&gt; PGME接觸角變化 除使用合成例9調製之PI-5以外,使用與實施例4 同樣順序製作2片聚醯亞胺膜,各設爲紫外線未照射膜、 照射紫外線lJ/cm2之膜’測定各膜之.pgme接觸角0 (。 結果示於表C。 201031687 &lt;實施例6&gt; PGME接觸角變化 除使用合成例調製之PI-6以外’使用與實施例4 同樣順序製作2片聚醯亞胺膜,各設爲紫外線未照射膜、 照射紫外線U/cm2之膜,測定各膜之PGME接觸角0 (。 )。 結果示於表C。 &lt;實施例7&gt; PGME接觸角變化 除使用合成例14調製之組成物A以外’使用與實施 例4同樣順序製作2片聚醯亞胺膜,各設爲紫外線未照射 膜、照射紫外線lJ/cm2之膜,測定各膜之PGME接觸角 Θ (°)。 結果不於表C。 &lt;實施例8&gt; PGME接觸角變化 除使用合成例16調製之組成物C以外,使用與實施 例6同樣順序製作2片聚醯亞胺膜,各設爲紫外線未照射 膜、照射紫外線lJ/cm2之膜,測定各膜之PGME接觸角 Θ ( °)。 結果示於表C。 -72- 201031687 [表5] 表A水之接觸角測定結果 使用聚合物 紫外線未照射 θ η 紫外線照射後0 (。) 20J/cm2 40J/cm2 實施例1 PI-1 98 72 15 實施例2 PI-2 95 43 7 比較例1 PI-3 88 - 81.8 [表6] 表B PGME之接觸角測 定結果 使用聚合物 紫外線未照射 θ η 紫外線照期 廢0 (。) 2J/cm2 6J/cm2 實施例3 PI-1 20.1 9.8 10 比較例2 PI-3 17.7 - 19.4 ❹ [表7] 表C PGME之接觸角測定結果 使用聚合物 紫外線照射暈Θ D 未照射 lJ/cm2 實施例4 PI-4 17.3 8.4 實施例5 PI-5 31.7 18.3 實施例6 PI-6 25 16.7 實施例7 PI-7/PI-9 18.5 9.3 實施例8 PI-8/PI-9 27.1 16.9 如表A、表B及表C所示’使用由側鏈上具有硫醇 鍵之二胺所製作之聚醯亞胺及聚醯亞胺前驅物之實施例中 ’紫外線照射後之P GME接觸角任一情況均有大幅變化。 另~方面,使用未利用側鏈上具有硫醇鍵之二胺所製 -73- 201031687 作之聚醯亞胺前驅物(PI-3 )之比較例1及2中,水或 PGME之接觸角變化量小。 此結果認爲是,若聚醯亞胺前驅物爲側鏈爲透過硫醇 酯基存在有疏水性機之構造,亦即該硫醇酯基因紫外線照 射而產生光分解,使側鏈之疏水性部分自主鏈切斷並分離 ,藉此使親疏水性產生大幅變化之結果。 &lt;實施例9&gt;電極圖型化性評估 ^ 於附有ΙΤΟ之玻璃基板(2.5 cm邊長,厚度〇.7mm) 上,使用附有0.2 // m孔過濾器之針筒滴加合成例8所調 製之PI-4之溶液,藉由旋轉塗佈法塗佈。隨後於大氣下 ’以80 °C之加熱板加熱處理5分鐘,使有機溶劑揮發, 接著於180°C之加熱板燒成30分鐘,獲得膜厚約400nm 之聚醯亞胺膜。於該聚醯亞胺薄膜上透過光罩(線寬100 // m、間距1 〇〇 # m之線及空間)照射紫外線1 j/cm2,使 聚醯亞胺之一部份親水化。接著於紫外線照射部微量滴加 ❹ 銀微粒子分散液,以1 8 0 °C之加熱板燒成6 0分鐘,形成 膜厚50nm之銀電極。 此銀電極之顯微鏡照片示於圖1。由PI-4所構成之膜 可形成成爲目的線寬之銀電極。 &lt;實施例1 〇&gt;電極圖型化性評估 除使用合成例1 4調製之組成物A以外,使用與實施 例9同樣順序成膜聚醯亞胺膜,於此聚醯亞胺薄膜上透過 -74- 201031687 光罩(線寬1 00 &quot; m、間距1 00 # m之線及空間)照射紫 外線U/cm2,使聚醯亞胺之一部份親水化。接著於紫外線 照射部微量滴加銀微粒子分散液,以1 8 0 °C之加熱板燒成 60分鐘,形成膜厚50nm之銀電極。 此銀電極之顯微鏡照片示於圖2。由組成物A所構成 之膜可形成成爲目的線寬之銀電極。 φ &lt;比較例3 &gt;電極圖型化性評估&lt;Example 1&gt; Water contact angle change φ On a glass substrate (2.5 cm side length, thickness 〇. 7 mm) to which ΙΤΟ was attached, a syringe with an ο. 2 # m hole filter was used to add Synthesis Example 2 The prepared PI-1 solution was applied by spin coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing at 21 (the hot plate of TC for 30 minutes to obtain a polyimide film having a film thickness of about 400 ηη. The water contact angle of the polyimide film is 0 (°). Two polyimide films are produced in the same order, and after irradiating ultraviolet rays with an irradiation amount of 20 J/cm 2 or 40 J/cm 2 , the water contact angle of the film is measured. 69-201031687 The results are shown in Table A. &lt;Example 2&gt; Change in water contact angle Three sheets of polyimine film were produced in the same manner as in Example 1 except that the solution of P1-2 prepared in Synthesis Example 3 was used. The film was irradiated with ultraviolet rays of 20 J/cm2 or a film irradiated with ultraviolet rays of 40 J/cm2, and the water contact angle of each film was measured by 0 (°). The results are shown in Table A. <Comparative Example 1 &gt; Water contact angle The film was prepared in the same manner as in Example 1 except that the solution of P1-3 prepared in Synthesis Example 4 was used, and each of the films was formed into an ultraviolet non-irradiation film or a film irradiated with ultraviolet rays of 40 Å/cm 2 . The water contact angle of the film was 0 (°). The results are shown in Table A. &lt;Example 3&gt; PGME contact angle change Three polyimine films were produced in the same manner as in Example 1, and each of them was an ultraviolet non-irradiated film, a film irradiated with ultraviolet rays 2J/cra2, or a film irradiated with ultraviolet rays of 6 J/cm 2 , and the contact angle of PGME of each film was measured 0 ( The results are shown in Table B. <Comparative Example 2> PGME contact angle change Two sheets of polyimine were produced in the same manner as in Example 70 except that the solution of PI_3 prepared in Synthesis Example 4 was used. Each of the films was an ultraviolet non-irradiated film or a film irradiated with ultraviolet rays of 6 J/cm 2 'The PGME contact angle of each film was 0 (°). The results are shown in Table B. <Example 4> PGME contact angle was changed with ITO On the glass substrate (2·5 cm side length, thickness 0.7 mm) φ, a solution of PI-4 prepared in Synthesis Example 8 was dropped using a syringe equipped with a 0.2 /zm hole filter, by spin coating After coating, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 nm. The contact angle of the PGME solution of the polyimide film was measured as 0 (°) °. One piece of poly was produced in the same order. The yttrium imide film was irradiated with ultraviolet rays at an irradiation dose of 1 J/cm 2 , and the PGME contact angle of the film was measured as 0 (.). The results are not shown in Table C. <Example 5> PGME contact angle change except Synthesis Example 9 In the same manner as in Example 4, two polyimine films were produced in the same manner as in Example 4, and each of the films was irradiated with an ultraviolet ray unirradiated film and irradiated with ultraviolet rays of 1 J/cm 2 to measure the pgme contact angle of each film. The results are shown in Table C. 201031687 &lt;Example 6&gt; The PGME contact angle was changed except that PI-6 prepared by the synthesis example was used. In the same procedure as in Example 4, two polyimide films were produced, each of which was an ultraviolet non-irradiated film, and irradiated with ultraviolet rays U/. The film of cm2 was measured for the PGME contact angle 0 (.) of each film. The results are shown in Table C. &lt;Example 7&gt; The PGME contact angle was changed except that the composition A prepared in Synthesis Example 14 was used. In the same procedure as in Example 4, two polyimide films were produced, each of which was an ultraviolet non-irradiated film, and irradiated with ultraviolet rays. The film of cm2 was measured for the PGME contact angle ° (°) of each film. The result is not in Table C. &lt;Example 8&gt; The PGME contact angle change was carried out in the same manner as in Example 6 except that the composition C prepared in Synthesis Example 16 was used, and each of the two films was formed into an ultraviolet non-irradiation film and irradiated with ultraviolet rays. The film of cm2 was measured for the PGME contact angle ° (°) of each film. The results are shown in Table C. -72- 201031687 [Table 5] Table A Water contact angle measurement results using polymer ultraviolet rays not irradiated θ η UV irradiation after 0 (.) 20 J/cm 2 40 J/cm 2 Example 1 PI-1 98 72 15 Example 2 PI -2 95 43 7 Comparative Example 1 PI-3 88 - 81.8 [Table 6] Table B Measurement results of contact angle of PGME Using polymer ultraviolet rays not irradiated θ η UV irradiation period waste 0 (.) 2 J/cm 2 6 J/cm 2 Example 3 PI-1 20.1 9.8 10 Comparative Example 2 PI-3 17.7 - 19.4 ❹ [Table 7] Table C Measurement results of contact angle of PGME Irradiation with polymer ultraviolet rays D Irradiation 1 J/cm 2 Example 4 PI-4 17.3 8.4 Example 5 PI-5 31.7 18.3 Example 6 PI-6 25 16.7 Example 7 PI-7/PI-9 18.5 9.3 Example 8 PI-8/PI-9 27.1 16.9 As shown in Table A, Table B and Table C In the examples using the polyimine and the polyimide precursor prepared by the diamine having a thiol bond in the side chain, the P GME contact angle after the ultraviolet irradiation greatly changed. On the other hand, in the comparative examples 1 and 2 of the poly-imine precursor (PI-3) made of -73-201031687 which is made of a diamine having a thiol bond in a side chain, the contact angle of water or PGME The amount of change is small. This result is considered to be that if the polyimine precursor is a structure in which a side chain is a thiol ester group, a hydrophobic machine exists, that is, the thiol ester gene is irradiated by ultraviolet light to cause photodecomposition, and the side chain is hydrophobic. Part of the autonomous chain is cut and separated, thereby causing a large change in the hydrophilicity and hydrophobicity. &lt;Example 9&gt; Electrode patterning evaluation ^ On a glass substrate (2.5 cm side length, thickness 〇. 7 mm) with a crucible attached thereto, a syringe drop addition example with a 0.2 // m hole filter was used. A solution of 8 prepared PI-4 was applied by spin coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 nm. On the polyimide film, a portion of the polyimine was hydrophilized by irradiating ultraviolet rays 1 j/cm 2 through a reticle (line width 100 // m, pitch 1 〇〇 # m line and space). Subsequently, a silver fine particle dispersion was added dropwise to the ultraviolet irradiation portion, and baked at a temperature of 180 ° C for 60 minutes to form a silver electrode having a film thickness of 50 nm. A micrograph of this silver electrode is shown in Fig. 1. A film composed of PI-4 can form a silver electrode which becomes a target line width. &lt;Example 1&gt; Electrode patterning evaluation In addition to the composition A prepared in Synthesis Example 14, a film-forming polyimide film was formed in the same procedure as in Example 9 on the polyimide film. Through the -74-201031687 mask (line width 1 00 &quot; m, spacing 1 00 # m line and space), UV U/cm2 is irradiated to make one part of the polyimine hydrophile. Subsequently, a silver fine particle dispersion was added dropwise to the ultraviolet irradiation portion, and baked at a temperature of 180 ° C for 60 minutes to form a silver electrode having a film thickness of 50 nm. A micrograph of this silver electrode is shown in Fig. 2. The film composed of the composition A can form a silver electrode which becomes a target line width. φ &lt;Comparative Example 3 &gt; Electrode patterning evaluation

除使用合成例4調製之PI-3,且燒成溫度設爲210 °C 以外’使用與實施例1 1同樣順序成膜聚醯亞胺膜,於此 聚醯亞胺薄膜上透過光罩(線寬l〇〇/zm、間距100/im 之線及空間)照射紫外線1 J/cm2。隨後微量滴加銀微粒子 分散液’但由於紫外線照射部未被親水化故無法形成電極 〇 實施例9至實施例10與比較例3之結果顯示於表〇 由具有硫醇酯鍵之P1-4以及組成物A所構成之膜, 以1 i/cm2之紫外線照射量親水性已充分變化,而可形成 1 0 0 &quot; m線寬之銀電極’相反地,由不具有硫醇酯鍵之組 成物D所構成之膜,以1 j/cm2之紫外線照射量親水性未 充分變化,而無法形成電極。 -75- 201031687A polyimide film was formed in the same order as in Example 1 except that PI-3 prepared in Synthesis Example 4 was used, and the firing temperature was 210 ° C. The polyimide film was passed through the mask ( The line width l〇〇/zm, the line of 100/im pitch and space) is irradiated with ultraviolet rays of 1 J/cm2. Subsequently, the silver fine particle dispersion liquid was added in a small amount. However, since the ultraviolet irradiation portion was not hydrophilized, the electrode could not be formed. The results of Example 9 to Example 10 and Comparative Example 3 are shown in the table by P1-4 having a thiol ester bond. And the film composed of the composition A, the hydrophilicity of the ultraviolet irradiation amount of 1 i / cm 2 has been sufficiently changed, and the silver electrode of the "m line width" can be formed 'instead, by having no thiol ester bond In the film composed of the composition D, the hydrophilicity of the ultraviolet irradiation amount of 1 j/cm 2 was not sufficiently changed, and the electrode could not be formed. -75- 201031687

表D電崔 巨形成能力(U/cm2) 使用聚合物 電極形成 實施例9 PI-4 可能 實施例10 組成物A 可能 比較例3 PI-3 不可能 &lt;實施例11&gt;絕緣性 於附有ITO之玻璃基板(2.5 cm邊長,厚度0.7mm) 上,使用附有〇.2#m孔過濾器之針筒滴加合成例2所調 製之PI-1之溶液,藉由旋轉塗佈法塗佈。隨後於大氣下 ,以80°C之加熱板加熱處理5分鐘,使有機溶劑揮發, 接著於210°C之加熱板燒成30分鐘,獲得膜厚約450nm 之聚醯亞胺膜。 接著爲獲得ITO電極與測定裝置之探針間之良好接觸 ,削取聚醯亞胺膜之一部份使ITO露出後,使用真空蒸鍍 裝置,在聚醯亞胺膜上及ITO上層合直徑1.0mm、膜厚 lOOnm之鋁電極。此時之真空蒸鍍條件設爲室溫、真空度 3xlO_3Pa以下、鋁蒸鎪速度〇.3nm/秒以下。藉由如此於聚 醯亞胺膜之上下形成電極,製作聚醯亞胺膜之電流-電壓 特性評價用樣品。 所製作之樣品立即於氮氣氛圍中,測定電流-電壓特 性。測定電壓設爲自0V每2V上升至90V。此時之聚醯 亞胺膜之比介電率爲3.37,洩漏電流密度爲3xl(T1()A/cm2 。又,聚醯亞胺膜於2MV/cm之電場絕緣未被破壞。 201031687 圖3顯示氮氣氛圍中之電流-電壓特性測定結果。 接著,與上述相同的樣品在大氣(25度,濕度45% )靜置1 5小時後,測定電流-電壓特性。測定電壓設爲自 0V每2V上升至90V。此時之樣品拽漏電流密度爲1.8x 1 Ο*7A/cm2 0 圖4顯示大氣中之電流-電壓特性測定結果。 φ &lt;實施例12&gt;絕緣性 除聚醯亞胺膜之燒成溫度設爲23 0°C以外,使用與實 施例1 1相同順序製作電流-電壓特性評價用樣品。此時之 聚醯亞胺膜之比介電率爲3.14,洩漏電流密度爲1. Οχ l(T1()A/cni2。又,聚醯亞胺膜於2MV/cm之電場絕緣未被 破壞。Table D Electric Cui Giant Formation Ability (U/cm2) Formation Using Polymer Electrode Example 9 PI-4 Possible Example 10 Composition A Possible Comparison Example 3 PI-3 Impossible &lt;Example 11&gt; Insulation is attached On a glass substrate of ITO (2.5 cm side length, thickness 0.7 mm), a solution of PI-1 prepared in Synthesis Example 2 was dropped by using a syringe equipped with a 〇.2#m-pore filter, by spin coating. Coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 210 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 450 nm. Then, in order to obtain good contact between the ITO electrode and the probe of the measuring device, one part of the polyimide film is peeled off to expose the ITO, and then the diameter is laminated on the polyimide film and the ITO by using a vacuum evaporation device. 1.0 mm, aluminum electrode with a film thickness of 100 nm. The vacuum vapor deposition conditions at this time were set to room temperature, the degree of vacuum was 3 x 10 3 Pa or less, and the aluminum vapor deposition rate was 3 3 nm / sec or less. A sample for evaluation of current-voltage characteristics of the polyimide film was prepared by forming an electrode above and below the polyimide film. The prepared sample was immediately subjected to a current-voltage characteristic in a nitrogen atmosphere. The measured voltage is set to rise from 0V every 2V to 90V. At this time, the specific dielectric ratio of the polyimide film was 3.37, and the leakage current density was 3×1 (T1() A/cm 2 . Further, the electric field insulation of the polyimide film at 2 MV/cm was not destroyed. 201031687 Fig. 3 The measurement results of the current-voltage characteristics in a nitrogen atmosphere are shown. Next, the same sample as above was allowed to stand in the atmosphere (25 degrees, humidity 45%) for 15 hours, and then the current-voltage characteristics were measured. The measurement voltage was set to 0 V per 2 V. The temperature rises to 90 V. At this time, the sample leakage current density is 1.8 x 1 Ο * 7 A / cm 2 0 Figure 4 shows the measurement results of the current-voltage characteristics in the atmosphere. φ &lt;Example 12&gt; Insulation except polyimine film A sample for current-voltage characteristic evaluation was produced in the same manner as in Example 1 except that the firing temperature was changed to 23 ° C. The specific dielectric constant of the polyimide film at this time was 3.14, and the leak current density was 1. Οχ l(T1()A/cni2. Further, the electric field insulation of the polyimide film at 2 MV/cm is not destroyed.

接著’與上述相同的樣品在大氣(25度,濕度45% )靜置1 5小時後,測定電流-電壓特性。測定電壓設爲自 Φ 0 V每2 V上升至9 0 V。此時之樣品洩漏電流密度爲1 . 8 X 1 O'8A/cm2 ° 圖3顯示於氮氣氛圍中之電流-電壓特性測定結果, 圖4顯示大氣中之電流-電壓特性測定結果。 &lt;實施例13&gt;絕緣性 於附有ITO之玻璃基板(2.5cm邊長,厚度0.7mm) 上’使用附有0.2 // m孔過濾器之針筒滴加合成例8所調 製之PI-4之溶液,藉由旋轉塗佈法塗佈。隨後於大氣下 -77- 201031687 ,以80°C之加熱板加熱處理5分鐘,使有機溶劑揮發’ 接著於180°C之加熱板燒成30分鐘,獲得膜厚約400nm 之聚醯亞胺膜。接著爲獲得ITO電極與測定裝置之探針間 之良好接觸,削取聚醯亞胺膜之一部份使ITO露出後’使 用真空蒸鍍裝置,在聚醯亞胺膜上及ITO上層合直徑 1.0mm、膜厚100nm之鋁電極。此時之真空蒸鍍條件設爲 室溫、真空度3xl(T3Pa以下、鋁蒸鍍速度0.3nm/秒以下 。藉由如此於聚醯亞胺膜之上下形成電極,製作聚醯亞胺 膜之電流-電壓特性評價用樣品。 所製作之樣品於23 °C ±3 °C、濕度45% ±5%之環境下 靜置1 5小時後,測定電流電壓特性。測定電壓設爲自0V 每2V上升至100V。此樣品於lMV/cm之洩漏電流密度爲 々^xlO — HA/cm2。又,聚醯亞胺膜直至2MV/cm絕緣仍未 被破壞。 圖5顯示電流-電壓特性測定結果。 &lt;實施例14&gt;絕緣性 除使用合成例14調製之組成物A以外,以與實施例 1 3相同順序製作電流-電壓特性評價用樣品。 此樣品於lMV/cm之洩漏電流密度爲1.7xl(T1()A/cm2 。又,聚醯亞胺膜直至2MV/cm絕緣仍未被破壞。 圖5顯示電流-電壓特性測定結果。 &lt;實施例15&gt;絕緣性 -78- 201031687 除使用合成例15調製之組成物B且燒成溫 2 3 0 °C以外,以與實施例1 3相同順序製作電流-電 評價用樣品。 此樣品於lMV/cm之洩漏電流密度爲1.2xl(T 。又,聚醯亞胺膜直至2MV/cm絕緣仍未被破壞。 圖5顯示電流-電壓特性測定結果。 φ &lt;實施例16&gt;絕緣性 除使用合成例16調製之組成物C且燒成溫 23 0°C以外,以與實施例13相同順序製作電流-電 評價用樣品。 此樣品於lMV/cm之洩漏電流密度爲3.4x10^ 。又,聚醯亞胺膜直至2MV/cm絕緣仍未被破壞。 圖5顯示電流-電壓特性測定結果。 如圖3所示,由PI-1所構成之膜在氮氣氛圍 φ 異之絕緣膜(實施例1 1及實施例12 )。 且如圖4所示,由PI-1所構成之膜,易受水 ’可見到於大氣中之洩漏電流密度比氮氣氛圍中更 但仍爲作爲形成畫像用下層膜之用途毫無問題之水 施例1 1及實施例1 2 )。 又,如圖5所示,由PI - 4及組成物A至C所 膜均爲優異之絕緣膜(實施例13至實施例16)。 亦即,本發明之形成畫像形成用下層膜爲具有 成畫像形成用下層膜之充分絕緣性能之下層膜。 度設爲 壓特性 0 A/cm2 度設爲 壓特性 °A/cm2 中爲優 分影響 增力口, 準(實 構成之 作爲形 -79 - 201031687 &lt;實施例17 :電晶體特性&gt; 於附有 Cr電極之玻璃基板(2.5cm邊長,厚度 0.7mm)上,使用附有〇.2/i m孔過濾器之針筒滴加合成 例8所調製之PI-4之溶液,藉由旋轉塗佈法塗佈。隨後 於大氣下,以80°C之加熱板加熱處理5分鐘,使有機溶 劑揮發,接著於180°C之加熱板燒成30分鐘,獲得膜厚 約450nm之聚醯亞胺膜。於此聚醯亞胺薄膜上透過光罩 照射紫外線2J/cm2,使聚醯亞胺之一部份親水化。接著於 紫外線照射部微量滴加銀微粒子分散液,以1 80t之加熱 板燒成60分鐘,形成膜厚5 Onm之源極.汲極電極。 於此銀電極上,藉由真空蒸鍍法使并五苯(Aldrich 製)成膜70nm。并五苯之蒸鍍速度設爲0.05nm/秒。 以上述所得之有機薄膜電晶體之電特性藉由測定源極 電流相對於閘極電壓之變化而予以評價。 詳言之,源極·汲極電壓(VD )設爲-80V,閘極電 壓(VG)自+20V至- 80V以2V步進變化,於各電壓在電 流充分安定之前保持1秒電壓後之値作爲汲極電流之測定 値予以記錄,重複5次此操作。且測定係使用半導體參數 分析儀HP415 6C ( AGILENT技術公司製),在氮氣氛圍 中測定。 通常,於飽和狀態之汲極電流Id可以下述式表示。 亦即有機半導體之移動度A可由以汲極電流Id之絕對値 平方根爲縱軸,以閘極電壓Vg爲橫軸作圖時之圖型斜率 -80- 201031687 求得。Then, the same sample as above was allowed to stand for 15 hours in the atmosphere (25 degrees, humidity 45%), and the current-voltage characteristics were measured. The measured voltage is set to rise from φ 0 V every 2 V to 90 V. The sample leakage current density at this time was 1. 8 X 1 O'8 A/cm 2 ° Fig. 3 shows the results of measurement of current-voltage characteristics in a nitrogen atmosphere, and Fig. 4 shows the results of measurement of current-voltage characteristics in the atmosphere. &lt;Example 13&gt; Insulation on a ITO-attached glass substrate (2.5 cm side length, thickness: 0.7 mm) was applied by using a syringe attached with a 0.2 // m hole filter to add PI prepared in Synthesis Example 8. The solution of 4 was applied by spin coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in an atmosphere at -77-201031687 to volatilize the organic solvent. Then, it was baked at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 nm. . Then, in order to obtain good contact between the ITO electrode and the probe of the measuring device, one part of the polyimide film is cut out to expose the ITO, and then the diameter is laminated on the polyimide film and the ITO by using a vacuum evaporation device. 1.0 mm aluminum electrode with a film thickness of 100 nm. The vacuum vapor deposition conditions at this time were set to room temperature, a vacuum degree of 3×l (T3 Pa or less, and an aluminum vapor deposition rate of 0.3 nm/sec or less. By forming an electrode above and below the polyimide film, a polyimide film was produced. Sample for evaluation of current-voltage characteristics. The prepared sample was allowed to stand at 23 ° C ± 3 ° C and humidity 45% ± 5% for 15 hours, and then the current-voltage characteristics were measured. The measured voltage was set to 0 V per 2 V. It rises to 100 V. The leakage current density of this sample at lMV/cm is 々^xlO — HA/cm 2 . Further, the polyimide film is still unbroken until 2 MV/cm. Figure 5 shows the results of current-voltage characteristics measurement. &lt;Example 14&gt; Insulation A sample for current-voltage characteristic evaluation was produced in the same order as in Example 13 except that the composition A prepared in Synthesis Example 14 was used. The leakage current density of this sample at 1 MV/cm was 1.7 x 1 (T1()A/cm2. Further, the polyimide film was not destroyed until 2 MV/cm. Fig. 5 shows the results of current-voltage characteristics measurement. &lt;Example 15&gt; Insulation-78-201031687 The composition B prepared in Example 15 was the same as in Example 13 except that the firing temperature was 2 3 0 °C. The sample for current-electrical evaluation was sequentially prepared. The leakage current density of this sample at lMV/cm was 1.2×1 (T. Further, the polyimide film was not destroyed until 2 MV/cm. Figure 5 shows the measurement of current-voltage characteristics. Results: φ &lt;Example 16&gt; Insulation A sample for current-electrical evaluation was produced in the same manner as in Example 13 except that the composition C prepared in Synthesis Example 16 was used and the baking temperature was 23 °C. The leakage current density of /cm is 3.4x10^. Further, the polyimide film is not destroyed until 2MV/cm. Figure 5 shows the results of current-voltage characteristics measurement. As shown in Figure 3, it consists of PI-1. The film is different in the atmosphere of nitrogen gas (Example 1 1 and Example 12). As shown in Fig. 4, the film composed of PI-1 is susceptible to water leakage current density visible in the atmosphere. In addition to the nitrogen atmosphere, the water is used as a method for forming an underlayer film for the image without any problem. Example 1 1 and Example 1 2). Further, as shown in Fig. 5, PI-4 and composition A to C The film is an excellent insulating film (Examples 13 to 16). That is, the formed image forming method of the present invention is used. The film is a layer film having sufficient insulating properties for forming an underlayer film for forming an image. The degree is set to a pressure characteristic of 0 A/cm 2 and the pressure characteristic is °A/cm 2 . As a shape-79 - 201031687 &lt;Example 17: Transistor characteristics&gt; On a glass substrate (2.5 cm side length, thickness 0.7 mm) with a Cr electrode, a needle with a 〇.2/im hole filter was used. A solution of PI-4 prepared in Synthesis Example 8 was added dropwise to the solution by spin coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to volatilize the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 450 nm. The polyimide film was irradiated with ultraviolet rays of 2 J/cm 2 through a mask to hydrophilize a part of the polyimide. Then, a silver fine particle dispersion liquid was added dropwise to the ultraviolet irradiation portion, and fired in a heating plate of 180 ° for 60 minutes to form a source and a drain electrode having a film thickness of 5 Onm. On the silver electrode, pentacene (manufactured by Aldrich) was formed into a film of 70 nm by vacuum evaporation. The vapor deposition rate of pentacene was set to 0.05 nm/second. The electrical characteristics of the organic thin film transistor obtained above were evaluated by measuring the change in the source current with respect to the gate voltage. In detail, the source and drain voltages (VD) are set to -80V, and the gate voltage (VG) varies from +20V to -80V in 2V steps, and the voltage is maintained for 1 second before the current is fully stabilized.値 is recorded as a measurement of the buckling current, and this operation is repeated 5 times. Further, the measurement was carried out in a nitrogen atmosphere using a semiconductor parameter analyzer HP415 6C (manufactured by AGILENT Technologies). Generally, the drain current Id in a saturated state can be expressed by the following equation. That is, the mobility A of the organic semiconductor can be obtained by taking the absolute square root of the drain current Id as the vertical axis and the slope of the pattern when the gate voltage Vg is plotted on the horizontal axis -80-201031687.

Id = WC β (Vg-Vt)2/2L 上述式中,W爲電晶體之通道寬度,L爲電晶體之通 道長度,C爲閘極絕緣膜之靜電電容,VT爲電晶體之閾 値電壓,#爲移動度。以本實施例作成之電晶體W = 2mm ,L = 1 Ο0 /z m » C = 6.4nF/cm2。 并五苯之移動度//基於該式計算後,平均爲5x 10_2cm2/Vs。又,閾値電壓自-18V至-20V,開(ON )狀 態與關(OFF)狀態之比(開/關比)爲1〇6等級。又進行 重複測_定亦未見到傳達特性(Transfer Characteristics ) 偏移而獲得安定特性(圖6)。 顯示由P 1-4所得之膜不僅作爲電極形成膜優異且作 爲有機電晶體用之閘極絕緣膜亦優異。 &lt;實施例18 :電晶體特性&gt; 除使用合成例14調製之組成物A以外,與實施例17 同樣地製作有機電晶體。於本實施例作成之電晶體 W = 2 m m,L = 1 0 0// m,C = 6 · 5 n F / c m 2。 并五苯之移動度//基於該式計算後,平均爲5x l(T2cm2/Vs。又,閾値電壓自-19V至-21 V,開狀態與關狀 態之比(開/關比)爲1 〇ό等級。又進行重複測定亦未見 到傳達特性偏移而獲得安定特性(圖7)。 顯示由組成物Α所得之膜不僅作爲電極形成膜優異 且作爲有機電晶體用之閘極絕緣膜亦優異。 -81 - 201031687 &lt;實施例19 :電晶體特性&gt; 除紫外線照射量設爲lJ/cm2以外,與實施例17同樣 地製作有機電晶體。於本實施例作成之電晶體W = 2mm, L= 1 00 /z m &gt; C = 6.4nF/cm2。 并五苯之移動度//基於該式計算後,平均爲3x l(T2cm2/VS。又,閾値電壓自-16V至-20V,開狀態與關狀 態之比(開/關比)爲1 06等級。又進行重複測定亦未見 到傳達特性偏移而獲得安定特性(圖8)。 顯示由組成物A所得之膜不僅作爲電極形成膜優異 且作爲有機電晶體用之閘極絕緣膜亦優異。 [產業上之可能利用性] 依據本發明之形成畫像用下層膜可實現縮短用以使親 疏水性產生變化之必要曝光時間,可期待縮減於形成電極 等之機能性材料之圖型化層時之製造成本。 此外,藉由照射偏光UV,亦可對由前述聚醯亞胺前 驅物及聚醯亞胺所得之膜賦予異向性。亦即,亦可使用作 爲液晶或半導體等之機能性材料之配向處理膜,與作爲形 成畫像用下層膜時同樣,可期待縮短製造時間。 【圖式簡單說明】 圖1爲表示實施例9所製作之PI_4上之銀電極的顯 微鏡照片圖(銀電極線寬爲100//m)。 -82 - 201031687 圖2爲表示實施例10所製作之組成物A上之銀電極 的顯微鏡照片圖(銀電極線寬爲1〇〇 A m )。 圖3爲顯示將聚醯亞胺前驅物(PI-1)燒成所得之聚 醯亞胺膜於氮氛圍中之電流-電壓特性之圖(實施例11及 實施例1 2 )。 圖4爲顯示將聚醯亞胺前驅物(PI-1 )燒成所得之聚 醯亞胺膜於大氣中之電流-電壓特性之圖(實施例11及實 ❺ 施例12 )。 圖5爲顯示於實施例13至實施例16所製作之聚醯亞 胺膜於大氣中之電流-電壓特性之圖。 圖6爲顯示對由PI-4所得之膜照射2J/cm2紫外線並 加工電極之有機電晶體之傳達特性之圖(實施例17)。 圖7爲顯示對由組成物a所得之膜照射2J/cm2紫外 線並加工電極之有機電晶體之傳達特性之圖(實施例18 )° ❹ 圖 8爲顯示對由PI-4所得之膜照射丨j/cm2紫外線並 加工電極之有機電晶體之傳達特性之圖(實施例19)。 -83-Id = WC β (Vg-Vt) 2/2L In the above formula, W is the channel width of the transistor, L is the channel length of the transistor, C is the electrostatic capacitance of the gate insulating film, and VT is the threshold voltage of the transistor. #为移动度. The transistor W made in this example has W = 2 mm, L = 1 Ο 0 /z m » C = 6.4 nF/cm 2 . The mobility of pentacene / / based on this formula, the average is 5 x 10 2 cm2 / Vs. Further, the threshold 値 voltage is from -18V to -20V, and the ratio of the ON state to the OFF state (on/off ratio) is 1〇6. Further, repeating the measurement and not transmitting the transfer characteristic (Transfer Characteristics) offset to obtain the stability characteristics (Fig. 6). The film obtained from P 1-4 is excellent not only as an electrode forming film but also as a gate insulating film for an organic transistor. &lt;Example 18: Transistor characteristics&gt; An organic transistor was produced in the same manner as in Example 17 except that the composition A prepared in Synthesis Example 14 was used. The transistor W made in this embodiment has W = 2 m m, L = 1 0 0 / / m, and C = 6 · 5 n F / c m 2 . The mobility of pentacene / / based on this formula, the average is 5x l (T2cm2 / Vs. Again, the threshold 値 voltage from -19V to -21 V, the ratio of open state to off state (on / off ratio) is 1 〇ό grade. Repeated measurement did not reveal the characteristic shift to obtain the stability characteristics (Fig. 7). It is shown that the film obtained from the composition 不仅 is excellent not only as an electrode forming film but also as a gate insulating film for an organic transistor. -81 - 201031687 &lt;Example 19: Transistor characteristics&gt; An organic transistor was produced in the same manner as in Example 17 except that the amount of ultraviolet irradiation was set to 1 J/cm 2 . 2mm, L = 1 00 /zm &gt; C = 6.4nF/cm2. The mobility of pentacene / / based on this formula, the average is 3x l (T2cm2 / VS. Again, the threshold 値 voltage from -16V to -20V The ratio of the on state to the off state (on/off ratio) is 1 06. Further, repeated measurement is performed to show that the characteristic shift is obtained to obtain the stability characteristic (Fig. 8). The film obtained from the composition A is not only used as the film. The electrode formation film is excellent and is also excellent as a gate insulating film for an organic transistor. [Industry may be advantageous According to the present invention, the underlayer film for forming an image can be used to shorten the necessary exposure time for changing the hydrophilicity and hydrophobicity, and it is expected to reduce the manufacturing cost when forming a patterned layer of a functional material such as an electrode. By irradiating the polarized light UV, it is also possible to impart anisotropy to the film obtained from the polyimine precursor and the polyimide, that is, an alignment treatment film which is a functional material such as a liquid crystal or a semiconductor, and In the same manner as in the case of forming an underlayer film for an image, it is expected to shorten the manufacturing time. [Schematic Description of the Drawing] Fig. 1 is a photomicrograph showing a silver electrode on PI_4 produced in Example 9 (silver electrode line width is 100//m) -82 - 201031687 Fig. 2 is a photomicrograph showing the silver electrode on the composition A produced in Example 10 (silver electrode line width is 1 〇〇A m ). Fig. 3 is a view showing the polyimine precursor A graph of current-voltage characteristics of a polyimide film obtained by firing (PI-1) in a nitrogen atmosphere (Example 11 and Example 1 2). Figure 4 shows a polyimide precursor (PI). -1) the polyimine film obtained by firing Fig. 5 is a graph showing the current-voltage characteristics of the polyimide film produced in Examples 13 to 16 in the atmosphere. Fig. 6 is a view showing the transmission characteristics of an organic transistor in which an electrode obtained by irradiating a film of PI-4 is irradiated with 2 J/cm 2 of ultraviolet rays and processing an electrode (Example 17). Fig. 7 is a view showing irradiation of a film obtained from the composition a. Figure 2 shows the transmission characteristics of an organic transistor with 2J/cm2 ultraviolet rays and processed electrodes (Example 18) ° ❹ Figure 8 shows the transmission of an organic transistor which irradiates the film obtained from PI-4 with 丨j/cm2 ultraviolet rays and processes the electrode. Figure of the characteristics (Example 19). -83-

Claims (1)

201031687 七、申請專利範圍: ι_ 一種形成畫像用下層膜,其特徵爲包含含有以下 述式(η表示之重複構造之聚醯亞胺前驅物或使該聚醯 亞胺前驅物脫水閉環所得之聚醯亞胺: [化1]201031687 VII. Patent application scope: ι_ An underlayer film for forming an image, which is characterized by comprising a polyimine precursor having a repetitive structure represented by the following formula (η) or a polycondensation of the polyimine precursor Yttrium imine: [Chemical 1] R1OOC COOR2 ~N—C—A—C—N—B I II II I HO OH (1 )R1OOC COOR2 ~N—C—A—C—N—B I II II I HO OH (1 ) (式中,A表示4價有機基,B表示以下述式(2)或(3 )表示之2價構造,I^、R2分別獨立表示氫原子或1價 有機基,η表示自然數); [化2] Ο u(wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2) or (3), and I^ and R2 each independently represent a hydrogen atom or a monovalent organic group, and η represents a natural number); [Chemical 2] Ο u S—C 一Χ—Υ-ΖS—C 一Χ—Υ-Ζ (3) (R)t (X表示單鍵或碳原子數6至20之2價芳香族基,Y表 · 示單鍵、-0-、-COO-、-OCO-、-CONH-、-CH20-、 -CH2COO-或-CH2CH2COO-,Z表示可經氟原子取代之碳 原子數3至26之脂肪族烴基,R各獨立表示氟原子、碳 原子數1至3之烷氧基或碳原子數1至3之烷基’t表示 〇至3之整數)。 2. —種形成畫像用下層膜’其特徵爲包含使含有以 下述式(6)表示之四羧酸二酐之四羧酸二酐成分與含有 以下述式(7)表示之二胺之二胺成分反應所得之聚醯亞 -84- 201031687 胺前驅物,或使該聚醯亞胺前驅物脫水閉環所得之聚醯亞(3) (R)t (X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -0-, -COO-, -OCO-, -CONH-, - CH20-, -CH2COO- or -CH2CH2COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon atom. The alkyl group 't of 1 to 3 represents an integer of 〇 to 3). 2. The underlayer film for forming an image is characterized in that it contains a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and a diamine containing a formula represented by the following formula (7) The polyamido-84-201031687 amine precursor obtained by the reaction of an amine component, or the polyazide obtained by dehydrating and ring-closing the polyimine precursor (6) h2n—b-nh2 (7)(6) h2n-b-nh2 (7) [式中,A表示4價有機基 表示之2價構造: B表示以式(2)或式(3) [化4]Wherein A represents a divalent structure represented by a tetravalent organic group: B represents a formula (2) or a formula (3) [Chemical 4] X—Y-Z (3) (式中,X表示單鍵或碳原子數6至20之2價芳香族基 ,γ 表示單鍵、-Ο-、-COO-、-OCO-、-CONH-、-CH20-、-ch2coo-或-ch2ch2coo-,Z表示可經氟原子取代之 碳原子數3至26之脂肪族烴基’ R各獨立表示氟原子、 碳原子數1至3之烷氧基或碳原子數1至3之烷基,t表 示0至3之整數)]。 3. 如申請專利範圍第1或2項之形成畫像用下層膜 ,其中式(2)或式(3)之Z表示任意氫原子經氟原子取 代之碳原子數3至26之脂肪族烴基。 4. 如申請專利範圍第1至3項中任一項之形成畫像 用下層膜,其中 A表示具有脂肪族環或僅由脂肪族所構 -85- 201031687 成之4價有機基。 5. 如申請專利範圍第1至4項中任一項之形成畫像 用下層膜,其中B表示以式(2)表示之2價構造。 6. 如申請專利範圔第1至5項中任一項之形成畫像 用下層膜,其中X及Y表示單鍵。 7. 一種有機電晶體,其特徵爲含有申請專利範圍第 1至6項中任一項之形成畫像下層膜。X—YZ (3) (wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and γ represents a single bond, -Ο-, -COO-, -OCO-, -CONH-, - CH20-, -ch2coo- or -ch2ch2coo-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom. R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon atom. An alkyl group of 1 to 3, and t represents an integer of 0 to 3)]. 3. The underlayer film for forming an image according to the first or second aspect of the patent application, wherein Z of the formula (2) or the formula (3) represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which is substituted by a fluorine atom of any hydrogen atom. 4. The underlayer film for forming an image according to any one of claims 1 to 3, wherein A represents a tetravalent organic group having an aliphatic ring or an aliphatic group only -85-201031687. 5. The lower layer film for forming an image according to any one of claims 1 to 4, wherein B represents a divalent structure represented by the formula (2). 6. The image forming the image according to any one of claims 1 to 5, wherein X and Y represent a single bond. An organic transistor characterized by comprising the underlayer film for forming an image according to any one of claims 1 to 6. 8. —種以下述式(14)或下述式(15)表示之二胺 化合物 [化5]8. A diamine compound represented by the following formula (14) or the following formula (15) [Chemical 5] (式中,X表示單鍵或碳原子數6至20之2價芳香族基 ,Y 表示單鍵、-Ο-、-COO-、-OCO-、-CONH-、-CH2〇-、-CH2COO -或- CH2CH2COO-’ Z表示任意的氫原子經氟 原子取代之碳原子數3至26之脂肪族烴基’ R各獨立表 示氟原子、碳原子數1至3之院氧基或碳原子數1至3之 烷基,t表示〇至3之整數)。 9. 一種聚醯亞胺,其特徵爲含有以下述式(Ο表示 之重複單位之聚醯亞胺前驅物或使該聚醯亞胺前驅物脫水 閉環所得, -86- (1)201031687 [化6](wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -Ο-, -COO-, -OCO-, -CONH-, -CH2〇-, -CH2COO -or- CH2CH2COO-'Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom of any hydrogen atom. R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon atom number of 1 To an alkyl group of 3, t represents an integer from 〇 to 3). A polyimine which is characterized by containing a polyimine precursor of a repeating unit represented by the following formula (Ο) or by dehydrating a ring of the polyimine precursor, -86- (1) 201031687 6] R1OOC /COOR2 N—C—A一C一N—B· I II II I HO OH n (式中,A表示4價有機基,B表示以下述式(2a)或( 3a)表示之2價構造,R1、R2分別獨立表示氫原子或1 價有機基,η表示自然數); [化7] ❿ 〇=C-S—X-Y-Z S-C- ~0~~ (23) (R)t (R), 〇 II S一C-X—Y_Z K (3a) (R)t (式中,x表示單鍵或碳原子數6至20之2價芳香族基 ,Y 表示單鍵、-Ο-、-COO-、-OCO-、-CONH-、-CH2〇-、-ch2coo -或-ch2ch2coo-,Z表示任意的氫原子經氟 原子取代之碳原子數3至26之脂肪族烴基,R各獨立表 # 示氟原子、碳原子數1至3之烷氧基或碳原子數1至3之 烷基,t表示0至3之整數)。 10. —種形成畫像下層膜塗佈液,其特徵爲包含使含 有以下述式(6)表示之四羧酸二酐之四羧酸二酐成分與 含有以下述式(7)表示之二胺之二胺成分反應所得之聚 醯亞胺前驅物,或使該聚醯亞胺前驅物脫水閉環所得之聚 醯亞胺: -87- 201031687 [化8] Ο ΟR1OOC /COOR2 N—C—A—C—N—B· I II II I HO OH n (wherein A represents a tetravalent organic group, and B represents a divalent structure represented by the following formula (2a) or (3a); , R1, R2 independently represent a hydrogen atom or a monovalent organic group, η represents a natural number); [Chemical 7] ❿ 〇 = CS - XYZ SC - ~ 0 ~ ~ (23) (R) t (R), 〇 II S-CX—Y_Z K (3a) (R)t (wherein x represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -Ο-, -COO-, -OCO -, -CONH-, -CH2〇-, -ch2coo- or -ch2ch2coo-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which is substituted by a fluorine atom of any hydrogen atom, and R each independently represents a fluorine atom, An alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3. 10. A formation film lower layer coating liquid comprising a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and a diamine represented by the following formula (7) The polyimine precursor obtained by the reaction of the diamine component, or the polyimine obtained by dehydrating and ring-closing the polyimine precursor: -87- 201031687 [Chem. 8] Ο Ο Ο Ο Η2Ν-Β-ΝΗ2 (7) Ο (6) (式中,Α表示4價有機基,Β表示以式(2)或式(3) 表示之2價構造: [化9] 〇=c—s —X—Y~z Ό&quot; (2, (R)t !? ⑩ S-C-X 一 Υ一 ζ _Λ_ Κ (3) (R)t R1、R2分別獨立表示氫原子或1價有機基,X表示單 鍵或碳原子數6至20之2價芳香族基’ Y表示單鍵、-0-、-COO-、-OCO-、-CONH-、-CH20-、-CH2COO-或 -CH2CH2COO- , Z表示可經氟原子取代之碳原子數3至26 之脂肪族烴基’ R獨立表示氟原子、碳原子數1至3之院 ❹ 氧基或碳原子數1至3之烷基,t表示0至3之整數)。 11.如申請專利範圍第10項之形成畫像下層膜塗佈 液,其中式(2)或式(3)之Z表示任意氫原子經氟原子 取代之碳原子數3至26之脂肪族烴基。 1 2 ·如申請專利範圍第1 〇或11項之形成畫像用下層 膜塗佈液,其中進一步含有醯亞胺化率爲80%以上之可 溶性聚醯亞胺。 13. —種形成畫像之下層膜,其特徵爲使申請專利範 -88 - 201031687 圍第10至12項之形成畫像下層膜塗佈液燒成而得。 14. 一種有機電晶體,其特徵爲具有使申請專利範圍 第10至13項之形成畫像下層膜塗佈液燒成而得之膜。Ο Ο Η2Ν-Β-ΝΗ2 (7) Ο (6) (wherein Α represents a tetravalent organic group, and Β represents a divalent structure represented by formula (2) or formula (3): [Chemical 9] 〇=c —s —X—Y~z Ό&quot; (2, (R)t !? 10 SCX 一Υ一ζ _Λ_ Κ (3) (R)t R1, R2 independently represent a hydrogen atom or a monovalent organic group, X represents A single bond or a divalent aromatic group of 6 to 20 carbon atoms 'Y represents a single bond, -0-, -COO-, -OCO-, -CONH-, -CH20-, -CH2COO- or -CH2CH2COO-, Z The aliphatic hydrocarbon group which represents 3 to 26 carbon atoms which may be substituted by a fluorine atom 'R independently represents a fluorine atom, a methoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents 0 to An integer of 3). 11. The image forming method of the underlayer film coating liquid according to claim 10, wherein Z of the formula (2) or the formula (3) represents an arbitrary hydrogen atom substituted with a fluorine atom and has 3 to 26 carbon atoms. The aliphatic hydrocarbon group of the image forming method according to the first or the eleventh aspect of the patent application, further comprising a soluble polyimine having a ruthenium iodide ratio of 80% or more. Forming an underlying film, characterized by Patent Application No. -88 - 201031687 The formation of the underlayer film coating liquid is obtained by the formation of the image of the 10th to 12th. 14. An organic transistor characterized by having the lower layer of the image forming of the patent claims 10th to 13th. A film obtained by firing a film coating liquid. -89 --89 -
TW098135951A 2008-10-23 2009-10-23 Underlayer film for forming image TWI453235B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2008273217 2008-10-23

Publications (2)

Publication Number Publication Date
TW201031687A true TW201031687A (en) 2010-09-01
TWI453235B TWI453235B (en) 2014-09-21

Family

ID=42119383

Family Applications (1)

Application Number Title Priority Date Filing Date
TW098135951A TWI453235B (en) 2008-10-23 2009-10-23 Underlayer film for forming image

Country Status (5)

Country Link
JP (1) JP5532259B2 (en)
KR (1) KR101674645B1 (en)
CN (1) CN102197489B (en)
TW (1) TWI453235B (en)
WO (1) WO2010047346A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5783380B2 (en) * 2012-03-23 2015-09-24 Jsr株式会社 Liquid crystal aligning agent and method for forming liquid crystal aligning film
CN104854205B (en) * 2012-12-18 2018-12-28 日产化学工业株式会社 The lower membrane formation composition of self-assembled film containing polycyclic aromatic acetyl compounds
JP2019001859A (en) * 2017-06-13 2019-01-10 Dic株式会社 Modification method of polymer film surface
JP7229354B2 (en) * 2019-07-11 2023-02-27 富士フイルム株式会社 Resin composition, film, color filter, solid-state imaging device, image display device, resin and compound

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0213573B1 (en) * 1985-08-30 1991-11-21 General Electric Company Crystalline polyimides containing cumulative phenylene sulfide units
US5288588A (en) * 1989-10-27 1994-02-22 Nissan Chemical Industries Ltd. Positive photosensitive polyimide resin composition comprising an o-quinone diazide as a photosensitive compound
US5449741A (en) * 1990-09-28 1995-09-12 Nippon Telegraph And Telephone Corporation Polyimide optical material
JP2743860B2 (en) * 1994-04-28 1998-04-22 日本電気株式会社 User program debug processing system
JPH08146431A (en) * 1994-11-24 1996-06-07 Hitachi Ltd Composition for liquid crystal oriented film, and liquid crystal oriented film
TW498091B (en) * 1998-11-09 2002-08-11 Kanegafuchi Chemical Ind Polyimide composition and its manufacture process
JP3635615B2 (en) 1999-02-02 2005-04-06 大日本印刷株式会社 ELECTROLUMINESCENT ELEMENT AND MANUFACTURING METHOD THEREOF
AU2001265390A1 (en) * 2000-06-06 2001-12-17 Ekc Technology, Inc. Method of making electronic materials
JP4894120B2 (en) * 2001-09-27 2012-03-14 Jnc株式会社 Phenylenediamine derivative, liquid crystal alignment film, and liquid crystal display element
JP3951886B2 (en) 2002-10-23 2007-08-01 株式会社日立製作所 WIRING BOARD, DISPLAY DEVICE, DISPLAY DEVICE COLOR FILTER, WIRING BOARD FORMING METHOD, DISPLAY DEVICE FORMING METHOD, DISPLAY DEVICE COLOR FILTER FORMING METHOD
JP4009181B2 (en) * 2002-11-08 2007-11-14 富士フイルム株式会社 Planographic printing plate precursor
JP4312476B2 (en) 2003-03-10 2009-08-12 株式会社リコー Pattern forming method, electronic device, electronic device array, and image display device
JP2006021491A (en) * 2004-07-09 2006-01-26 Ricoh Co Ltd Laminated structure, optics using laminated structure, display element, arithmetic element and method for manufacturing these elements
JP4678574B2 (en) * 2004-08-23 2011-04-27 株式会社リコー Multilayer structure, electronic element using the multilayer structure, electronic element array, and display device
JP4614349B2 (en) * 2004-09-30 2011-01-19 信越化学工業株式会社 Polyimide having alcoholic hydroxyl group and method for producing the same
JP5209844B2 (en) * 2004-11-30 2013-06-12 株式会社リコー ELECTRONIC DEVICE AND METHOD FOR MANUFACTURING THE SAME, OPERATION ELEMENT AND DISPLAY ELEMENT
JP4386454B2 (en) * 2006-08-22 2009-12-16 信越化学工業株式会社 Photosensitive polyimide resin soluble in alkaline aqueous solution, composition containing the resin, and film obtained from the composition
WO2009113549A1 (en) * 2008-03-10 2009-09-17 日産化学工業株式会社 Composition for forming underlayer film for image formation

Also Published As

Publication number Publication date
WO2010047346A1 (en) 2010-04-29
JP5532259B2 (en) 2014-06-25
CN102197489B (en) 2013-08-21
CN102197489A (en) 2011-09-21
KR20110082051A (en) 2011-07-15
JPWO2010047346A1 (en) 2012-03-22
KR101674645B1 (en) 2016-11-09
TWI453235B (en) 2014-09-21

Similar Documents

Publication Publication Date Title
TWI461459B (en) Polyimide precursor and polyimide, and image-forming underlayer application solution
JP4027384B2 (en) Insulating film containing soluble polyimide resin and all-organic thin-film transistor using the same
TWI461461B (en) Underlayer film composition for forming image
JP5212596B2 (en) Organic transistor
TWI471359B (en) An electrode patterning layer containing polyamic acid or polyimide, and an electronic device using the same
WO2010061886A1 (en) Composition for forming gate dielectric of thin film transistor
TW201031687A (en) Underlayer film for forming image
US10573834B2 (en) Coating liquid for gate insulating film, gate insulating film and organic transistor
JPWO2010047346A6 (en) Underlayer film for image formation
CN105229812B (en) Soluble cyclic imide-containing polymers as dielectrics in organic electronic applications
KR100552989B1 (en) Photosensitive polyamic acid derivatives and polyimides for insulator of organic thin film transistor
KR101187609B1 (en) Low temperature processable and photo-crosslinkable organic gate insulator, and organic thin film transistor device using the same
KR101411830B1 (en) Low temperature processable and photo-crosslinkable organic gate insulator, and organic thin film transistor device using the same
KR20230024064A (en) Fluorine polymer gate dielectric and electric device using the same