TW201313781A

TW201313781A - Polyamic acid resin composition, polyimide resin composition and polyimide oxazole resin composition and flexible substrate containing the same

Info

Publication number: TW201313781A
Application number: TW101129649A
Authority: TW
Inventors: Junji Wakita; Daichi Miyazaki; Kazuto Miyoshi; Masao Tomikawa
Original assignee: Toray Industries
Priority date: 2011-08-18
Filing date: 2012-08-16
Publication date: 2013-04-01
Also published as: JPWO2013024849A1; TWI570156B; KR101921919B1; CN103842408B; SG2014013874A; JP5928447B2; KR20140051430A; CN103842408A; WO2013024849A1

Abstract

The present invention provide a polyamic acid resin composition, a polyimide resin composition and a polyimide oxazole resin composition, and a flexible substrate containing the same, which have excellent heat resistance, optical transparency, and low birefringence after treating film by heat. A polyamic acid resin composition is characterized by comprising the main component (a) a polyamic acid represented by general formula (1) as the structural unit, and (b) a solvent. (in general formula (1), X1 and X2 are each independently hydrogen or an monovalent organic group having carbon number of 1 to 10; R1 is an tetravalent organic group with carbon number of 4 to 40 having monocyclic or multicyclic alicyclic structure, or an tetravalent organic group with carbon number of 4 to 40 formed by an organic group having monocyclic alicyclic structure bonding each other directly or crosslinking each other; R2 is a divalent organic group with carbon number of 2 to 40 having at least two hydroxyl groups).

Description

聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物、以及含有其之可撓性基板Polylysine resin composition, polyimine resin composition, and polyamidiazole resin composition, and flexible substrate containing the same

本發明係關於一種聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物、以及含有其之可撓性基板者。更詳言之，關於一種適用於平板顯示器、觸控面板、電子紙、彩色濾光片基板、太陽能電池等之可撓性基板、可撓性印刷基板等之聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物、以及含有其之可撓性基板者。 The present invention relates to a polyaminic acid resin composition, a polyimide composition, and a polyimine The azole resin composition and the flexible substrate containing the same. More specifically, a polyamic acid resin composition suitable for use in a flexible display substrate such as a flat panel display, a touch panel, an electronic paper, a color filter substrate, a solar cell, or the like, a flexible printed circuit board, or the like Yttrium imine resin composition and polyimine The azole resin composition and the flexible substrate containing the same.

與玻璃作一比較，有機膜具有下列之優點：富彎曲性、難以破裂、重量輕。最近，藉由將平板顯示器之基板更換成有機膜，使顯示器可撓化之動作活潑化。 Compared with glass, organic film has the following advantages: rich in flexibility, difficult to break, and light in weight. Recently, by changing the substrate of the flat panel display to an organic film, the operation of the display can be made flexible.

在有機膜上製作顯示器之情形，一般係在受載基板上長成有機膜，於元件製作後，再從受載基板剝離的製程。針對於受載基板長成有機膜，有以下之方法。例如，有使用黏著劑等而將有機膜貼附於玻璃基板上之方法(例如，專利文獻1)。或是，有將含有成為薄膜原料之樹脂等之溶液塗布於受載基板上，利用熱等使其硬化而製作之方法(例如，專利文獻2)。前者必須在受載基板與薄膜之間設置黏著劑，有因黏著劑之耐熱性而限制以後之製程溫度。另一方面，後者係在未使用黏著劑、所製膜之膜表面平滑性高等之點上為優異。 When a display is produced on an organic film, it is generally a process in which an organic film is grown on a carrier substrate and then peeled off from the carrier substrate after the device is fabricated. There are the following methods for growing the substrate into an organic film. For example, there is a method of attaching an organic film to a glass substrate using an adhesive or the like (for example, Patent Document 1). Alternatively, a method of applying a solution containing a resin or the like as a raw material of a film onto a substrate to be carried and curing it by heat or the like (for example, Patent Document 2). The former must be provided with an adhesive between the substrate to be loaded and the film, and the subsequent process temperature is limited by the heat resistance of the adhesive. On the other hand, the latter is excellent in that the surface of the film to be formed is high in smoothness without using an adhesive.

作為可用於有機膜之樹脂，可舉例：聚酯、聚醯胺、聚醯亞胺、聚碳酸酯、聚醚碸、壓克力(丙烯酸)、環氧樹脂等。其中，聚醯亞胺樹脂係作為高耐熱性樹脂且適合於顯示器基板。尤其，聚醯亞胺樹脂係除了高的耐熱性之外，由於也同時具有高機械強度、耐磨耗性、尺寸安定性、耐藥品性等之優異的機械特性、絕緣性等之優異的電特性而在電‧電子產業領域被廣泛利用。利用上述之塗布法而長成聚醯亞胺膜之情形，可使用塗布含有先質之聚醯胺酸溶液，使其硬化而轉換成聚醯亞胺之方法。一般而言，聚醯胺酸係藉由使酸酐與二胺反應而能夠容易合成。 As the resin which can be used for the organic film, for example, polyester, polyamide, polyimine, polycarbonate, polyether oxime, acrylic (acrylic acid), ring Oxygen resin, etc. Among them, the polyimide resin is suitable as a high heat resistant resin and is suitable for a display substrate. In particular, in addition to high heat resistance, the polyimide resin has excellent mechanical properties such as high mechanical strength, abrasion resistance, dimensional stability, and chemical resistance, and excellent electrical properties such as insulation properties. Characteristics are widely used in the field of electricity and electronics. In the case where the polyimine film is grown by the above-described coating method, a method in which a precursor containing polyamic acid solution is applied and hardened to be converted into a polyimide may be used. In general, polylysine can be easily synthesized by reacting an acid anhydride with a diamine.

雖然由芳香族酸二酐與芳香族二胺所衍生的全部芳香族聚醯亞胺係具有高的耐熱性，但由於存在源自分子內.分子間電荷轉移錯合物之可見光波長區域的吸收帶，所得之聚醯亞胺膜將會著色成黃至茶褐色。又，一般具有大的雙折射性。因此，無法作為要求高透明性、低雙折射性的顯示基板使用。作為玻璃基板之代替材料使用時，一般尋求膜厚10微米且400nm之光透射率為80%以上、具有玻璃轉移溫度(Tg)或熱分解開始溫度為300℃以上、在可見光波長區域(400nm至800nm)之雙折射率為0.01以下的低雙折射性。 Although all aromatic polyimines derived from aromatic acid dianhydrides and aromatic diamines have high heat resistance, they are absorbed by visible light wavelength regions derived from intramolecular and intermolecular charge transfer complexes. The resulting polyimine film will be colored yellow to brown. Also, it generally has a large birefringence. Therefore, it cannot be used as a display substrate requiring high transparency and low birefringence. When used as a substitute material for a glass substrate, generally, a light transmittance of 10 μm and 400 nm is required to be 80% or more, a glass transition temperature (Tg) or a thermal decomposition initiation temperature is 300° C. or more, and a visible light wavelength region (400 nm to The birefringence of 800 nm) is low birefringence of 0.01 or less.

作為抑制聚醯亞胺之電荷轉移相互作用、使光透射性提高之方法，可舉例：將脂環式單體使用於酸二酐與二胺中之至少任一種成分之方法。 As a method of suppressing the charge-transfer interaction of the polyimine and improving the light transmittance, a method of using the alicyclic monomer in at least one of the acid dianhydride and the diamine can be exemplified.

例如，於專利文獻3中揭示由脂環式酸二酐與各種芳香族或脂環式二胺所得之聚醯亞胺係具有高透明性、低雙折射率。 For example, Patent Document 3 discloses that a polyfluorene imide obtained from an alicyclic acid dianhydride and various aromatic or alicyclic diamines has high transparency and low birefringence.

於專利文獻4中，揭示由1S,2S,4R,5R-環己烷四羧酸二酐與2,2’-雙(三氟甲基)聯苯胺(TFMB)所得之聚醯亞胺係具有高透明性、高Tg。又，於專利文獻4中，已記載使用2,2’-雙(4-(4-胺基苯氧基)苯基)六氟丙烷(HFBAPP)以取代2,2’-雙(三氟甲基)聯苯胺之聚醯亞胺膜係具有高透明性。 Patent Document 4 discloses that a polyimide obtained from 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 2,2'-bis(trifluoromethyl)benzidine (TFMB) has High transparency and high Tg. Further, in Patent Document 4, it has been described that 2,2'-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane (HFBAPP) is used in place of 2,2'-bis(trifluoromethyl). The polyimine film of phenylenebenzamide has high transparency.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2006-091822號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-091822

[專利文獻2]日本特表2007-512568號公報 [Patent Document 2] Japanese Patent Publication No. 2007-512568

[專利文獻3]日本特開平11-080350號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 11-080350

[專利文獻4]日本特開2010-085992號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-085992

但是，在專利文獻3中記載的聚醯亞胺群係Tg不夠高。又，在專利文獻4中記載的聚醯亞胺群中，Tg及雙折射率不符合一般之要求特性。 However, the poly-imine group Tg described in Patent Document 3 is not sufficiently high. Further, in the polyamidene group described in Patent Document 4, Tg and birefringence do not conform to the general requirements.

如此方式，符合高透明性、高耐熱性、低雙折射性全部之要求特性的聚醯亞胺材料現狀尚未明確。 In this manner, the current state of polyimine materials that meet all of the required properties of high transparency, high heat resistance, and low birefringence is not clear.

本發明係有鑒於上述之問題，提供一種聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物、以及含有其之可撓性基板，熱處理後之膜具有優異的耐熱性、光透射性、低雙折射性，將其作為課題。 The present invention provides a polyamido resin composition, a polyimide resin composition, and a polyimine in view of the above problems. The azole resin composition and the flexible substrate containing the same have excellent heat resistance, light transmittance, and low birefringence as a film after heat treatment, which is a problem.

為了解決上述之問題、達成目的，有關本發明之聚醯胺酸樹脂組成物，其特徵為含有(a)以通式(1)所表示之構造單元作為主要成分之聚醯胺酸與(b)溶劑； (通式(1)中，X₁、X₂係各自獨立地表示氫原子或是碳數1至10之1價有機基；R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基；R₂係表示具有至少2個羥基的碳數2至40之2價有機基)。 In order to solve the above problems and achieve the object, the polyaminic acid resin composition of the present invention is characterized in that it contains (a) a polyamic acid having a structural unit represented by the general formula (1) as a main component and (b) ) solvent; (In the formula (1), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and R ₁ represents an alicyclic structure having a monocyclic or condensed polycyclic ring type; a tetravalent organic group having 4 to 40 carbon atoms, or an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 4 to 40 carbon atoms which are interlinked by a crosslinked structure; R ₂ represents a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups.

又，有關本發明之聚醯亞胺樹脂組成物，其特徵為含有以(a’)通式(2)所表示之構造單元作為主要成分的聚醯亞胺與(b)溶劑； (通式(2)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基；R₂係表示具有至少2個羥基的碳數2至40之2價有機基)。 Further, the polyimine resin composition of the present invention is characterized in that it contains a polyimine which has a structural unit represented by (a') general formula (2) as a main component and (b) a solvent; (In the formula (2), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in the intermediate structure; and R ₂ means a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups.

又，有關本發明之聚醯亞胺唑樹脂組成物，其特徵為含有以(a”)通式(3)所表示之構造單元作為主要成分的聚醯亞胺唑與(b)溶劑； (通式(3)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基；R₃係表示碳數2至40之4價有機基)。 Further, the polyimine of the present invention An azole resin composition characterized by containing a polyimine which has a structural unit represented by the formula (3) (3) as a main component Oxazole and (b) solvent; (In the formula (3), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in a crosslinked structure; R ₃ means a tetravalent organic group having 2 to 40 carbon atoms.

若根據本發明，能夠獲得一種聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物、以及含有其之可撓性基板，熱處理後之膜具有優異的耐熱性、在可見光區域之高的光透射性、低雙折射性。 According to the present invention, a polyamido resin composition, a polyimide composition, and a polyimine can be obtained. The azole resin composition and the flexible substrate containing the same have excellent heat resistance, high light transmittance in the visible light region, and low birefringence.

[實施發明之形態] [Formation of the Invention]

以下，與圖示一併詳細說明為了實施本發明之形態。還有，藉由下列之實施形態，本發明並非受限定者。又，於以下之說明中所參閱的各圖只不過是可理解本發明內容之程度而概略地顯示形狀、大小、及位置關係。亦即，本發明並不僅限定於各圖所例示之形狀、大小、及位置關係。 Hereinafter, the form for carrying out the present invention will be described in detail together with the drawings. Further, the present invention is not limited by the following embodiments. Moreover, the drawings referred to in the following description are merely schematic to show the shape, size, and positional relationship to the extent that the content of the present invention can be understood. That is, the present invention is not limited to the shapes, sizes, and positional relationships illustrated in the respective drawings.

本發明之第1形態係一種聚醯胺酸樹脂組成物，其特徵為含有(a)以通式(1)所表示之構造單元作為主要成分之聚醯胺酸與(b)溶劑。本發明之第2形態係一種聚醯亞胺樹脂組成物，其特徵為含有以(a’)通式(2)所表示之構造單元作為主要成分的聚醯亞胺與(b)溶劑。本發明之第3形態係一種聚醯亞胺唑樹脂組成物，其特徵為含有以(a”)通式(3)所表示之構造單元作為主要成分的聚醯亞胺唑與(b)溶劑。 The first aspect of the present invention is a polyacetic acid resin composition comprising (a) a polyamic acid having a structural unit represented by the formula (1) as a main component and (b) a solvent. The second aspect of the present invention is a polyimine resin composition comprising a polyimine which has a structural unit represented by the formula (2) (a) as a main component and (b) a solvent. The third aspect of the present invention is a polyimine An azole resin composition characterized by containing a polyimine which has a structural unit represented by the formula (3) (3) as a main component Oxazole and (b) solvent.

通式(1)中，X₁、X₂係各自獨立地表示氫原子或是碳數1至10之1價有機基。通式(1)至(3)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基。通式(1)、(2)中，R₂係表示具有至少2個羥基的碳數2至40之2價有機基。通式(3)中，R₃係表示碳數2至40之4價有機基。 In the formula (1), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. In the general formulae (1) to (3), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or a monocyclic alicyclic structure. The organic group is a tetravalent organic group having 4 to 40 carbon atoms directly or in a crosslinked structure interposed therebetween. In the general formulae (1) and (2), R ₂ represents a divalent organic group having 2 to 40 carbon atoms and having at least two hydroxyl groups. In the formula (3), R ₃ represents a tetravalent organic group having 2 to 40 carbon atoms.

若本發明之聚醯胺酸為以該通式(1)所表示之構造單元作為主要成分的話，亦可含有其他之構造單元。其他之構造單元，可舉例：酸二酐與二胺化合物之聚縮合物的聚醯胺酸、二羧酸衍生物與羥基二胺之聚縮合物的聚羥基醯胺、聚醯胺酸之脫水閉環物的聚醯亞胺、聚羥基醯胺之脫水閉環物的聚醯亞胺唑等，例如，亦可含有以該通式(2)所表示之構造單元、以該通式(3)所表示之構造單元、該通式(1)中之R₁為芳香環的聚醯胺酸、該通式(2)中之R₁為芳香環的聚醯亞胺、該通式(3)中之R₁為芳香環的聚醯亞胺唑。全部之50%以上較佳為含有以該通式(1)所表示之構造單元，更佳為含有70%以上，進一步較佳為含有90%以上。 When the polyglycolic acid of the present invention has a structural unit represented by the above formula (1) as a main component, it may contain other structural units. Other structural units may, for example, be a polyglycolic acid of a polycondensate of an acid dianhydride and a diamine compound, a polyhydroxyguanamine of a polycondensate of a dicarboxylic acid derivative and a hydroxydiamine, and a dehydration of polyglycine. Closed-loop polyimine, polyhydroxyimide, dehydration ring closure For example, the azole or the like may contain a structural unit represented by the general formula (2), a structural unit represented by the general formula (3), and a polyfluorene in which the R ₁ in the general formula (1) is an aromatic ring. An amino acid, a polyimine in which R ₁ in the formula (2) is an aromatic ring, and a polyimine in which the R ₁ in the formula (3) is an aromatic ring Oxazole. It is preferable that 50% or more of all the structural units represented by the above formula (1) are contained, more preferably 70% or more, and still more preferably 90% or more.

聚醯胺酸係如後所述，能夠藉由二胺化合物與酸二酐或其衍生物之反應而合成。作為衍生物可舉例：該酸二酐之四羧酸、其四羧酸之一、二、三或四酯、酸氯化物等。 Polylysine can be synthesized by a reaction of a diamine compound with an acid dianhydride or a derivative thereof as described later. The derivative may, for example, be a tetracarboxylic acid of the acid dianhydride, one of the tetracarboxylic acids, a di-, tri- or tetra-ester, an acid chloride or the like.

若本發明之聚醯亞胺為以該通式(2)所表示之構造單元作為主要成分者的話，亦可含有其他之構造單元。作為其他之構造單元，可舉例：聚醯胺酸、聚羥基醯胺、聚醯亞胺、聚苯并唑等。例如，亦可含有以該通式(1)所表示之構造單元、以該通式(3)所表示之構造單元、該通式(1)中之R₁為芳香環的聚醯胺酸、該通式(2)中之R₁為芳香環的聚醯亞胺、該通式(3)中之R₁為芳香環的聚醯亞胺唑。全部之50%以上較佳為含有以該通式(2)所表示之構造單元，更佳為含有70%以上，進一步較佳為含有90%以上。 When the polyimine of the present invention is a structural unit represented by the above formula (2) as a main component, other structural units may be contained. As other structural units, for example, polylysine, polyhydroxyguanamine, polyimine, polybenzo Oxazole and the like. For example, it may contain a structural unit represented by the general formula (1), a structural unit represented by the general formula (3), and a polyamic acid in which R ₁ in the general formula (1) is an aromatic ring, In the formula (2), R _{1 which} is an aromatic ring, a polyimine in which the R ₁ in the formula (3) is an aromatic ring Oxazole. It is preferable that 50% or more of all the structural units represented by the above formula (2) are contained, more preferably 70% or more, and still more preferably 90% or more.

聚醯亞胺係如後述，藉由經二胺化合物與酸二酐或其衍生物之反應所合成的聚醯胺酸之加熱脫水閉環、化學脫水閉環反應而能夠合成。 Polyimine is described later by a diamine compound and acid dianhydride or The polyglycine synthesized by the reaction of the derivative can be synthesized by heating dehydration ring closure or chemical dehydration ring closure reaction.

若本發明之聚醯亞胺唑為以該通式(3)所表示之構造單元作為主要成分者的話，亦可含有其他之構造單元。作為其他之構造單元，可舉例：聚醯胺酸、聚羥基醯胺、聚醯亞胺、聚苯并唑等。例如，亦可含有以該通式(1)所表示之構造單元、以該通式(2)所表示之構造單元、該通式(1)中之R₁為芳香環的聚醯胺酸、該通式(2)中之R₁為芳香環的聚醯亞胺、該通式(3)中之R₁為芳香環的聚醯亞胺唑。全部之50%以上較佳為含有以該通式(3)所表示之構造單元，更佳為含有70%以上，進一步較佳為含有90%以上。 Polyimine of the present invention When the azole is a structural unit represented by the above formula (3), it may contain other structural units. As other structural units, for example, polylysine, polyhydroxyguanamine, polyimine, polybenzo Oxazole and the like. For example, it may contain a structural unit represented by the general formula (1), a structural unit represented by the general formula (2), and a polyamic acid in which the R ₁ in the general formula (1) is an aromatic ring. In the formula (2), R _{1 which} is an aromatic ring, a polyimine in which the R ₁ in the formula (3) is an aromatic ring Oxazole. It is preferable that 50% or more of all the structural units represented by the above formula (3) are contained, more preferably 70% or more, and still more preferably 90% or more.

聚醯亞胺唑係如後述，藉由經具有羥醯胺基之二胺化合物與酸二酐或其衍生物之反應所合成的聚醯胺酸之加熱脫水閉環、化學脫水閉環反應而能夠合成。藉由經具有唑環之二胺化合物與酸二酐或其衍生物之反應所合成的聚醯胺酸之加熱脫水閉環、化學脫水閉環反應而能夠合成。 Polyimine The azole can be synthesized by a heating dehydration ring closure or a chemical dehydration ring closure reaction of polyglycine synthesized by a reaction of a hydroxyguanamine group-containing diamine compound with an acid dianhydride or a derivative thereof as described later. By having The polyamino acid synthesized by the reaction of the diamine compound of the azole ring with the acid dianhydride or its derivative can be synthesized by heating dehydration ring closure or chemical dehydration ring closure reaction.

在通式(1)至(3)之R₁係表示酸成分之結構，表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基。於此，該脂環結構係一部分之氫原子亦可被鹵素所取代。又，可單獨地或組合複數之此等酸成分而作為酸成分使用。 R ₁ in the general formulae (1) to (3) represents a structure of an acid component, and represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or has a single The organic group of the cyclic alicyclic structure directly or crosslinks the interconnected structure with a carbon number of 4 to 40 tetravalent organic groups bonded to each other. Here, a part of the hydrogen atom of the alicyclic structure may be substituted by a halogen. Further, these acid components may be used singly or in combination as an acid component.

若舉例具有能夠用於本發明之脂環結構的酸二酐時，可舉例：1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,3,4-環己烷四羧酸二酐、1,2,4,5-環戊烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環庚烷四羧酸二酐、2,3,4,5-四氫呋喃四羧酸二酐、3,4-二羧基-1-環己基琥珀酸二酐、2,3,5-三羧基環戊基乙酸二酐、3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐、雙環[3.3.0]辛烷-2,4,6,8-四羧酸二酐、雙環[4.3.0]壬烷-2,4,7,9-四羧酸二酐、雙環[4.4.0]癸烷-2,4,7,9-四羧酸二酐、雙環[4.4.0]癸烷-2,4,8,10-四羧酸二酐、三環[6.3.0.0<2,6>]十一烷-3,5,9,11-四羧酸二酐、雙環[2.2.2]辛烷-2,3,5,6-四羧酸二酐、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、雙環[2.2.1]庚烷四羧酸二酐、雙環[2.2.1]庚烷-5-羧甲基-2,3,6-三羧酸二酐、7-雙環[2.2.1]庚烷-2,4,6,8-四羧酸二酐、八氫萘-1,2,6,7-四羧酸二酐、十四氫蒽-1,2,8,9-四羧酸二酐、3,3’,4,4’-二環己烷四羧酸二酐、3,3’,4,4’-氧二環己烷四羧酸二酐、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基-環己烯-1,2-二羧酸酐、及“Rikacid”(註冊商標)BT-100(以上商品名、新日本理化股份有限公司製)及此等之衍生物等。 When an acid dianhydride which can be used in the alicyclic structure of the present invention is exemplified, examples thereof include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-cyclopentane IV. Carboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 -Naphthalene succinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic acid Dihydride, bicyclo[4.4.0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4.4.0]nonane-2,4,8,10-tetracarboxylic dianhydride, three Ring [6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid Anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane -5-carboxymethyl-2,3,6-tricarboxylic acid Dihydride, 7- Bicyclo[2.2.1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetrahydroanthracene-1,2, 8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride , 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, and "Rikacid" (registered trademark) BT-100 (above) Trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.) and derivatives of these.

於上述結構之中，作為在通式(1)至(3)之R₁較佳之物，例如，可舉例：以下列通式(4)至(10)所表示之結構。 Among the above structures, as the preferable ones of R ₁ in the general formulae (1) to (3), for example, the structures represented by the following general formulae (4) to (10) can be exemplified.

通式(4)至(10)中，R₄至R₇₉係各自獨立地表示氫原子、鹵素原子或是氫原子亦可被鹵素原子所取代的碳數1至3之1價有機基。作為通式(4)至(6)之脂環結構，可舉例：分別為環丁烷、環戊烷、環己烷等。通式(7)中，X₃係氧原子、硫原子、磺醯基或氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基或是由此等2個以上連結構成之2價交聯結構。作為如此之脂環結構，可舉例：雙環[2.2.1]庚烷、雙環[2.2.1]辛-2-烯、7-雙環[2.2.1]庚烷等。作為通式(8)、(9)之脂環結構，可舉例：分別為十氫萘、十四蒽。於通式(10)中，X₄係直接鍵結、氧原子、硫原子、磺醯基、氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基或氫原子亦可被鹵素原子所取代的伸芳基、或是氧原子、硫原子、磺醯基、氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基及氫原子亦可被鹵素原子所取代的伸芳基所選出的由2個以上連結構成之2價交聯結構。作為如此之脂環結構，可舉例：1,1-雙環己烷、氧二環己烷等。 In the general formulae (4) to (10), R ₄ to R ₇₉ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom. The alicyclic structure of the general formulae (4) to (6) may, for example, be cyclobutane, cyclopentane or cyclohexane. In the formula (7), the X ₃ -based oxygen atom, the sulfur atom, the sulfonyl group or the hydrogen atom may be substituted by a halogen atom, and the divalent organic group having 1 to 3 carbon atoms may be substituted or two or more The two-valent crosslinked structure. As such an alicyclic structure, bicyclo [2.2.1] heptane, bicyclo [2.2.1] oct-2-ene, 7- Bicyclo [2.2.1] heptane and the like. Examples of the alicyclic structure of the general formulae (8) and (9) include decalin and tetradecyl. In the formula (10), X ₄ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a hydrogen atom or a hydrogen atom having 1 to 3 carbon atoms or a hydrogen atom which may be substituted by a halogen atom. a aryl group having a carbon number of 1 to 3 and a hydrogen atom which may be substituted by a halogen atom or an oxygen atom, a sulfur atom, a sulfonyl group or a hydrogen atom may be substituted by a halogen atom or a halogen atom. A divalent crosslinked structure composed of two or more linked groups selected by the substituted aryl group. As such an alicyclic structure, 1,1-bicyclohexane, oxybicyclohexane, etc. are mentioned.

若舉例上述之酸二酐時，可舉例：1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,3,4-環己烷四羧酸二酐、1,2,4,5-環戊烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環庚烷四羧酸二酐、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、雙環[2.2.1]庚烷四羧酸二酐、7-雙環[2.2.1]庚烷-2,4,6,8-四羧酸二酐、八氫萘-1,2,6,7-四羧酸二酐、十四氫蒽-1,2,8,9-四羧酸二酐、3,3’,4,4’-二環己烷四羧酸二酐、3,3’,4,4’-氧二環己烷四羧酸二酐等。 When the above acid dianhydride is exemplified, examples thereof include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2, 3,4-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, bicyclo [2.2.1] heptane tetracarboxylic dianhydride, 7- Bicyclo[2.2.1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetrahydroanthracene-1,2, 8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride Wait.

其中，從市售容易取得之觀點，及從與二胺化合物的反應性之觀點，通式(1)中之R₁為以下列化學式(11)至(13)所表示之1S,2S,4R,5R-環己烷四羧酸二酐、1R,2S,4S,5R-環己烷四羧酸二酐、3,3’,4,4’-二環己烷四羧酸二酐。此等之酸二酐係由岩谷瓦斯股份有限公司作成製品名「PMDA-HH」、「PMDA-HS」、「BPDA-H」而被市售。還有，此等之酸二酐能夠單獨地或組合2種以上而使用。 Among them, R ₁ in the general formula (1) is 1S, 2S, 4R represented by the following chemical formulas (11) to (13) from the viewpoint of being readily available in the market and from the viewpoint of reactivity with a diamine compound. 5R-cyclohexanetetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride. These acid dianhydrides are commercially available from Iwatani Gas Co., Ltd. under the product names "PMDA-HH", "PMDA-HS", and "BPDA-H". Further, these acid dianhydrides can be used singly or in combination of two or more.

又，於不妨礙本發明之效果的範圍內，能夠將該酸二酐之一部分置換成其他酸二酐而使用。作為其他之酸二酐，可舉例：芳香族酸二酐或脂肪族酸二酐。例如，作為芳香族酸二酐可舉例：焦蜜石酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,3,3’,4’-聯苯四羧酸二酐、2,2’,3,3’-聯苯四羧酸二酐、3,3’,4,4’-聯三苯四羧酸二酐、3,3’,4,4’- 氧鄰苯二甲酸二酐、2,3,3’,4’-氧鄰苯二甲酸二酐、2,3,2’,3’-氧鄰苯二甲酸二酐、二苯基碸-3,3’,4,4’-四羧酸二酐、二苯甲酮-3,3’,4,4’-四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)醚二酐、雙(1,3-二側氧-1,3-二氫異丙并呋喃-5-羧酸)-1,4-伸苯、2,2-雙(4-(4-胺基苯氧基)苯基)丙烷、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、2,3,5,6-吡啶四羧酸二酐、3,4,9,10-苝四羧酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、2,2-雙(4-(3,4-二羧基苯氧基)苯基)六氟丙烷二酐、2,2-雙(4-(3,4-二羧苄氧基)苯基)六氟丙烷二酐、1,6-二氟焦蜜石酸二酐、1-三氟甲基焦蜜石酸二酐、1,6-二(三氟甲基)焦蜜石酸二酐、2,2’-雙(三氟甲基)-4,4’-雙(3,4-二羧基苯氧基)聯苯二酐、“Rikacid”(註冊商標)TMEG-100(商品名、新日本理化股份有限公司製)等之芳香族四羧酸二酐及此等之衍生物等。作為脂肪族酸二酐，可舉例：1,2,3,4-丁烷四羧酸二酐、1,2,3,4-戊烷四羧酸二酐及此等之衍生物等，但並非受此等所限定。又，此等其他之酸二酐能夠單獨地或組合2種以上而使用。 Moreover, it is possible to use one of the acid dianhydrides in place of other acid dianhydrides within a range that does not impair the effects of the present invention. As another acid dianhydride, an aromatic acid dianhydride or an aliphatic acid dianhydride can be exemplified. For example, as the aromatic acid dianhydride, pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylate can be exemplified. Acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' - Oxyphthalic acid dianhydride, 2,3,3',4'-oxyphthalic acid dianhydride, 2,3,2',3'-oxyphthalic dianhydride, diphenylphosphonium-3 , 3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-double ( 2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis (3,4- Dicarboxyphenyl)ether dianhydride, bis(1,3-di-oxo-1,3-dihydroisopropylfuran-5-carboxylic acid)-1,4-benzobenzene, 2,2-bis (4 -(4-Aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5 , 6-pyridine tetracarboxylic dianhydride, 3,4,9,10-decane tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2- Bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane Anhydride, 1,6-difluoropyroic acid dianhydride, 1-trifluoromethylpyramine dianhydride, 1,6-bis(trifluoromethyl)pyroic acid dianhydride, 2,2 - bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, "Rikacid" (registered trademark) TMEG-100 (trade name, New Japan Physical and Chemical Co., Ltd.) An aromatic tetracarboxylic dianhydride such as a company, and the like. Examples of the aliphatic acid dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and the like, but Not limited by these. Further, these other acid dianhydrides can be used singly or in combination of two or more.

通式(1)、(2)中之R₂係具有至少2個羥基之碳數2至40之2價有機基，例如，可舉例：以化學式(14)至(23)所表示之結構。 R ₂ in the general formulae (1) and (2) has a divalent organic group having 2 to 40 carbon atoms and having at least two hydroxyl groups. For example, a structure represented by the chemical formulas (14) to (23) can be exemplified.

此等之中，從透明性之觀點，較佳為化學式(14)之結構，更佳為使用以下式(24)所表示之二胺。 Among these, from the viewpoint of transparency, the structure of the chemical formula (14) is preferred, and the diamine represented by the following formula (24) is more preferably used.

通式(3)中之R₃係表示碳數2至40之4價有機基，例如，可舉例：以化學式(25)至(34)所表示之結構。此等之中，從透明性之觀點，較佳為化學式(25)之結構。 R ₃ in the general formula (3) represents a tetravalent organic group having 2 to 40 carbon atoms, and examples thereof include the structures represented by the chemical formulas (25) to (34). Among these, from the viewpoint of transparency, the structure of the chemical formula (25) is preferred.

還有，通式(3)中之R₃為以化學式(25)所表示之聚醯亞胺唑係由以上述化學式(24)所表示之二胺所合成的以通式(1)所表示之聚醯胺酸、及以通式(2)所表示之聚醯亞胺的脫水閉環物。 Further, R ₃ in the formula (3) is a polyimine represented by the formula (25) The azole is a dehydrated ring-closing product of the polyaminic acid represented by the formula (1) and the polyimine represented by the formula (2) synthesized from the diamine represented by the above formula (24).

又，於不妨礙本發明之效果的範圍內，能夠將該二胺化合物之一部分置換成其他之二胺化合物。作為其他之二胺化合物，可舉例：芳香族二胺化合物、脂環式二胺化合物、或脂肪族二胺化合物。例如，作為芳香族二胺化合物，可舉例：3,4’-二胺基二苯基醚、4,4’-二胺基二苯基醚、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基碸、4,4’-二胺基二苯基碸、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2-雙(3-胺基-4-羥基苯基)六氟丙烷、3,3’-二胺基二苯基硫醚、4,4’-二胺基二苯基硫醚、1,4-雙(4-胺基苯氧基)苯、聯苯胺、2,2’-雙(三氟甲基)聯苯胺、3,3’-雙(三氟甲基)聯苯胺、2,2’-二甲基聯苯胺、3,3’-二甲基聯苯胺、2,2’,3,3’-四甲基聯苯胺、間伸苯基二胺、對伸苯基二胺、1,5-萘二胺、2,6-萘二胺、雙{4-(4-胺基苯氧基苯基)}碸、雙{4-(3-胺基苯氧基苯基)}碸、雙(4-胺基苯氧基)聯苯、雙{4-(4-胺基苯氧基)苯基}醚、1,4-雙(4-胺基苯基)苯、9,9-雙(4-胺基苯氧基)茀、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、4,4-二胺基苯甲醯胺苯、3,4-二胺基苯甲醯胺苯、4,4-二胺基二苯甲酮、3,3-二胺基二苯甲酮或是在此等之芳香族環上利用烷基、烷氧基、鹵素原子等所取代之二胺化合物，但並不受此等所限定。 Further, one of the diamine compounds may be partially substituted with another diamine compound within a range that does not impair the effects of the present invention. As the other diamine compound, an aromatic diamine compound, an alicyclic diamine compound, or an aliphatic diamine compound can be exemplified. For example, as the aromatic diamine compound, for example, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenylmethane can be exemplified. , 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 2,2-bis(4-amino group Phenyl) hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexa Fluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide Ether, 1,4-bis(4-aminophenoxy)benzene, benzidine, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine , 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2',3,3'-tetramethylbenzidine, meta-phenylenediamine, p-phenylene Diamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis{4-(4-aminophenoxyphenyl)}indole, bis{4-(3-aminophenoxybenzene)碸, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenyl)benzene 9,9-bis(4-aminophenoxy)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4- Aminophenoxy)phenyl]hexafluoropropane, 4,4-diaminobenzamide, 3,4-diaminobenzamide, 4,4-diaminobenzophenone And 3,3-diaminobenzophenone or a diamine compound substituted with an alkyl group, an alkoxy group, a halogen atom or the like on the aromatic ring, but is not limited thereto.

作為脂環式二胺化合物，可舉例：環丁烷二胺、異佛酮二胺、雙環[2.2.1]庚烷雙甲基胺、三環[3.3.1.13,7]癸烷-1,3-二胺、1,2-環己基二胺、1,3-環己基二胺、1,4-環己基二胺、4,4’-二胺基二環己基甲烷、3,3’-二甲基-4,4’-二胺基二環己基甲烷、3,3’-二乙基-4,4’-二胺基二環己基甲烷、3,3’,5,5’-四甲基-4,4’-二胺基二環己基甲烷、3,3’,5,5’-四乙基-4,4’-二胺基二環己基甲烷、3,5-二乙基-3’,5’-二甲基-4,4’-二胺基二環己基甲烷、4,4’-二胺基二環己基醚、3,3’-二甲基-4,4’-二胺基二環己基醚、3,3’-二乙基-4,4’-二胺基二環己基醚、3,3’,5,5’-四甲基-4,4’-二胺基二環己基醚、3,3’,5,5’-四乙基-4,4’-二胺基二環己基醚、3,5-二乙基-3’,5’-二甲基-4,4’-二胺基二環己基醚、2,2-雙(4-胺基環己基)丙烷、2,2-雙(3-甲基-4-胺基環己基)丙烷、2,2-雙(3-乙基-4-胺基環己基)丙烷、2,2-雙(3,5-二甲基-4-胺基環己基)丙烷、2,2-雙(3,5-二乙基-4-胺基環己基)丙烷、2,2-(3,5-二乙基-3’,5’-二甲基-4,4’-二胺基二環己基)丙烷、2,2’-雙(4-胺基環己基)六氟丙烷、2,2’-二甲基-4,4’-二胺基雙環己烷、2,2’-雙(三氟甲基)-4,4’-二胺基雙環己烷、或是在此等之脂環上利用烷基、烷氧基、鹵素原子等所取代之二胺化合物，但並不受此等所限定。 As the alicyclic diamine compound, for example, cyclobutanediamine, isophoronediamine, bicyclo[2.2.1]heptane dimethylamine, tricyclo[3.3.1.13,7]decane-1, 3-Diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 3,3'- Dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-four Methyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5-diethyl -3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl-4,4' -diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetramethyl-4,4'- Diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminobicyclohexane Ether, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2 , 2-bis(3-methyl-4-aminocyclohexyl)propane, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-di Methyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-diethyl-4-aminocyclohexyl)propane, 2,2-(3,5-diethyl-3' , 5'-Dimethyl-4,4'-diaminodicyclohexyl)propane, 2,2'-bis(4-aminocyclohexyl)hexafluoropropane, 2,2'-dimethyl-4 , 4'-diaminobicyclohexane, 2,2'-bis(trifluoromethyl)-4,4'-diaminobicyclohexane, or an alkyl group or an alkane on the alicyclic ring A diamine compound substituted with an oxy group, a halogen atom or the like, but is not limited thereto.

作為脂肪族二胺化合物，可舉例：伸乙基二胺、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷等之伸烷基二胺類；雙(胺基甲基)醚、雙(2-胺基乙基)醚、雙(3-胺基丙基)醚等之乙二醇二胺類；及1,3-雙(3-胺基丙基)四甲基二環己烷、1,3-雙(4-胺基丁基)四甲基二環己烷、α,ω-雙(3-胺基丙基)聚二甲基環己烷等之環己烷二胺類，但並不受此等所限定。 As the aliphatic diamine compound, for example, ethyl diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-di Alkyl hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, etc. Amines; ethylene glycol diamines such as bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether; and 1,3-bis(3) -aminopropyl)tetramethyldicyclohexane, 1,3-bis(4-aminobutyl)tetramethyldicyclohexane, α,ω-bis(3-aminopropyl)poly A cyclohexanediamine such as methylcyclohexane, but is not limited thereto.

此等之芳香族二胺化合物、脂環式二胺化合物、或脂肪族二胺化合物能夠單獨地或組合2種以上而使用。 These aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds can be used individually or in combination of 2 or more types.

此等之中，較佳為使用以下列化學式(35)所表示之9,9-(4-胺基苯基)茀二胺，煅燒膜之透明性或機械特性維持之狀態下，發現能夠使玻璃轉移溫度上升、減低雙折射率。 Among these, it is preferred to use 9,9-(4-aminophenyl)phosphonium diamine represented by the following chemical formula (35), and it is found that the transparency or mechanical properties of the calcined film are maintained. The glass transition temperature rises and the birefringence is reduced.

藉由使用以化學式(35)所表示之二胺而能夠將以下列通式(36)、或下列通式(37)所表示之構造單元導入分子鏈中。 The structural unit represented by the following general formula (36) or the following general formula (37) can be introduced into the molecular chain by using the diamine represented by the chemical formula (35).

(通式(36)中，X₁、X₂係各自獨立地表示氫原子或是碳數1至10之1價有機基。通式(36)、(37)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基)。 (In the formula (36), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. In the general formulae (36) and (37), R ₁ represents a single a tetravalent organic group having 4 to 40 carbon atoms of a cyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure, or a carbon having an interconnected structure interposed therebetween 4 to 40 of the 4 organic groups).

一般而言，使用以化學式(35)所表示之二胺的聚醯亞胺膜中，大多觀察到著色。與本發明之聚醯亞胺及聚醯亞胺唑膜作一比較，如後所述(比較例8)之使用作為透明PI之原料單體所用之4,4’-(六氟亞異丙基)二鄰苯二甲酸酐與以上述化學式(35)所表示之二胺等之聚醯亞胺膜之情形，透明性將會惡化。有關本發明之聚醯亞胺及聚醯亞胺唑膜，由於使用脂環式酸二酐而能夠抑制著色。 In general, coloring is often observed in a polyimide film using a diamine represented by the chemical formula (35). Polyimine and polyimine with the present invention As a comparison of the azole film, as described later (Comparative Example 8), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride used as a raw material monomer for transparent PI was used in the above chemical formula ( In the case of the polyimine film of the diamine or the like represented by 35), the transparency is deteriorated. Polyimine and polyimine of the present invention The azole film can suppress coloration by using an alicyclic acid dianhydride.

較佳在全部二胺殘基之10%以上50%以下之範圍內含有以該化學式(35)所表示之二胺，更佳在30%以上50%以下之範圍內含有，進一步較佳在40%以上50%以下之範圍內含有。藉此，於本發明之聚醯胺酸、聚醯亞胺及聚醯亞胺唑中，以通式(36)或通式(37)所表示之構造單元係含有10%至50%。 It is preferable to contain the diamine represented by the chemical formula (35) in a range of 10% or more and 50% or less of the total diamine residue, more preferably 30% or more and 50% or less, and still more preferably 40. % is included in the range of 50% or less. Thereby, the polyglycolic acid, the polyimine and the polyimine in the invention In the azole, the structural unit represented by the formula (36) or the formula (37) contains 10% to 50%.

為了將分子量調整至較佳的範圍內，本發明之聚醯胺酸、聚醯亞胺及聚醯亞胺唑亦可藉末端密封劑而密封兩末端。作為與酸二酐反應之末端密封劑，可舉例：一胺或一元醇等。又，作為與二胺化合物反應之末端密封劑，可舉例：酸酐、單羧酸、單酸氯化合物、單活性酯化合物等。又，藉由使末端密封劑反應而能夠導入作為末端之各種有機基。 In order to adjust the molecular weight to a preferred range, the polylysine, polyimine and polyimine of the present invention The azole can also seal both ends by an end sealant. As the terminal sealant to be reacted with the acid dianhydride, a monoamine or a monohydric alcohol or the like can be exemplified. Further, examples of the terminal sealant to be reacted with the diamine compound include an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a mono-active ester compound. Further, various organic groups as a terminal can be introduced by reacting the terminal sealant.

可用於末端密封劑之一胺，可舉例：5-胺基-8-羥基喹啉、4-胺基-8-羥基喹啉、1-羥基-8-胺基萘、1-羥基-7-胺基萘、1-羥基-6-胺基萘、1-羥基-5-胺基萘、1-羥基-4-胺基萘、1-羥基-3-胺基萘、1-羥基-2-胺基萘、1-胺基-7-羥基萘、2-羥基-7-胺基萘、2-羥基-6-胺基萘、2-羥基-5-胺基萘、2-羥基-4-胺基萘、2-羥基-3-胺基萘、1-胺基-2-羥基萘、1-羧基-8-胺基萘、1-羧基-7-胺基萘、1-羧基-6- 胺基萘、1-羧基-5-胺基萘、1-羧基-4-胺基萘、1-羧基-3-胺基萘、1-羧基-2-胺基萘、1-胺基-7-羧基萘、2-羧基-7-胺基萘、2-羧基-6-胺基萘、2-羧基-5-胺基萘、2-羧基-4-胺基萘、2-羧基-3-胺基萘、1-胺基-2-羧基萘、2-胺基菸鹼酸、4-胺基菸鹼酸、5-胺基菸鹼酸、6-胺基菸鹼酸、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、三聚氰酸一醯胺、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、2-胺基苯磺酸、3-胺基苯磺酸、4-胺基苯磺酸、3-胺基-4,6-二羥基嘧啶、2-胺基苯酚、3-胺基苯酚、4-胺基苯酚、5-胺基-8-巰基喹啉、4-胺基-8-巰基喹啉、1-巰基-8-胺基萘、1-巰基-7-胺基萘、1-巰基-6-胺基萘、1-巰基-5-胺基萘、1-巰基-4-胺基萘、1-巰基-3-胺基萘、1-巰基-2-胺基萘、1-胺基-7-巰基萘、2-巰基-7-胺基萘、2-巰基-6-胺基萘、2-巰基-5-胺基萘、2-巰基-4-胺基萘、2-巰基-3-胺基萘、1-胺基-2-巰基萘、3-胺基-4,6-二巰基嘧啶、2-胺基苯硫酚、3-胺基苯硫酚、4-胺基苯硫酚、2-乙炔基苯胺、3-乙炔基苯胺、4-乙炔基苯胺、2,4-二乙炔基苯胺、2,5-二乙炔基苯胺、2,6-二乙炔基苯胺、3,4-二乙炔基苯胺、3,5-二乙炔基苯胺、1-乙炔基-2-胺基萘、1-乙炔基-3-胺基萘、1-乙炔基-4-胺基萘、1-乙炔基-5-胺基萘、1-乙炔基-6-胺基萘、1-乙炔基-7-胺基萘、1-乙炔基-8-胺基萘、2-乙炔基-1-胺基萘、2-乙炔基-3-胺基萘、2-乙炔基-4-胺基萘、2-乙炔基-5-胺基萘、2-乙炔基-6-胺基萘、2-乙炔基-7-胺基萘、2-乙炔基-8-胺基萘、3,5-二乙炔基-1-胺基萘、3,5-二乙炔基-2-胺基萘、3,6-二乙炔基-1-胺基萘、3,6- 二乙炔基-2-胺基萘、3,7-二乙炔基-1-胺基萘、3,7-二乙炔基-2-胺基萘、4,8-二乙炔基-1-胺基萘、4,8-二乙炔基-2-胺基萘等，但並不受此等所限定。 It can be used as an amine for one of the terminal sealants, and examples thereof include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, and 1-hydroxy-7-. Amino naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2- Amino naphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4- Aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6- Amino naphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7 -carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3- Amino naphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-amino group Salicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, monodecylamine cyanamide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2 -aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4- Aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-indolyl-8-aminonaphthalene, 1-indolyl-7-aminonaphthalene, 1-indenyl- 6-Aminonaphthalene, 1-indolyl-5-aminonaphthalene, 1-indolyl-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino group -7-decylnaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto- 3-aminonaphthalene, 1-amino-2-indenyl , 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline , 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl- 6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8 - amino naphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6 - Diacetylenyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-amine Naphthalene, 4,8-diethynyl-2-aminonaphthalene, etc., but are not limited by these.

又，作為末端密封劑所用之一元醇，可舉例：甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、1-己醇、2-己醇、3己醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、3-辛醇、1-壬醇、2-壬醇、1-癸醇、2-癸醇、1-十一烷醇、2-十一烷醇、1-十二烷醇、2-十二烷醇、1-十三烷醇、2-十三烷醇、1-十四烷醇、2-十四烷醇、1-十四烷醇、2-十四烷醇、1-十五烷醇、2-十五烷醇、1-十六烷醇、2-十六烷醇、1-十七烷醇、2-十七烷醇、1-十八烷醇、2-十八烷醇、1-十九烷醇、2-十九烷醇、1-二十烷醇、2-甲基-1-丙醇、2-甲基-2-丙醇、2-甲基-1-丁醇、3-甲基-1-丁醇、2-甲基-2-丁醇、3-甲基-2-丁醇、2-丙基-1-戊醇、2-乙基-1-己醇、4-甲基-3-庚醇、6-甲基-2-庚醇、2,4,4-三甲基-1-己醇、2,6-二甲基-4-庚醇、異壬醇、3,7-二甲基-3-辛醇、2,4-二甲基-1-庚醇、2-庚基十一醇、乙二醇一乙基醚、乙二醇一甲基醚、乙二醇一丁基醚、丙二醇一甲基醚、二乙二醇一乙基醚、二乙二醇一甲基醚、二乙二醇一丁基醚、環戊醇、環己醇、一羥甲基環戊烷、一羥甲基二環戊烷、一羥甲基三環戊烷、降醇、萜品醇等，但並不受此等所限定。 Further, as the monohydric alcohol used for the terminal sealant, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3- Pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-oxime Alcohol, 2-nonanol, 1-nonanol, 2-nonanol, 1-undecyl alcohol, 2-undecyl alcohol, 1-dodecanol, 2-dodecanol, 1-tridecane Alcohol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol , 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-eicosyl alcohol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-1-butanol, 3-methyl-1 -butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3 -heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl-1-hexanol, 2,6-dimethyl-4-heptanol, isodecyl alcohol, 3,7- Dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-heptyl undecyl alcohol, ethylene glycol Ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl Ether, cyclopentanol, cyclohexanol, monomethylolcyclopentane, monomethylol dicyclopentane, monomethylol tricyclopentane, lower Alcohol, terpineol, etc., but are not limited by these.

作為末端密封劑所用之酸酐、單羧酸、單酸氯化合物及作為單活性酯化合物，可舉例：藉由鄰苯二甲酸酐、順丁烯二酸酐、納迪克酸酐、環己烷二羧酸酐、3-羥基鄰苯二甲酸酐等之酸酐；2-羧基苯酚、3-羧基苯酚、4-羧基苯酚、2-羧基苯硫酚、3-羧基苯硫酚、4-羧基苯硫酚、1-羥基-8-羧基萘、1-羥基-7-羧基萘、1-羥基-6-羧基萘、1-羥基-5-羧基萘、1-羥基-4-羧基萘、1-羥基-3-羧基萘、1-羥基-2-羧基萘、1-巰基-8-羧基萘、1-巰基-7-羧基萘、1-巰基-6-羧基萘、1-巰基-5-羧基萘、1-巰基-4-羧基萘、1-巰基-3-羧基萘、1-巰基-2-羧基萘、2-羧基苯磺酸、3-羧基苯磺酸、4-羧基苯磺酸、2-乙炔基苯甲酸、3-乙炔基苯甲酸、4-乙炔基苯甲酸、2,4-二乙炔基苯甲酸、2,5-二乙炔基苯甲酸、2,6-二乙炔基苯甲酸、3,4-二乙炔基苯甲酸、3,5-二乙炔基苯甲酸、2-乙炔基-1-萘甲酸、3-乙炔基-1-萘甲酸、4-乙炔基-1-萘甲酸、5-乙炔基-1-萘甲酸、6-乙炔基-1-萘甲酸、7-乙炔基-1-萘甲酸、8-乙炔基-1-萘甲酸、2-乙炔基-2-萘甲酸、3-乙炔基-2-萘甲酸、4-乙炔基-2-萘甲酸、5-乙炔基-2-萘甲酸、6-乙炔基-2-萘甲酸、7-乙炔基-2-萘甲酸、8-乙炔基-2-萘甲酸等之單羧酸類及此等之羧基為酸氯化的單酸氯化合物、及對苯二甲酸、鄰苯二甲酸、順丁烯二酸、環己烷二甲酸、3-羥基鄰苯二甲酸、5-降烯-2,3-二甲酸、1,2-二羧基萘、1,3-二羧基萘、1,4-二羧基萘、1,5-二羧基萘、1,6-二羧基萘、1,7-二羧基萘、1,8-二羧基萘、2,3-二羧基萘、2,6-二羧基萘、2,7-二羧基萘等之二羧酸類之僅使單羧基酸氯化之單酸氯化合物、單酸氯化合物與N-羥基苯并***或N-羥基-5-降烯-2,3-二羧基醯亞胺之反應所得之活性酯化合物。 As the terminal sealant, an acid anhydride, a monocarboxylic acid, a monoacid chlorine compound, and a single active ester compound can be exemplified by phthalic anhydride, maleic anhydride, nadic anhydride, and cyclohexane dicarboxylic anhydride. An anhydride such as 3-hydroxyphthalic anhydride; 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1 -hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3- Carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1- Mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynyl Benzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diacetylenebenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4 -diacetylenebenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4 -ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2 -ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7 a monocarboxylic acid such as ethynyl-2-naphthoic acid or 8-ethynyl-2-naphthoic acid and such a carboxyl group is an acid chlorided monoacid chlorine compound, and terephthalic acid, phthalic acid, and cis Butenedioic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-nor Aceene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1 a dicarboxylic acid such as 7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene or 2,7-dicarboxynaphthalene Mono-acid chlorine compound, mono acid chlorine compound and N-hydroxybenzotriazole or N-hydroxy-5-lower An active ester compound obtained by the reaction of a ene-2,3-dicarboxy quinone imine.

相對於全部胺成分而言，末端密封劑所用之一胺、一元醇之導入比例較佳為0.1至60莫耳%之範圍，特佳為5至50莫耳%。相對於二胺成分而言，作為末端密封劑所用之酸酐、單羧酸、單酸氯化合物及單活性酯化合物導入比例較佳為0.1至100莫耳%之範圍，特佳為5至90莫耳%。藉由使複數個末端密封劑反應而亦可導入複數個不同的末端基。 The ratio of introduction of one of the amines and monohydric alcohol used in the terminal sealant is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component. The introduction ratio of the acid anhydride, the monocarboxylic acid, the monoacid chloride compound, and the mono-active ester compound used as the terminal sealant is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol, based on the diamine component. ear%. A plurality of different terminal groups can also be introduced by reacting a plurality of terminal sealants.

在聚醯胺酸、聚醯亞胺及聚醯亞胺唑中所導入的末端密封劑係利用以下之方法而能夠容易地被檢測出。例如，藉由將已導入末端密封劑之聚合物溶解於酸性溶液中，分解成聚合物之構造單元之胺成分與酸酐成分，再經氣相層析儀(GC)或NMR測定而能夠容易檢測出末端密封劑。另外，亦能直接地、經熱分解氣相層析儀(PGC)或紅外線光譜及¹³C NMR光譜測定已導入末端密封劑之聚合物而可容易檢測出。 In polylysine, polyimine and polyimine The terminal sealant introduced into the azole can be easily detected by the following method. For example, by dissolving the polymer into which the terminal sealant has been introduced in an acidic solution, the amine component and the acid anhydride component of the structural unit of the polymer are decomposed, and then can be easily detected by gas chromatography (GC) or NMR measurement. The end sealant is removed. Further, the polymer to which the terminal sealant has been introduced can be directly detected by thermal decomposition gas chromatography (PGC), infrared spectroscopy, and ¹³ C NMR spectroscopy, and can be easily detected.

本發明之聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物係含有(b)溶劑。作為溶劑能夠使用單獨或2種以上之下列溶劑：N-甲基-2-吡咯啶酮、γ-丁內酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸等之極性非質子性溶劑、四氫呋喃、二烷、丙二醇一甲基醚等之醚類；丙酮、甲基乙基酮、二異丁基酮、二丙酮醇等之酮類；乙酸乙酯、丙二醇一甲基醚乙酸酯、乳酸乙酯等之酯類；甲苯、二甲苯等之芳香族烴類等。 Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition contains (b) a solvent. As the solvent, it is possible to use two or more of the following solvents: N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamidine. A polar, aprotic solvent such as amine or dimethyl hydrazine, tetrahydrofuran, An ether such as an alkane or a propylene glycol monomethyl ether; a ketone such as acetone, methyl ethyl ketone, diisobutyl ketone or diacetone; ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate Esters such as esters; aromatic hydrocarbons such as toluene and xylene;

相對於聚醯胺酸、聚醯亞胺及聚醯亞胺唑100重量份而言，(b)溶劑之含量較佳為50重量份以上，更佳為100重量份以上，較佳為2000重量份以下，更佳為1500重量份以下。若為50至2000重量份之範圍的話，能夠成為適合於塗布之黏度，容易調節塗布後之膜厚。 Relative to polylysine, polyimine and polyimine The content of the solvent (b) is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, more preferably 2,000 parts by weight or less, still more preferably 1,500 parts by weight or less based on 100 parts by weight of the azole. When it is in the range of 50 to 2000 parts by weight, the viscosity suitable for coating can be made, and the film thickness after coating can be easily adjusted.

以下，針對(a)以通式(1)所表示之構造單元作為主要成分的聚醯胺酸之製造方法而加以說明。聚合反應之反應方法只要為能製造目的之聚醯胺酸的話，並無特別之限制，能夠利用習知之反應方法。 In the following, a method for producing polyacrylic acid having (a) a structural unit represented by the general formula (1) as a main component will be described. The reaction method of the polymerization reaction is not particularly limited as long as it is a polylysine which can be produced, and a known reaction method can be used.

具體之反應方法，可舉例：使既定量之全部二胺成分與反應溶劑進料於反應器內而使其溶解之後，進料既定量之酸二酐成分，在室溫至80℃下攪拌0.5至30小時之方法等。 For the specific reaction method, for example, after all the diamine components and the reaction solvent are fed into the reactor to be dissolved, the acid dianhydride component of the quantitative amount is fed, and the mixture is stirred at room temperature to 80 ° C. The method to 30 hours, etc.

由作為以化學式(24)所表示之二胺化合物與1S,2S,4R,5R-環己烷四羧酸二酐、1R,2S,4S,5R-環己烷四羧酸二酐、3,3’,4,4’-二環己烷四羧酸二酐所得之聚醯胺酸之構造單元可舉例下列化學式(38)至(42)。 From the diamine compound represented by the chemical formula (24) to 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride, 3, The structural unit of the polyamic acid obtained from 3',4,4'-dicyclohexanetetracarboxylic dianhydride can be exemplified by the following chemical formulas (38) to (42).

以下，針對(a’)以通式(2)所表示之構造單元作為主要成分的聚醯亞胺之製造方法而加以說明。只要為能夠醯亞胺化利用上述習知之反應方法所得之以通式(1)所表示之聚醯胺酸的製造方法的話，並未予以特別限制，能夠利用習知之反應方法。 In the following, a method for producing poly(imine) having (a') a structural unit represented by the formula (2) as a main component will be described. The method for producing polylysine represented by the formula (1) obtained by the above-described conventional reaction method can be used without any particular limitation, and a conventional reaction method can be used.

作為具體之反應方法，可舉例：將進行如上所述所得之聚醯胺酸溶液，在室溫至200℃下攪拌0.5至30小時之方法等。 Specific examples of the reaction method include a method in which the polyamic acid solution obtained as described above is stirred at room temperature to 200 ° C for 0.5 to 30 hours.

由作為以化學式(24)所表示之二胺化合物與1S,2S,4R,5R-環己烷四羧酸二酐、1R,2S,4S,5R-環己烷四羧酸二酐、3,3’,4,4’-二環己烷四羧酸二酐所得之聚醯亞胺之構造單元可舉例下列化學式(43)至(45)。 From the diamine compound represented by the chemical formula (24) to 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride, 3, The structural unit of the polyimine obtained by 3',4,4'-dicyclohexanetetracarboxylic dianhydride can be exemplified by the following chemical formulas (43) to (45).

接著，針對(a”)以通式(3)所表示之構造單元作為主要成分的聚醯亞胺唑之製造方法而加以說明。作為第1方法，可舉例：脫水閉環利用上述習知之反應方法所得之以通式(2)所表示之聚醯亞胺。於反應方法中，並未無特別之限制，能夠利用習知之反應方法。作為具體之反應方法，可舉例：在300至400℃下0.5至30小時熱處理聚醯亞胺粉末之方法；將熱酸產生劑等之酸觸媒加入聚醯亞胺溶液中，在室溫至250℃下攪拌0.5至30小時之方法等。 Next, (a") a polyimine which has a structural unit represented by the general formula (3) as a main component The method of producing the azole will be described. As the first method, for example, a polyfluorene ring represented by the formula (2) obtained by the above-described reaction method can be used for the dehydration ring closure. In the reaction method, it is not particularly limited, and a conventional reaction method can be utilized. As a specific reaction method, for example, a method of heat-treating a polyimide pigment at a temperature of 300 to 400 ° C for 0.5 to 30 hours; adding an acid catalyst such as a thermal acid generator to a polyimide solution at room temperature to The method of stirring at 250 ° C for 0.5 to 30 hours, and the like.

作為第2方法，可舉例：醯亞胺化由含有以下列通式(46)所表示之唑環之二胺與酸二酐所得之聚醯胺酸。作為具體之反應方法，可舉例：進料既定量之酸二酐成分，在室溫至80℃下攪拌0.5至30小時之後，在室溫至200℃下攪拌0.5至30小時之方法等。 As the second method, for example, hydrazine imidation is represented by containing the following formula (46). Polylysine obtained from the diamine of the azole ring and the acid dianhydride. Specific examples of the reaction method include a method of feeding a predetermined amount of the acid dianhydride component, stirring at room temperature to 80 ° C for 0.5 to 30 hours, and then stirring at room temperature to 200 ° C for 0.5 to 30 hours.

(通式(46)中，R₃係表示碳數2至40之4價有機基)。 (In the formula (46), R ₃ represents a tetravalent organic group having 2 to 40 carbon atoms).

由脫水閉環以化學式(24)所表示之二胺化合物與1S,2S,4R,5R-環己烷四羧酸二酐、1R,2S,4S,5R-環己烷四羧酸二酐、3,3’,4,4’-二環己烷四羧酸二酐所得之聚醯胺酸之情形，或是由脫水閉環以化學式(47)所表示之二胺化合物與1S,2S,4R,5R-環己烷四羧酸二酐、1R,2S,4S,5R-環己烷四羧酸二酐、3,3’,4,4’-二環己烷四羧酸二酐所得之聚醯胺酸之情形下所得之作為聚醯亞胺唑之構造單元，可舉例：下列化學式(48)至(50)。 A diamine compound represented by the chemical formula (24) and a 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride, 3 a poly-proline acid obtained from 3', 4, 4'-dicyclohexane tetracarboxylic dianhydride, or a diamine compound represented by the chemical formula (47) and 1S, 2S, 4R, which is closed by dehydration. Aggregation of 5R-cyclohexanetetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride Polyimine The structural unit of the azole can be exemplified by the following chemical formulas (48) to (50).

本發明之聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物能夠含有界面活性劑。作為界面活性劑可舉例：Fluorad(商品名、住友3M股份有限公司製)、Megafac(商品名、DIC股份有限公司製)、Sulflon(商品名、旭硝子股份有限公司製)等之氟系界面活性劑。又，可舉例：KP341(商品名、信越化學工業股份有限公司製)、DBE(商品名、Chisso股份有限公司製)、Polyflow、GLANOL(商品名、共榮社化學股份有限公司製)、BYK(商品名、BYK Chieme股份有限公司製)等之有機矽氧烷界面活性劑。進一步可舉例：Polyflow(商品名、共榮社化學股份有限公司製)等之丙烯酸聚合物界面活性劑。 Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain a surfactant. Examples of the surfactants include fluorine-based surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by DIC Corporation), and Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.). . Further, for example, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.), Polyflow, GLANOL (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), BYK (for example) An organic oxoxane surfactant such as a trade name, manufactured by BYK Chieme Co., Ltd.). Further, an acrylic polymer surfactant such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) can be exemplified.

相對於聚醯胺酸、聚醯亞胺及聚醯亞胺唑100重量份而言，界面活性劑較佳為含有0.01至10重量份。 Relative to polylysine, polyimine and polyimine The surfactant preferably contains 0.01 to 10 parts by weight based on 100 parts by weight of the azole.

本發明之聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物能夠含有內部脫模劑。作為內部脫模劑，可舉例：長鏈脂肪酸等。 Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain an internal mold release agent. As the internal mold release agent, long-chain fatty acids and the like can be exemplified.

本發明之聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物能夠含有熱交聯劑。作為熱交聯劑較佳為環氧化合物或具有至少2個烷氧甲基或羥甲基之化合物。藉由具有至少2個此等基而能夠與樹脂及同種分子進行縮合反應而形成交聯結構物，使機械強度或耐藥品性得以提高。 Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain a thermal crosslinking agent. The thermal crosslinking agent is preferably an epoxy compound or a compound having at least two alkoxymethyl groups or a methylol group. By having at least two such groups, a condensation reaction can be carried out with a resin and a molecule of the same type to form a crosslinked structure, thereby improving mechanical strength or chemical resistance.

作為環氧化合物之較佳例，例如，可舉例：雙酚A型環氧樹脂、雙酚F型環氧樹脂、丙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、聚甲基(環氧丙氧基丙基)、矽氧烷等之含有環氧基之聚矽氧烷等；本發明並不受此等所任何限定。具體而言，可舉例：Epiclon 850-S、Epiclon HP-4032、Epiclon HP-7200、Epiclon HP-820、Epiclon HP-4700、Epiclon EXA-4710、Epiclon HP-4770、Epiclon EXA-859CRP、Epiclon EXA-1514、Epiclon EXA-4880、Epiclon EXA-4850-150、Epiclon EXA-4850-1000、Epiclon EXA-4816、Epiclon EXA-4822(以上商品名、大日本Ink化學工業股份有限公司製)；Rika Resin BEO-60E、Rika Resin BPO-20E、Rika Resin HBE-100、Rika Resin DME-100(以上商品名、新日本理化股份有限公司製)；EP-4003S、EP-4000S(以上商品名、Adeka股份有限公司製)；PG-100、CG-500、EG-200(以上商品名、大阪Gas Chemical股份有限公司製)；NC-3000、NC-6000(以上商品名、日本化藥股份有限公司製)；EPOX-MK R508、EPOX-MK R540、EPOX-MK R710、EPOX-MK R1710、VG3101L、VG3101M80(以上商品名、Printech股份有限公司製)；Celloxide 2021P、Celloxide 2081、Celloxide 2083、Celloxide 2085(以上商品名、Daicel化學工業股份有限公司製)等。 As preferred examples of the epoxy compound, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, polymethyl group can be exemplified. An epoxy group-containing polyoxyalkylene such as (glycidoxypropyl) or a decyl oxide; the present invention is not limited thereto. Specifically, for example: Epiclon 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA-859CRP, Epiclon EXA- 1514, Epiclon EXA-4880, Epiclon EXA-4850-150, Epiclon EXA-4850-1000, Epiclon EXA-4816, Epiclon EXA-4822 (above trade name, manufactured by Dainippon Ink Chemical Industry Co., Ltd.); Rika Resin BEO- 60E, Rika Resin BPO-20E, Rika Resin HBE-100, Rika Resin DME-100 (above trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.); EP-4003S, EP-4000S (above trade name, manufactured by Adeka Co., Ltd.) ); PG-100, CG-500, EG-200 (above trade name, manufactured by Osaka Gas Chemical Co., Ltd.); NC-3000, NC-6000 (above Product name, manufactured by Nippon Kayaku Co., Ltd.; EPOX-MK R508, EPOX-MK R540, EPOX-MK R710, EPOX-MK R1710, VG3101L, VG3101M80 (above trade name, manufactured by Printech Co., Ltd.); Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085 (trade name, manufactured by Daicel Chemical Industry Co., Ltd.), and the like.

作為具有至少2個烷氧甲基或羥甲基之化合物，例如，可舉例：DML-PC、DML-PEP、DML-OC、DML-OEP、DML-34X、DML-PTBP、DML-PCHP、DML-OCHP、DML-PFP、DML-PSBP、DML-POP、DML-MBOC、DML-MBPC、DML-MTrisPC、DML-BisOC-Z、DML-BisOCHP-Z、DML-BPC、DML-BisOC-P、DMOM-PC、DMOM-PTBP、DMOM-MBPC、TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPE、TML-BPA、TML-BPAF、TML-BPAP、TMOM-BP、TMOM-BPE、TMOM-BPA、TMOM-BPAF、TMOM-BPAP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP(以上商品名、本州化學工業股份有限公司製)；NIKALAC(註冊商標)MX-290、NIKALAC MX-280、NIKALAC MX-270、NIKALAC MX-279、NIKALAC MW-100LM、NIKALAC MX-750LM(以上商品名、三和Chemical股份有限公司製)。亦可含有2種以上此等化合物。 As the compound having at least 2 alkoxymethyl groups or hydroxymethyl groups, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML can be exemplified. -OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM -PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM -BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above trade name, manufactured by Honshu Chemical Industry Co., Ltd.); NIKALAC ( Registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade name, manufactured by Sanhe Chemical Co., Ltd.). It is also possible to contain two or more of these compounds.

本發明之聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物、聚醯亞胺唑樹脂組成物能夠含有著色劑。藉由添加著色劑而能夠調節聚醯胺酸、聚醯亞胺、聚醯亞胺唑膜之色調。 The polyaminic acid resin composition of the present invention, the polyimine resin composition, the polyimine The azole resin composition can contain a colorant. Polyamine, polyimine, polyimine can be adjusted by adding a colorant The color of the azole film.

作為著色劑，能夠使用染料、有機顏料、無機顏料等，從耐熱性、透明性方面，較佳為有機顏料。其中，較佳為透明性高、具優越之耐光性、耐熱性、耐藥品性者。若色指數(CI)號數表示代表性有機顏料之具體例時，較佳為使用如下之物，但並非受任一種此等著色劑所限定者。 As the colorant, a dye, an organic pigment, an inorganic pigment or the like can be used, and from the viewpoint of heat resistance and transparency, an organic pigment is preferable. Among them, those having high transparency, excellent light resistance, heat resistance, and chemical resistance are preferred. When the color index (CI) number indicates a specific example of a representative organic pigment, it is preferred to use the following ones, but it is not limited by any of these coloring agents.

作為黃色顏料之例子，使用顏料黃(以下簡稱為PY)12、13、17、20、24、83、86、93、95、109、110、117、125、129、137、138、139、147、148、150、153、154、166、168、185等。又，作為橙色顏料之例子，使用顏料橙(以下簡稱為PO)13、36、38、43、51、55、59、61、64、65、71等。又，作為紅色顏料之例子，使用顏料紅(以下簡稱為PR)9、48、97、122、123、144、149、166、168、177、179、180、192、209、215、216、217、220、223、224、226、227、228、240、254等。又，作為紫色顏料之例子，使用顏料紫(以下簡稱為PV)19、23、29、30、32、37、40、50等。又，作為藍色顏料之例子，使用顏料藍(以下簡稱為PB)15、15：3、15：4、15：6、22、60、64等。又，作為綠色顏料之例子，使用顏料綠(以下簡稱為PG)7、10、36、58等。必要時，此等顏料亦可進行松香處理、酸性基處理、鹼性處理等之表面處理也無妨。 As an example of the yellow pigment, pigment yellow (hereinafter abbreviated as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147 is used. , 148, 150, 153, 154, 166, 168, 185, and the like. Further, as an example of the orange pigment, pigment orange (hereinafter abbreviated as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71 and the like are used. Further, as an example of the red pigment, Pigment Red (hereinafter abbreviated as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217 is used. , 220, 223, 224, 226, 227, 228, 240, 254, and the like. Further, as an example of the violet pigment, pigment violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 32, 37, 40, 50 or the like is used. Further, as an example of the blue pigment, Pigment Blue (hereinafter abbreviated as PB) 15, 15:3, 15:4, 15:6, 22, 60, 64 and the like are used. Further, as an example of the green pigment, pigment green (hereinafter abbreviated as PG) 7, 10, 36, 58, and the like are used. If necessary, these pigments may also be subjected to surface treatment such as rosin treatment, acid-based treatment, alkaline treatment, and the like.

本發明之聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物能夠含有無機填料。作為無機填料，可舉例：二氧化矽微粒、氧化鋁微粒、氧化鈦微粒、氧化鋯微粒等。 Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain an inorganic filler. Examples of the inorganic filler include cerium oxide fine particles, alumina fine particles, titanium oxide fine particles, and zirconia fine particles.

無機填料之形狀並未予以特別限定，可舉例：球狀、橢圓狀、扁平狀、桿狀、纖維狀等。 The shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a rod shape, and a fibrous shape.

為了防止光之散射，所含有之無機填料較佳為粒徑小者。平均粒徑為0.5至100nm，較佳為0.5至30nm之範圍。 In order to prevent scattering of light, the inorganic filler contained is preferably small in particle diameter. The average particle diameter is from 0.5 to 100 nm, preferably from 0.5 to 30 nm.

相對於聚醯胺酸、聚醯亞胺或聚醯亞胺唑而言，無機填料之含量較佳為1至50重量%，更佳為10至30重量%。隨著含量之增加，可撓性或耐折性將會降低。 Relative to polylysine, polyimine or polyimine In the case of azole, the content of the inorganic filler is preferably from 1 to 50% by weight, more preferably from 10 to 30% by weight. As the content increases, the flexibility or folding endurance will decrease.

作為使聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物或聚醯亞胺唑樹脂組成物中含有無機填料之方法，能力利用各種習知方法。例如，可舉例：使有機無機填料與聚醯胺酸、聚醯亞胺或聚醯亞胺唑混合。有機無機填料係以30重量%左右之比例分散於有機溶劑中者，作為有機溶劑，可舉例：甲醇、異丙醇、正丁醇、乙二醇、甲基乙基酮、甲基異丁基酮、丙二醇一甲基乙酸酯、丙二醇一甲基醚、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、1,3-二甲基咪唑啉酮、γ-丁內酯等。 As a polyamine resin composition, a polyimide resin composition or a polyimine The method of containing an inorganic filler in the azole resin composition is capable of utilizing various conventional methods. For example, it can be exemplified by making an organic inorganic filler with polyglycine, polyimine or polyimine The azole is mixed. The organic-inorganic filler is dispersed in an organic solvent at a ratio of about 30% by weight. Examples of the organic solvent include methanol, isopropanol, n-butanol, ethylene glycol, methyl ethyl ketone, and methyl isobutyl. Ketone, propylene glycol monomethyl acetate, propylene glycol monomethyl ether, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1 , 3-dimethylimidazolidinone, γ-butyrolactone, and the like.

為了使對於無機填料之聚醯胺酸、聚醯亞胺或聚醯亞胺唑之分散性提高，亦可利用矽烷偶合劑處理有機無機填料。若在矽烷偶合劑之末端官能基具有環氧基或胺基時，藉由與聚醯胺酸之羧酸鍵結，能夠提高與聚醯胺酸、聚醯亞胺及聚醯亞胺唑之親和性而進行更有效的分散。 In order to make polyamic acid, polyimine or polyimine for inorganic fillers The dispersibility of the azole is improved, and the organic inorganic filler can also be treated with a decane coupling agent. When the terminal functional group of the decane coupling agent has an epoxy group or an amine group, it can be combined with polyglycine, polyimine, and polyimine by bonding with a carboxylic acid of polyphthalic acid. More effective dispersion is achieved by the affinity of the azole.

作為具有環氧基者，可舉例：2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷等。 As the epoxy group, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-epoxy Propoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and the like.

作為具有胺基者，可舉例：N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、N-2-(胺乙基)-3-胺丙基三甲氧基矽烷、3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基亞丁基)丙基胺、N-苯基-3-胺丙基三甲氧基矽烷等。 As the amine group, an example is: N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxy Decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethylbutylidene)propylamine, N -Phenyl-3-aminopropyltrimethoxydecane, and the like.

作為藉有機無機填料溶膠之矽烷偶合劑所進行的處理方法，能夠利用各種習知之方法。例如藉由將矽烷偶合劑添加於調整濃度之有機無機填料溶膠中，在室溫至80℃下攪拌0.5至2小時而能夠處理。 As a treatment method by a decane coupling agent of an organic inorganic filler sol, various conventional methods can be utilized. For example, by adding a decane coupling agent to the organic inorganic filler sol having a adjusted concentration, it can be treated by stirring at room temperature to 80 ° C for 0.5 to 2 hours.

本發明之聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物能夠含有光酸產生劑。藉由含光酸產生劑，若使描繪曝光圖案之光罩介於中間而照射光時，由於在曝光部中產生酸而增加曝光部對鹼水溶液之溶解性，能夠作為正型感光性樹脂組成物使用。 Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain a photoacid generator. When the photoreceptor for drawing the exposure pattern is irradiated with light, the acid is generated in the exposed portion to increase the solubility of the exposed portion in the aqueous alkali solution, and it can be used as a positive photosensitive resin. Use.

作為可用於本發明之光酸產生劑，可舉例：醌二疊氮化合物、鋶鹽、重氮鹽、錪鹽等。其中，從發現優異的溶解抑止效果、可獲得高感度且低膜減少之正型感光性樹脂組成物之觀點，較佳為使用醌二疊氮化合物。又亦可含有2種以上之光酸產生劑。藉此，能夠更增大曝光部與未曝光部之溶解速度比，故能夠獲得高感度之正型感光性樹脂組成物。 As the photoacid generator which can be used in the present invention, a quinonediazide compound, a phosphonium salt, a diazonium salt, a phosphonium salt or the like can be exemplified. Among them, a quinonediazide compound is preferably used from the viewpoint of obtaining an excellent dissolution inhibiting effect and obtaining a positive photosensitive resin composition having high sensitivity and low film reduction. Further, it may contain two or more kinds of photoacid generators. Thereby, the exposure can be increased Since the dissolution rate of the portion and the unexposed portion is higher, a positive photosensitive resin composition having a high sensitivity can be obtained.

作為醌二疊氮化合物，可舉例：醌二疊氮之磺酸以酯鍵結於聚羥基化合物之物、醌二疊氮之磺酸以磺醯胺鍵結於聚胺基化合物之物、醌二疊氮之磺酸以酯鍵及/或磺醯胺鍵結於聚羥基聚胺化合物之物等。此等之聚羥基化合物或聚胺基化合物的全部官能基亦可未被醌二疊氮所取代，較佳為官能基整體之50莫耳%以上被醌二疊氮所取代。藉由使用如此之醌二疊氮化合物，能夠藉由為一般紫外線之水銀燈i線(波長365nm)、h線(波長405nm)、g線(波長436nm)所反應的正型感光性樹脂組成物。 As the quinonediazide compound, for example, a quinonediazide sulfonic acid is ester-bonded to a polyhydroxy compound, a quinonediazide sulfonic acid is sulfonamide bonded to a polyamine compound, and hydrazine is used. The diazonium sulfonic acid is bonded to the polyhydroxy polyamine compound by an ester bond and/or a sulfonamide. All of the functional groups of the polyhydroxy compound or the polyamino compound may not be substituted by quinonediazide, and it is preferred that 50 mol% or more of the entire functional group is substituted with quinonediazide. By using such a quinonediazide compound, it is possible to form a positive photosensitive resin composition which is a reaction of a general ultraviolet light mercury lamp i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm).

於本發明中，醌二疊氮化合物較佳為使用5-萘醌二疊氮磺醯基、4-萘醌二疊氮磺醯基中任一種。在同一分子中可使用具有兩者此種基之化合物，亦可併用使用不同基之化合物。 In the present invention, the quinonediazide compound is preferably any one of a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group. A compound having such a group may be used in the same molecule, and a compound having a different group may also be used in combination.

可用於本發明之醌二疊氮化合物係從特定之苯酚化合物，依照下列方法所合成。例如，可舉例：在三乙基胺存在下，使5-萘醌二疊氮磺醯氯與苯酚化合物反應之方法。苯酚化合物之合成方法，可舉例：在酸觸媒下，使α-(羥苯基)苯乙烯衍生物與多元酚化合物反應之方法等。 The quinonediazide compound which can be used in the present invention is synthesized from a specific phenol compound according to the following method. For example, a method of reacting 5-naphthoquinonediazidesulfonium chloride with a phenol compound in the presence of triethylamine can be exemplified. The method for synthesizing the phenol compound is, for example, a method of reacting an α-(hydroxyphenyl)styrene derivative with a polyhydric phenol compound under an acid catalyst.

相對於聚醯胺酸、聚醯亞胺或聚醯亞胺唑100重量份而言，光酸產生劑之含量較佳為3至40重量份。藉由將光酸產生劑之含量設為此範圍，能夠謀求更高感度化。必要時亦可進一步含有增感劑等。 Relative to polylysine, polyimine or polyimine The content of the photoacid generator is preferably from 3 to 40 parts by weight based on 100 parts by weight of the azole. By setting the content of the photo-acid generator to this range, it is possible to achieve higher sensitivity. Further, a sensitizer or the like may be further contained as necessary.

於形成正型感光性樹脂之圖案中，在基板上塗布正型感光性樹脂之清漆，曝光後，使用顯影液而去除曝光部。作為顯影液，較佳為氫氧化四甲基銨、二乙醇胺、二乙胺基乙醇、氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、三乙基胺、二乙基胺、甲基胺、二甲基胺、乙酸二甲胺基乙酯、二甲胺基乙醇、甲基丙烯酸二甲胺基乙酯、環己胺、伸乙二胺、六亞甲二胺等之顯示鹼性的化合物水溶液。又，視情形而定，亦可單獨地或組合數種下列之化合物後添加於上述之鹼水溶液中：N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸、γ-丁內酯、二甲基丙烯醯胺等之極性溶劑；甲醇、乙醇、異丙醇等之醇類；乳酸乙酯、丙二醇一甲基醚乙酸酯等之酯類；環戊酮、環己酮、異丁基酮、甲基異丁基酮等之酮類等。顯影後，較佳為利用水進行沖洗處理。於此，亦可將乙醇、異丙醇等之醇類；乳酸乙酯、丙二醇一甲基醚乙酸酯等之酯類等加入水中之後，進行沖洗處理。 In the pattern in which the positive photosensitive resin is formed, a varnish of a positive photosensitive resin is applied onto the substrate, and after exposure, the exposed portion is removed using a developing solution. As the developer, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine is preferred. , dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc. An aqueous solution of the compound. Further, depending on the case, a plurality of the following compounds may be added singly or in combination with the above aqueous alkali solution: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N , polar solvents such as N-dimethylacetamide, dimethyl hydrazine, γ-butyrolactone, dimethyl acrylamide; alcohols such as methanol, ethanol, isopropanol; ethyl lactate, propylene glycol An ester such as monomethyl ether acetate; a ketone such as cyclopentanone, cyclohexanone, isobutyl ketone or methyl isobutyl ketone. After development, it is preferred to carry out a rinsing treatment with water. Here, an alcohol such as ethanol or isopropyl alcohol; an ester such as ethyl lactate or propylene glycol monomethyl ether acetate may be added to water and then rinsed.

以下，針對使用本發明之聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物而製造耐熱性樹脂膜之方法而加以說明。 Hereinafter, the polyphthalic acid resin composition, the polyimine resin composition, and the polyimine of the present invention are used. A method of producing a heat resistant resin film by using an azole resin composition will be described.

首先，將聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物或聚醯亞胺唑樹脂組成物塗布於基板上。可將例如矽晶圓、陶瓷類、砷化鎵、鈉鈣玻璃、無鹼玻璃等作為基板使用，但並不受此等所限定。塗布方法例如有狹縫模頭塗布法、旋轉塗布法、輥塗布法、桿塗布法等之方法，亦可組合此等之手法而塗布。 First, a polyamine resin composition, a polyimide composition, or a polyimine The azole resin composition is coated on the substrate. For example, a germanium wafer, a ceramic, a gallium arsenide, a soda lime glass, an alkali-free glass, or the like can be used as the substrate, but is not limited thereto. The coating method may be, for example, a method such as a slit die coating method, a spin coating method, a roll coating method, or a rod coating method, or may be applied by a combination of these methods.

接著，乾燥已塗布聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物或聚醯亞胺唑樹脂組成物之基板，獲得聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物或聚醯亞胺唑樹脂組成物被覆膜。乾燥係使用熱板、烘箱、紫外線、真空室等。使用熱板之情形，在板上直接加熱，或是將被加熱物保持於板上所設置的近接針等之夾具上而加熱。作為近接針之材質有鋁或不鏽鋼等之金屬材料、或是聚醯亞胺樹脂或“Teflon(註冊商標)”等之合成樹脂，不論使用任一種材質之近接針皆可。近接針之高度係根據基板之尺寸、被加熱物之樹脂層種類、加熱目的等而為各種式樣，例如加熱在300mm×350mm×0.7mm之玻璃基板上所塗布的樹脂層之情形，近接針之高度較佳為2至12mm左右。加熱溫度係根據被加熱物之種類或目的而為各種式樣，較佳為從室溫至180℃之範圍內進行1分鐘至數小時。 Next, drying the coated polyamine resin composition, the polyimide component, or the polyimine a substrate of an azole resin composition, which is obtained as a polyphthalic acid resin composition, a polyimine resin composition or a polyimine The azole resin composition is coated with a film. The drying system uses a hot plate, an oven, an ultraviolet ray, a vacuum chamber, or the like. In the case of using a hot plate, it is heated directly on the plate, or the object to be heated is held on a jig provided by a close pin or the like provided on the plate. The material of the proximity pin may be a metal material such as aluminum or stainless steel, or a synthetic resin such as a polyimide resin or a "Teflon (registered trademark)", and may be used as a proximity pin of any of the materials. The height of the proximity pin is various depending on the size of the substrate, the type of the resin layer of the object to be heated, the purpose of heating, and the like, for example, heating the resin layer applied on a glass substrate of 300 mm × 350 mm × 0.7 mm, and the proximity of the needle The height is preferably about 2 to 12 mm. The heating temperature is in various forms depending on the kind or purpose of the object to be heated, and it is preferably from 1 minute to several hours from room temperature to 180 °C.

接著，在180℃以上400℃以下之範圍內，提高溫度而轉換成耐熱性樹脂膜。針對從基板剝離此耐熱性樹脂膜，不論利用浸漬於氟酸等之藥液中之方法、或將雷射照射於耐熱性樹脂被覆膜與基板界面之方法等之任一種方法皆可。 Then, the temperature is increased to a heat resistant resin film in a range of from 180 ° C to 400 ° C. The method of peeling the heat-resistant resin film from the substrate may be performed by any method such as a method of immersing in a chemical solution such as fluoric acid or a method of irradiating a laser to the interface between the heat-resistant resin coating film and the substrate.

還有，如上所述，藉由熱處理以通式(1)、(2)所表示之構造單元作為主要成分的本發明之聚醯胺酸、聚醯亞胺，可獲得以通式(2)所表示之構造單元作為主要成分的聚醯亞胺、或是以通式(3)所表示之構造單元作為主要成分的聚醯亞胺唑。 Further, as described above, by the heat treatment of the polyglycolic acid or polyimine of the present invention having the structural unit represented by the general formulae (1) and (2) as a main component, the general formula (2) can be obtained. Polyimine which is a main component of the structural unit represented, or a polyimine which has a structural unit represented by the general formula (3) as a main component Oxazole.

如上述方式所得之耐熱性樹脂膜係具有高透明性、高耐熱性、低雙折射性、可撓性，能夠適用於作為可撓性基板。關於透明性，在波長400nm之透射率較佳為85%以上，更佳為90%以上，進一步較佳為95%以上。關於玻璃轉移溫度，較佳為250℃以上，更佳為300C以上，進一步較佳為350℃以上。關於雙折射率，較佳為0.01以下，更佳為0.005以下，進一步較佳為0.003以下。 The heat resistant resin film obtained as described above has high transparency, high heat resistance, low birefringence, and flexibility, and can be suitably used as a flexible substrate. Regarding the transparency, the transmittance at a wavelength of 400 nm is preferably 85% or more, more preferably 90% or more, still more preferably 95% or more. The glass transition temperature is preferably 250 ° C or higher, more preferably 300 C or higher, and still more preferably 350 ° C or higher. The birefringence is preferably 0.01 or less, more preferably 0.005 or less, still more preferably 0.003 or less.

含有本發明之樹脂組成物之可撓性基板能夠使用於液晶顯示器、有機EL顯示器、觸控面板、電子紙、彩色濾光片等之顯示器；太陽能電池、CMOS等之受光顯示器等之可撓性顯示器。 The flexible substrate containing the resin composition of the present invention can be used for displays such as liquid crystal displays, organic EL displays, touch panels, electronic papers, color filters, and the like, and flexible displays such as solar cells and CMOS. monitor.

於可撓性顯示器之製造步驟中，包含在基板上所形成的耐熱性樹脂膜之上形成顯示元件、受光元件所必要的電路之步驟。例如，能夠在可撓性基板上形成非晶質矽之TFT。還有，也能夠利用習知方法而在其上形成元件所必要的構造。如上述般進行，利用雷射照射等之習知方法，能夠從基板剝離在表面形成有電路等之固體狀耐熱性樹脂膜而獲得可撓性元件。 In the manufacturing step of the flexible display, a step of forming a circuit necessary for the display element and the light receiving element on the heat resistant resin film formed on the substrate is included. For example, an amorphous germanium TFT can be formed on a flexible substrate. Further, it is also possible to form a configuration necessary for the element thereon by a conventional method. As described above, a solid heat-resistant resin film having a circuit or the like formed on the surface thereof can be peeled off from the substrate by a conventional method such as laser irradiation to obtain a flexible element.

[實施例] [Examples]

以下，列舉實施例等而說明本發明，但本發明並不受此等實施例所限定。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples.

(1)耐熱性樹脂膜之製作 (1) Production of heat resistant resin film

在6吋之鏡面矽晶圓上，使用東京Electron股份有限公司製之塗布顯影裝置Mark-7，使140℃×4分鐘預烤後之膜厚成為15±0.5μm的方式來旋轉塗布清漆。之後，同樣地使用Mark-7之熱板而進行140℃×4分鐘之預烤處理。使用惰性烘箱(光洋Thermo System股份有限公司製INH-21CD)而在氮氣流下(氧濃度20ppm以下)，將預烤膜以3.5℃/min升溫直到300℃或350℃，保持30分鐘，再以5℃/min冷卻直到50℃而製得耐熱性樹脂膜。接著，在氟酸中浸漬1至4分鐘後，從基板剝離耐熱性樹脂膜，經風乾後獲得耐熱性樹脂膜。 On a 6-inch mirror-finished wafer, a coating development device Mark-7 manufactured by Tokyo Electron Co., Ltd. was used to pre-bake at 140 ° C for 4 minutes. The varnish was spin-coated so that the film thickness became 15±0.5 μm. Thereafter, a hot plate of Mark-7 was used in the same manner to perform a prebaking treatment at 140 ° C for 4 minutes. Using a inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) and under a nitrogen stream (oxygen concentration of 20 ppm or less), the prebaked film was heated at 3.5 ° C / min up to 300 ° C or 350 ° C for 30 minutes, and then 5 The heat resistant resin film was obtained by cooling to ° ° C / min until 50 ° C. Next, after immersing in fluoric acid for 1 to 4 minutes, the heat resistant resin film is peeled off from the substrate, and air-dried to obtain a heat resistant resin film.

(2)耐熱性樹脂膜(玻璃基板上)之製作 (2) Production of heat-resistant resin film (on glass substrate)

在50mm×50mm×1.1mm厚之玻璃基板上(TEMPAX)，使用Mikasa股份有限公司製之旋轉塗布器MS-A200，使140℃×4分鐘預烤後之膜厚成為15±0.5μm的方式來旋轉塗布清漆。之後，使用大日本Screen股份有限公司製熱板D-SPIN而進行140℃×4分鐘之預烤處理。使用惰性烘箱(光洋Thermo System股份有限公司製INH-21CD)而在氮氣流下(氧濃度20ppm以下)，將預烤膜以3.5℃/min升溫直到300℃或350℃，保持30分鐘，以5℃/min冷卻直到50℃而製得耐熱性樹脂膜(玻璃基板上)。 On a 50 mm × 50 mm × 1.1 mm thick glass substrate (TEMPAX), a spin coater MS-A200 manufactured by Mikasa Co., Ltd. was used, and the film thickness after prebaking at 140 ° C for 4 minutes was 15 ± 0.5 μm. Rotating coated varnish. Thereafter, pre-baking treatment at 140 ° C for 4 minutes was carried out using a hot plate D-SPIN of Dainippon Screen Co., Ltd. Using a inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) and under a nitrogen stream (oxygen concentration: 20 ppm or less), the prebaked film was heated at 3.5 ° C / min up to 300 ° C or 350 ° C for 30 minutes at 5 ° C. /min was cooled until 50 ° C to prepare a heat resistant resin film (on a glass substrate).

(3)耐熱性樹脂膜(矽基板上)之製作 (3) Production of heat-resistant resin film (on a substrate)

在切斷成1/4之4吋矽基板上，使用Mikasa股份有限公司製之旋轉塗布器MS-A200，使140℃×4分鐘預烤後之膜厚成為5±0.5μm的方式來旋轉塗布清漆。之後，使用大日本Screen股份有限公司製熱板D-SPIN而進行140℃×4分鐘之預烤處理。使用惰性烘箱(光洋Thermo System股份有限公司製INH-21CD)而在氮氣流下(氧濃度20ppm以下)，將預烤膜以3.5℃/min升溫直到300℃或350℃，保持30分鐘，以5℃/min冷卻直到50℃而製得耐熱性樹脂膜(矽基板上)。 Spin coating was performed on a substrate of 1/4 of 1/4, using a spin coater MS-A200 manufactured by Mikasa Co., Ltd., and the film thickness after prebaking at 140 ° C for 4 minutes was 5 ± 0.5 μm. Varnish. Thereafter, pre-baking treatment at 140 ° C for 4 minutes was carried out using a hot plate D-SPIN of Dainippon Screen Co., Ltd. An inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) was used under a nitrogen stream (oxygen concentration: 20 ppm). Next, the prebaked film was heated at 3.5 ° C / min up to 300 ° C or 350 ° C for 30 minutes, and cooled at 5 ° C / min to 50 ° C to obtain a heat resistant resin film (on the substrate).

(4)光透射率(T)之測定 (4) Determination of light transmittance (T)

使用紫外可見分光光度計(島津製作所股份有限公司製MultiSpec1500)，測定在400nm之光透射率。還有，於測定中係使用在(2)所製得之耐熱性樹脂膜。 The light transmittance at 400 nm was measured using an ultraviolet-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation). Further, in the measurement, the heat resistant resin film obtained in (2) was used.

(5)全部光線透射率(Tt)之測定 (5) Determination of total light transmittance (Tt)

使用直接讀取式霧度(Suga試驗機股份有限公司製HGM2DP、C光源)，測定在(1)所製得之耐熱性樹脂膜的全部光線透射率。還有，使用1次測定之值作為Tt。還有，於測定中係使用在(1)所製得之耐熱性樹脂膜。 The total light transmittance of the heat resistant resin film obtained in (1) was measured using a direct reading type haze (HGM2DP manufactured by Suga Test Machine Co., Ltd., C light source). Also, the value of one measurement was used as Tt. Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(6)折射率、面內/面外雙折射之測定 (6) Determination of refractive index, in-plane/out-of-plane birefringence

使用稜鏡偶合器(METRICON公司製、PC2010)，測定波長632.8nm之TE折射率(n(TE))與TM折射率(n(TM))。n(TE)、n(TM)係分別相對於聚醯亞胺膜面而言，平行、垂直方向之折射率。平均折射率n(AV)係從((2×n(TE)²+n(TM)²)/3)^0.5所算出，面內/面外雙折射率係設為n(TE)與n(TM)之差(n(TE)-n(TM))而算出。還有，於測定中係使用在(3)所製得之耐熱性樹脂膜。 The TE refractive index (n(TE)) and the TM refractive index (n(TM)) of a wavelength of 632.8 nm were measured using a 稜鏡 coupling (manufactured by METRICON Co., Ltd., PC2010). n (TE) and n (TM) are refractive indices in parallel and perpendicular directions with respect to the polyimide film surface. The average refractive index n (AV) is calculated from ((2 × n(TE) ² + n(TM) ² ) / 3) ^0.5 , and the in-plane/out-of-plane birefringence is set to n (TE) and n ( Calculated by the difference (n(TE)-n(TM)) of TM). Further, in the measurement, the heat resistant resin film obtained in (3) was used.

(7)玻璃轉移溫度(Tg)、線膨脹係數(CTE)之測定 (7) Determination of glass transition temperature (Tg) and coefficient of linear expansion (CTE)

使用熱機械分析裝置(SII Nanotechnology股份有限公司製EXST AR6000 TMA/SS6000)而在氮氣流下進行測定。升溫方法係以下列條件進行。在第1階段，以升溫速率5℃/min升溫至150℃而去除試料之吸附水；在第2階段，以降溫速率5℃/min空氣冷卻至室溫。於第3階段中以升溫速率5℃/min進行本測定，以求得玻璃轉移溫度。又，從第3階段中之50至200℃之線膨脹係數的平均而求出線膨脹係數(CTE)。還有，於測定中係使用在(1)所製得之耐熱性樹脂膜。 The measurement was carried out under a nitrogen flow using a thermomechanical analyzer (EXST AR6000 TMA/SS6000 manufactured by SII Nanotechnology Co., Ltd.). The heating method was carried out under the following conditions. In the first stage, the temperature is raised to 150 ° C at a heating rate of 5 ° C / min to remove the adsorbed water of the sample; in the second stage Cool to room temperature at a cooling rate of 5 ° C / min. The measurement was carried out in the third stage at a heating rate of 5 ° C/min to determine the glass transition temperature. Further, the linear expansion coefficient (CTE) was obtained from the average of the linear expansion coefficients of 50 to 200 ° C in the third stage. Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(8)1%熱重量減少溫度(Td1)之測定 (8) Determination of 1% thermal weight reduction temperature (Td1)

使用熱重量測定裝置(島津製作所股份有限公司製TGA-50)而在氮氣流下進行測定。升溫方法係以下列條件進行。在第1階段，以升溫速率3.5℃/min升溫至350℃而去除試料之吸附水；在第2階段，以降溫速率10℃/min冷卻至室溫。在第3階段，以升溫速率10℃/min進行本測定，求出1%熱重量減少溫度。還有，於測定中係使用在(1)所製得之耐熱性樹脂膜。 The measurement was carried out under a nitrogen flow using a thermogravimetric measuring apparatus (TGA-50 manufactured by Shimadzu Corporation). The heating method was carried out under the following conditions. In the first stage, the adsorbed water of the sample was removed by raising the temperature to 350 ° C at a heating rate of 3.5 ° C / min; in the second stage, it was cooled to room temperature at a cooling rate of 10 ° C / min. In the third stage, the measurement was carried out at a heating rate of 10 ° C/min, and a 1% thermogravimetric reduction temperature was determined. Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(9)斷裂應力、斷裂伸度、楊氏模數之測定 (9) Determination of fracture stress, elongation at break, and Young's modulus

使用Tensilon(Orientec股份有限公司RTM-100)而進行測定。針對各試料，進行10個試樣以上之測定，利用JIS個數平均(JIS K-6301)而算出JIS平均值。還有，於測定中係使用在(1)所製得之耐熱性樹脂膜。 The measurement was carried out using Tensilon (Orientec Co., Ltd. RTM-100). For each sample, 10 samples or more were measured, and the JIS average value was calculated using JIS number average (JIS K-6301). Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(10)b^＊值之測定 (10) Determination of b ^* value

使用SM彩色電腦(Suga試驗機股份有限公司SM-7-CH)而進行代表性色空間的CIELAB的b^＊值之測定。光源中係使用C光源，測定係以透射光模式而進行。還有，於CIELAB中，對應於b^＊值係黃色與藍色之座標，b^＊>0係偏黃色，b^＊<0係偏藍色。還有，於測定中係使用在(1)所製得之耐熱性樹脂膜。 The b ^* value of CIELAB in the representative color space was measured using an SM color computer (Suga Test Machine Co., Ltd. SM-7-CH). A C light source was used in the light source, and the measurement was performed in a transmitted light mode. Also, in CIELAB, the b ^* value corresponds to the coordinates of yellow and blue, b ^* >0 is yellowish, and b ^* <0 is blueish. Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(11)起伏圖案(relief pattern)之製作 (11) Production of relief pattern

將在實施例所製作的感光性樹脂組成物(清漆)旋轉塗布於8吋矽晶圓上，接著，使用熱板(東京Electron股份有限公司製之塗布顯影裝置Mark-7)，在120℃進行3分鐘熱處理(預烤)，製作厚度2至4μm之預烤膜。使用i線步進機(GCA公司製、DSW-8000)，以20至320mJ/cm²之曝光量且以10mJ/cm²步進而曝光所得之預烤膜。用於曝光之線&間隙圖案係1、2、3、4、5、6、7、8、9、10、15、20、30、50、100μm。曝光後，利用2.38重量%之四甲基銨(TMAH)水溶液(三菱Gas化學股份有限公司製、ELM-D)顯影60秒鐘，接著，利用純水沖洗，獲得起伏圖案。還有，預烤後及顯影後之膜厚係使用大日本Screen製造股份有限公司製光干涉式膜厚測定裝置Lambda Ace SM-602，測出折射率1.63。 The photosensitive resin composition (varnish) produced in the Example was spin-coated on an 8-inch wafer, and then hot plate (Marking and developing device Mark-7 manufactured by Tokyo Electron Co., Ltd.) was used at 120 ° C. Heat treatment (pre-bake) for 3 minutes to prepare a pre-baked film having a thickness of 2 to 4 μm. The obtained prebaked film was exposed by an i line stepper (manufactured by GCA Corporation, DSW-8000) at an exposure amount of 20 to 320 mJ/cm ² and in a step of 10 mJ/cm ² . The line & gap pattern for exposure is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 50, 100 μm. After the exposure, development was carried out for 60 seconds using a 2.38 wt% aqueous solution of tetramethylammonium (TMAH) (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D), followed by rinsing with pure water to obtain an undulating pattern. Further, the film thickness after prebaking and after development was measured using a light interferometric film thickness measuring device Lambda Ace SM-602 manufactured by Dainippon Screen Manufacturing Co., Ltd., and a refractive index of 1.63 was measured.

(12)顯影膜減少量之算出 (12) Calculation of reduction amount of developing film

顯影膜減少量係依照下式而算出。 The amount of development film reduction was calculated according to the following formula.

顯影膜減少量(μm)=預烤後之膜厚-顯影後之膜厚 Development film reduction (μm) = film thickness after pre-baking - film thickness after development

(13)感度之算出 (13) Calculation of sensitivity

曝光、顯影後，將10μm及20μm之線&間隙圖案(1L/1S)形成1對1之最小曝光量設為感度。 After the exposure and development, a line-and gap pattern of 10 μm and 20 μm (1L/1S) was formed to have a sensitivity of 1 to 1 as the minimum exposure amount.

以下，記載實施例所使用的化合物之縮寫。 Hereinafter, the abbreviations of the compounds used in the examples are described.

PMDA-HH：1S,2S,4R,5R-環己烷四羧酸二酐 PMDA-HH: 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride

PMDA-HS：1R,2S,4R,5R-二環己烷四羧酸二酐 PMDA-HS: 1R, 2S, 4R, 5R-dicyclohexane tetracarboxylic dianhydride

BPDA-H：3,3’,4,4’-二環己烷四羧酸二酐 BPDA-H: 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride

PMDA：焦蜜石酸二酐 PMDA: pyrethic acid dianhydride

BPDA：3,3’,4,4’-聯苯四羧酸二酐 BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

ODPA：3,3’,4,4’-氧二鄰苯二甲酸二酐 ODPA: 3,3',4,4'-oxydiphthalic dianhydride

6FDA：4,4’-(六氟亞異丙基)二鄰苯二甲酸酐 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

HFHA：2,2’-雙[3-(3-胺基苯甲醯胺基)-4-羥基苯基]六氟丙烷 HFHA: 2,2'-bis[3-(3-aminobenzylideneamino)-4-hydroxyphenyl]hexafluoropropane

FDA：9,9-雙(4-胺基苯基)茀 FDA: 9,9-bis(4-aminophenyl)anthracene

CHDA：反-1,4-二胺基環己烷 CHDA: trans-1,4-diaminocyclohexane

PDA：對伸苯二胺 PDA: p-phenylenediamine

m-TB：2,2’-二甲基-4,4’-二胺基聯苯 m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

TFMB：2,2’-雙(三氟甲基)聯苯胺 TFMB: 2,2'-bis(trifluoromethyl)benzidine

m-BAPS：雙[4-(3-胺基苯氧基)苯基]碸 m-BAPS: bis[4-(3-aminophenoxy)phenyl]indole

SiDA：1,3-雙(3-胺基丙基)四甲基二矽氧烷 SiDA: 1,3-bis(3-aminopropyl)tetramethyldioxane

MAP：間胺基苯酚 MAP: m-aminophenol

NMP：N-甲基-2-吡咯啶酮 NMP: N-methyl-2-pyrrolidone

GBL：γ-丁內酯 GBL: γ-butyrolactone

EL：乳酸乙酯 EL: ethyl lactate

DFA：二甲基甲醯胺二甲基縮醛 DFA: dimethylformamide dimethyl acetal

實施例1 Example 1

乾燥氮氣流下，將2.7704g(12mmol)之PMDA-HH、7.4706g(12mmol)之HFHA、50g之NMP加入100mL之四頸燒瓶中，在80℃下加熱攪拌。8小時後，冷卻而作成清漆。 Under a nitrogen stream, 2.7704 g (12 mmol) of PMDA-HH, 7.4706 g (12 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 80 °C. After 8 hours, it was cooled to make a varnish.

實施例2 Example 2

乾燥氮氣流下，將2.7704g(12mmol)之PMDA-HS、7.4706g(12mmol)之HFHA、50g之NMP加入100mL之四頸燒瓶中，在80℃下加熱攪拌。8小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 2.7704 g (12 mmol) of PMDA-HS, 7.4706 g (12 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 80 °C. After 8 hours, it was cooled to make a varnish.

實施例3 Example 3

乾燥氮氣流下，將3.4441g(11mmol)之BPDA-H、6.7969g(11mmol)之HFHA、50g之NMP加入100mL之四頸燒瓶中，在80℃下加熱攪拌。8小時後，冷卻而作成清漆。 Under dry nitrogen flow, 3.4441 g (11 mmol) of BPDA-H, 6.7969 g (11 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 80 °C. After 8 hours, it was cooled to make a varnish.

實施例4 Example 4

乾燥氮氣流下，將2.7704g(12mmol)之PMDA-HH、6.5286g(10.8mmol)之HFHA、0.4181g(1.2mmol)之FDA、50g之NMP加入100mL之四頸燒瓶中，在80℃下加熱攪拌。8小時後，冷卻而作成清漆。 Under dry nitrogen flow, 2.7704 g (12 mmol) of PMDA-HH, 6.5286 g (10.8 mmol) of HFHA, 0.4181 g (1.2 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated and stirred at 80 ° C. . After 8 hours, it was cooled to make a varnish.

實施例5 Example 5

乾燥氮氣流下，將1.0238g(3.48mmol)之BPDA、1.9099g(8.52mmol)之PMDA-HH、0.4110g(3.60mmol)之CHDA、5.0778g(8.40mmol)之HFHA、50g之NMP加入100mL之四頸燒瓶中，在80℃下加熱攪拌。8小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 1.0238 g (3.48 mmol) of BPDA, 1.9099 g (8.52 mmol) of PMDA-HH, 0.4110 g (3.60 mmol) of CHDA, 5.0778 g (8.40 mmol) of HFHA, 50 g of NMP were added to 100 mL of four. In a neck flask, the mixture was heated and stirred at 80 °C. After 8 hours, it was cooled to make a varnish.

實施例6 Example 6

乾燥氮氣流下，將3.4345g(15.3mmol)之PMDA-HS、8.7985g(14.5mmol)之HFHA、0.2669g(0.8mmol)之FDA、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under dry nitrogen flow, 3.4345 g (15.3 mmol) of PMDA-HS, 8.7985 g (14.5 mmol) of HFHA, 0.2669 g (0.8 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

實施例7 Example 7

乾燥氮氣流下，將3.4893g(15.6mmol)之PMDA-HS、8.4683g(14.0mmol)之HFHA、0.5424g(1.6mmol)之FDA、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。8小時後，冷卻而作成清漆。 Under dry nitrogen flow, 3.4893 g (15.6 mmol) of PMDA-HS, 8.4683 g (14.0 mmol) of HFHA, 0.5424 g (1.6 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 8 hours, it was cooled to make a varnish.

實施例8 Example 8

乾燥氮氣流下，將3.6402g(16.1mmol)之PMDA-HS、7.7753g(12.9mmol)之HFHA、1.1204g(3.2mmol)之FDA、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under dry nitrogen flow, 3.6402 g (16.1 mmol) of PMDA-HS, 7.7753 g (12.9 mmol) of HFHA, 1.1204 g (3.2 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

實施例9 Example 9

乾燥氮氣流下，將3.7270g(16.6mmol)之PMDA-HS、7.0351g(11.6mmol)之HFHA、1.7379g(5.0mmol)之FDA、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under dry nitrogen flow, 3.7270 g (16.6 mmol) of PMDA-HS, 7.0351 g (11.6 mmol) of HFHA, 1.7379 g (5.0 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

實施例10 Example 10

乾燥氮氣流下，將3.8584g(17.2mmol)之PMDA-HS、6.2427g(10.3mmol)之HFHA、2.3989g(6.9mmol)之FDA、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 3.8584 g (17.2 mmol) of PMDA-HS, 6.2427 g (10.3 mmol) of HFHA, 2.3989 g (6.9 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask under a stream of dry nitrogen, and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

實施例11 Example 11

乾燥氮氣流下，將3.9994g(17.8mmol)之PMDA-HS、5.3924g(8.9mmol)之HFHA、3.1082g(8.9mmol)之FDA、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under dry nitrogen flow, 3.9994 g (17.8 mmol) of PMDA-HS, 5.3924 g (8.9 mmol) of HFHA, 3.1082 g (8.9 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

比較例1 Comparative example 1

乾燥氮氣流下，將2.7154g(12mmol)之PMDA、7.5255g(12mmol)之HFHA、50g之NMP加入100mL之四頸燒瓶中，在50℃下加熱攪拌。2小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 2.7154 g (12 mmol) of PMDA, 7.5255 g (12 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 2 hours, it was cooled to make a varnish.

比較例2 Comparative example 2

乾燥氮氣流下，將3.3527g(11mmol)之BPDA、6.8883g(11mmol)之HFHA、50g之NMP加入100mL之四頸燒瓶中，在50℃下加熱攪拌。2小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 3.3527 g (11 mmol) of BPDA, 6.8883 g (11 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 2 hours, it was cooled to make a varnish.

比較例3 Comparative example 3

乾燥氮氣流下，將3.4731g(11mmol)之ODPA、6.7679g(11mmol)之HFHA、50g之NMP加入100mL之四頸燒瓶中，在50℃下加熱攪拌。2小時後，冷卻而作成清漆。 Under dry nitrogen flow, 3.4731 g (11 mmol) of ODPA, 6.7679 g (11 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 2 hours, it was cooled to make a varnish.

比較例4 Comparative example 4

乾燥氮氣流下，將5.2599g(23mmol)之PMDA-HH、4.9811g(23mmol)之m-TB、50g之NMP加入100mL之四頸燒瓶中，在50℃下加熱攪拌。2小時後，冷卻而作成清漆。 Under a nitrogen stream, 5.2599 g (23 mmol) of PMDA-HH, 4.9811 g (23 mmol) of m-TB, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 2 hours, it was cooled to make a varnish.

比較例5 Comparative Example 5

乾燥氮氣流下，將7.0599g(15.9mmol)之6FDA、9.6068g(15.9mmol)之HFHA、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 7.0599 g (15.9 mmol) of 6FDA, 9.6068 g (15.9 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 30 °C. After 6 hours, it was cooled to make a varnish.

比較例6 Comparative Example 6

乾燥氮氣流下，將7.2639g(16.4mmol)之6FDA、5.2361g(16.4mmol)之TFMB、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 7.2639 g (16.4 mmol) of 6FDA, 5.2361 g (16.4 mmol) of TFMB, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 30 °C. After 6 hours, it was cooled to make a varnish.

比較例7 Comparative Example 7

乾燥氮氣流下，將8.4450g(19.0mmol)之6FDA、8.2216g(19.0mmol)之m-BAPS、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 8.4450 g (19.0 mmol) of 6FDA, 8.2216 g (19.0 mmol) of m-BAPS, and 50 g of NMP were added to 100 mL under a stream of dry nitrogen. In a four-necked flask, the mixture was heated and stirred at 30 °C. After 6 hours, it was cooled to make a varnish.

比較例8 Comparative Example 8

乾燥氮氣流下，將7.824g(17.6mmol)之6FDA、2.4547g(7.0mmol)之FDA、6.3879g(10.6mmol)之HFHA、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 7.824 g (17.6 mmol) of 6FDA, 2.4547 g (7.0 mmol) of FDA, 6.3879 g (10.6 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 30 °C. After 6 hours, it was cooled to make a varnish.

比較例9 Comparative Example 9

乾燥氮氣流下，將5.1472g(23mmol)之PMDA-HH、7.3528g(23mmol)之TFMB、50g之NMP加入100mL之四頸燒瓶中，在50℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 5.1472 g (23 mmol) of PMDA-HH, 7.3528 g (23 mmol) of TFMB, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 6 hours, it was cooled to make a varnish.

比較例10 Comparative Example 10

乾燥氮氣流下，將5.6897g(25.4mmol)之PMDA-HS、10.9770g(25.4mmol)之m-BAPS、50g之NMP加入100mL之四頸燒瓶中，在50℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under a nitrogen stream, 5.6897 g (25.4 mmol) of PMDA-HS, 10.9770 g (25.4 mmol) of m-BAPS, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 6 hours, it was cooled to make a varnish.

比較例11 Comparative Example 11

乾燥氮氣流下，將9.2384g(30.2mmol)之BPDA-H、3.2616g(30.2mmol)之PDA、50g之NMP加入100mL之四頸燒瓶中，在50℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 9.2384 g (30.2 mmol) of BPDA-H, 3.2616 g (30.2 mmol) of PDA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 6 hours, it was cooled to make a varnish.

比較例12 Comparative Example 12

乾燥氮氣流下，將4.1511g(18.5mmol)之PMDA-HS、4.4776g(7.4mmol)之HFHA、3.8714g(11.1mmol)之FDA、50g之NMP加入100mL之四頸燒瓶中，在30℃下加熱攪拌。6小時後，冷卻而作成清漆。 Under a dry nitrogen stream, 4.1511 g (18.5 mmol) of PMDA-HS, 4.4776 g (7.4 mmol) of HFHA, 3.8714 g (11.1 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

於表1中顯示實施例1至11、及比較例1至12所合成的清漆組成。又，於表1中顯示使用此等之清漆而測定藉由在350℃下之煅燒所得之耐熱性樹脂膜的光透射率(T)、全部光線透射率(Tt)、TE折射率(n(TE))、TM折射率(n(TM))、平均折射率(n(AV))、面內/面外雙折射率、玻璃轉移溫度(Tg)、線膨脹係數(CTE)、1%熱重量減少溫度(Td1)之結果。 The varnish compositions synthesized in Examples 1 to 11 and Comparative Examples 1 to 12 are shown in Table 1. Further, in Table 1, the light transmittance (T), the total light transmittance (Tt), and the TE refractive index (n (the light transmittance) of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes. TE)), TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% heat The result of the weight reduction temperature (Td1).

實施例12 Example 12

乾燥氮氣流下，將121.5804g(0.201mol)之HFHA溶解於400g之NMP中。將45.5372g(0.203mol)之PMDA-HS與100g之NMP一併加入其中，在30℃下攪拌6小時。之後，在室溫下攪拌12小時。然後，在180℃下攪拌4小時。攪拌結束後，將溶液倒入3L之水中，過濾聚合物固體之沉澱物後收集。進一步利用3L之水進行5次洗淨，利用50℃之乾燥機，進行所收集的聚合物固體之72小時乾燥，獲得聚醯亞胺粉末。將47.5g之GBL加至所得之15g之聚醯亞胺粉末而獲得聚醯亞胺清漆。 Under a dry nitrogen stream, 121.5804 g (0.201 mol) of HFHA was dissolved in 400 g of NMP. 45.5372 g (0.203 mol) of PMDA-HS was added together with 100 g of NMP, and stirred at 30 ° C for 6 hours. Thereafter, it was stirred at room temperature for 12 hours. Then, it was stirred at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyimide pigment powder. 47.5 g of GBL was added to the obtained 15 g of the polyimine powder to obtain a polyimide pigment varnish.

實施例13 Example 13

乾燥氮氣流下，將62.4272g(0.103mol)之HFHA、23.9891g(0.069mol)之FDA溶解於400g之NMP中。將38.9695g(0.174mol)之PMDA-HS與100g之NMP一併加入其中，在30℃下攪拌6小時。之後，在室溫下攪拌12小時。然後，在180℃下攪拌4小時。攪拌結束後，將溶液倒入3L之水中，過濾聚合物固體之沉澱物後收集。進一步利用3L之水進行5次洗淨，利用50℃之乾燥機，進行所收集的聚合物固體之72小時乾燥，獲得聚醯亞胺粉末。將47.5g之GBL加至所得之15g之聚醯亞胺粉末而獲得聚醯亞胺清漆。 Under dry nitrogen flow, 62.4272 g (0.103 mol) of HFHA and 23.9891 g (0.069 mol) of FDA were dissolved in 400 g of NMP. 38.9695 g (0.174 mol) of PMDA-HS was added together with 100 g of NMP, and stirred at 30 ° C for 6 hours. Thereafter, it was stirred at room temperature for 12 hours. Then, it was stirred at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyimide pigment powder. 47.5 g of GBL was added to the obtained 15 g of the polyimine powder to obtain a polyimide pigment varnish.

於表2中顯示使用實施例12、13之清漆而測定藉由在350℃下之煅燒所得之耐熱性樹脂膜的光透射率(T)、全部光線透射率(Tt)、TE折射率(n(TE))、TM折射率(n(TM))、平均折射率(n(AV))、面內/面外雙折射率、玻璃轉移溫度(Tg)、線膨脹係數(CTE)、1%熱重量減少溫度(Td1)之結果。 The light transmittance (T), total light transmittance (Tt), and TE refractive index of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes of Examples 12 and 13 in Table 2. (TE)), TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transfer Temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight reduction temperature (Td1).

實施例14 Example 14

乾燥氮氣流下，將121.5804g(0.201mol)之HFHA溶解於400g之NMP中。將45.5372g(0.203mol)之PMDA-HS與100g之NMP一併加入其中，在30℃下攪拌6小時。之後，在室溫下攪拌12小時。然後，在180℃下攪拌4小時。攪拌結束後，將溶液倒入3L之水中，過濾聚合物固體之沉澱物後收集。進一步利用3L之水進行5次洗淨，利用50℃之乾燥機，進行所收集的聚合物固體之72小時乾燥，獲得聚醯亞胺粉末。氮氣流下，利用350℃之烘箱進行所得之聚醯亞胺粉末的30分鐘熱處理，獲得聚醯亞胺唑粉末。將47.5g之NMP加至所得之15g之聚醯亞胺唑粉末而獲得聚醯亞胺唑清漆。 Under a dry nitrogen stream, 121.5804 g (0.201 mol) of HFHA was dissolved in 400 g of NMP. 45.5372 g (0.203 mol) of PMDA-HS was added together with 100 g of NMP, and stirred at 30 ° C for 6 hours. Thereafter, it was stirred at room temperature for 12 hours. Then, it was stirred at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyimide pigment powder. The heat treatment of the obtained polyimide pigment powder was carried out in an oven at 350 ° C for 30 minutes under a nitrogen stream to obtain a polyimine. Oxazole powder. 47.5 g of NMP was added to the obtained 15 g of polyimine Polyazole Azole varnish.

實施例15 Example 15

乾燥氮氣流下，將62.4272g(0.103mol)之HFHA、23.9891g(0.069mol)之FDA溶解於400g之NMP中。將38.9695g(0.174mol)之PMDA-HS與100g之NMP一併加入其中，在30℃下攪拌6小時。之後，在室溫下攪拌12小時。然後，在180℃下攪拌4小時。攪拌結束後，將溶液倒入3L之水中，過濾聚合物固體之沉澱物後收集。進一步利用3L之水進行5次洗淨，利用50℃之乾燥機，進行所收集的聚合物固體之72小時乾燥，獲得聚醯亞胺粉末。乾燥氮氣流下，利用350℃之烘箱進行所得之聚醯亞胺粉末的30分鐘熱處理，獲得聚醯亞胺唑粉末。將47.5g之NMP加至所得之15g之聚醯亞胺唑粉末而獲得聚醯亞胺唑清漆。 Under dry nitrogen flow, 62.4272 g (0.103 mol) of HFHA and 23.9891 g (0.069 mol) of FDA were dissolved in 400 g of NMP. 38.9695 g (0.174 mol) of PMDA-HS was added together with 100 g of NMP, and stirred at 30 ° C for 6 hours. Thereafter, it was stirred at room temperature for 12 hours. Then, it was stirred at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyimide pigment powder. Under the dry nitrogen flow, the obtained polyimine powder was heat-treated in an oven at 350 ° C for 30 minutes to obtain a polyimide. Oxazole powder. 47.5 g of NMP was added to the obtained 15 g of polyimine Polyazole Azole varnish.

於表3中顯示使用實施例14、15之清漆而測定藉由在350℃下之煅燒所得之耐熱性樹脂膜的光透射率(T)、全部光線透射率(Tt)、TE折射率(n(TE))、TM折射率(n(TM))、平均折射率(n(AV))、面內/面外雙折射率、玻璃轉移溫度(Tg)、線膨脹係數(CTE)、1%熱重量減少溫度(Td1)之結果。 The light transmittance (T), total light transmittance (Tt), and TE refractive index of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes of Examples 14 and 15 in Table 3. (TE)), TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% The result of the thermogravimetric reduction temperature (Td1).

實施例16 Example 16

相對於實施例1所得之100重量份之清漆而言，使二氧化矽微粒成為10重量份的方式來將有機矽溶膠(日產化學工業股份有限公司製、商品名PMA-ST、粒徑10至30nm)添加至聚醯胺酸清漆，獲得聚醯胺酸-二氧化矽奈米粒子清漆。 The organic cerium sol (manufactured by Nissan Chemical Industry Co., Ltd., trade name: PMA-ST, particle size 10 to 10 parts by weight of the cerium oxide microparticles obtained in the first embodiment) 30 nm) was added to the polyamic acid varnish to obtain a poly-proline-niobium oxide nanoparticle varnish.

實施例17 Example 17

相對於實施例1所得之100重量份之清漆而言，使二氧化矽微粒成為20重量份的方式來將有機矽溶膠(日產化學工業股份有限公司製、商品名PMA-ST、粒徑10至30nm)添加至聚醯胺酸清漆，獲得聚醯胺酸-二氧化矽奈米粒子清漆。 The organic cerium sol (manufactured by Nissan Chemical Industries, Ltd., trade name: PMA-ST, particle size 10 to 10 parts by weight) of the cerium oxide particles obtained in the first embodiment. 30 nm) was added to the polyamic acid varnish to obtain a poly-proline-niobium oxide nanoparticle varnish.

實施例18 Example 18

相對於實施例1所得之100重量份之清漆而言，使二氧化矽微粒成為30重量份的方式來將有機矽溶膠(日產化學工業股份有限公司製、商品名PMA-ST、粒徑10至30nm)添加至聚醯胺酸清漆，獲得聚醯胺酸-二氧化矽奈米粒子清漆。 The organic cerium sol (manufactured by Nissan Chemical Industries, Ltd., trade name: PMA-ST, particle size 10 to 10 parts by weight) of the cerium sulphide granules obtained in the first embodiment. 30 nm) was added to the polyamic acid varnish to obtain a poly-proline-niobium oxide nanoparticle varnish.

於表4中顯示實施例16至18所調整的清漆組成。又，於表4中顯示使用此等之清漆而測定藉由350℃煅燒所得之耐熱性樹脂膜的光透射率(T)、全部光線透射率(Tt)、TE折射率(n(TE))、TM折射率(n(TM))、平均折射率(n(AV))、面內/面外雙折射率、玻璃轉移溫度(Tg)、線膨脹係數(CTE)、1%熱重量減少溫度(Td1)之結果。 The varnish compositions adjusted in Examples 16 to 18 are shown in Table 4. Moreover, in Table 4, the light transmittance (T), the total light transmittance (Tt), and the TE refractive index (n (TE)) of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes. , TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermogravimetric reduction temperature The result of (Td1).

實施例19 Example 19

將0.044g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、13.47g之GBL加至4g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.044 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and 13.47 g of GBL were added to 4 g of the polyimine powder obtained in Example 13 to obtain a polyimide pigment varnish.

實施例20 Example 20

將0.044g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、0.2g之Epiclon 850-S(商品名、大日本Ink化學工業股份有限公司)、13.47g之GBL加至4g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.044 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 g of Epiclon 850-S (trade name, Dainippon Ink Chemical Co., Ltd.), and 13.47 g of GBL were added to 4 g of the polyimine powder obtained in Example 13 was used to obtain a polyimide pigment varnish.

實施例21 Example 21

將0.044g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、0.4g之Epiclon 850-S(商品名、大日本Ink化學工業股份有限公司)、13.47g之GBL加至4g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.044 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.4 g of Epiclon 850-S (trade name, Dainippon Ink Chemical Co., Ltd.), and 13.47 g of GBL were added to 4 g of the polyimine powder obtained in Example 13 was used to obtain a polyimide pigment varnish.

實施例22 Example 22

將0.044g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、0.8g之Epiclon 850-S(商品名、大日本Ink化學工業股份有限公司)、13.47g之GBL加至4g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.044 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.8 g of Epiclon 850-S (trade name, Dainippon Ink Chemical Co., Ltd.), and 13.47 g of GBL were added to 4 g of the polyimine powder obtained in Example 13 was used to obtain a polyimide pigment varnish.

於表5中顯示使用實施例19至22之清漆而測定藉由在300℃下之煅燒所得之耐熱性樹脂膜的光透射率(T)、全部光線透射率(Tt)、TE折射率(n(TE))、TM折射率(n(TM))、平均折射率(n(AV))、面內/面外雙折射率、玻璃轉移溫度(Tg)、線膨脹係數(CTE)、1%熱重量減少溫度(Td1)、斷裂應力、斷裂伸度、楊氏模數之結果。 The light transmittance (T), total light transmittance (Tt), and TE refractive index (n) of the heat resistant resin film obtained by calcination at 300 ° C were measured using the varnishes of Examples 19 to 22 in Table 5. (TE)), TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% Thermal weight reduction temperature (Td1), fracture stress, elongation at break, and Young's modulus.

參考例1 Reference example 1

利用均質器攪拌117g之PB15：6(平均一次粒徑30nm)、140g之味之素Fine-Techno製“Ajisper”PB821之丙二醇一甲基醚乙酸酯溶液(30重量%)、93g之Daicel化學工業股份有限公司製“Cyclomer”ACA250(45重量%溶液)、及627g之丙二醇一甲基醚乙酸酯而製作糊。利用管將裝入此糊之燒杯與循環式珠磨機分散機(WAB A Bachofen公司製“DYNO-MILL”KDL-A)相連接，將直徑0.3mm之氧化鋯珠作為介質使用，進行3200rpm、3小時之分散處理，獲得藍色顏料分散液。將49.5833g之GBL加至所得之0.4167g之藍色顏料分散液而獲得稀釋溶液。 Stirring 117 g of PB15:6 (average primary particle size 30 nm), 140 g of Ajsper PB821 propylene glycol monomethyl ether acetate solution (30% by weight), 93 g of Daicel chemistry using a homogenizer Industrial Co., Ltd. "Cyclomer" ACA250 (45% by weight solution) and 627 g of propylene glycol monomethyl ether acetate were prepared to prepare a paste. The paste beaker was connected to a circulating bead mill disperser ("DYNO-MILL" KDL-A, manufactured by WAB A Bachofen Co., Ltd.), and a zirconia bead having a diameter of 0.3 mm was used as a medium at 3,200 rpm. After 3 hours of dispersion treatment, a blue pigment dispersion was obtained. 49.5833 g of GBL was added to the obtained 0.4167 g of the blue pigment dispersion to obtain a diluted solution.

實施例23 Example 23

將0.013g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、36.3g之GBL加至13g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and 36.3 g of GBL were added to 13 g of the polyimine powder obtained in Example 13 to obtain a polyimide pigment varnish.

實施例24 Example 24

將0.013g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、0.325g之參考例1所得之藍色顏料分散液、36.3g之GBL加至13g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.325 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

實施例25 Example 25

將0.013g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、0.650g之參考例1所得之藍色顏料分散液、36.3g之GBL加至13g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.650 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

實施例26 Example 26

將0.013g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、0.975g之參考例1所得之藍色顏料分散液、36.3g之GBL加至13g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.975 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

實施例27 Example 27

將0.013g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、1.300g之參考例1所得之藍色顏料分散液、36.3g之GBL加至13g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 1.300 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

實施例28 Example 28

將0.013g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、1.625g之參考例1所得之藍色顏料分散液、36.3g之GBL加至13g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 1.625 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

實施例29 Example 29

將0.013g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、2.600g之參考例1所得之藍色顏料分散液、36.3g之GBL加至13g之實施例13所得之聚醯亞胺粉末而獲得聚醯亞胺清漆。 0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 2.600 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

於表6中顯示使用實施例23至29之清漆而測定藉由在350℃下之煅燒所得之耐熱性樹脂膜的光透射率(T)、b^＊值、TE折射率(n(TE))、TM折射率(n(TM))、平均折射率(n(AV))、面內/面外雙折射率之結果。 The light transmittance (T), b ^* value, and TE refractive index (n(TE)) of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes of Examples 23 to 29 in Table 6. , TM refractive index (n (TM)), average refractive index (n (AV)), in-plane / out-of-plane birefringence results.

實施例30 Example 30

乾燥氮氣流下，將22.4g之HFHA(0.037莫耳)、0.58g之SiDA(0.0023莫耳)溶解於105g之NMP中。將5.75g之ODPA(0.018莫耳)與20g之NMP一併加入其中，在40℃下攪拌1小時。之後，將6.23g之PMDA-HH與20g之NMP一併加入，在80℃下攪拌8小時。接著，在室溫下攪拌11小時。之後，將1.011g之MAP與15g之NMP一併加入，在60℃下攪拌1小時。之後，滴入以10g之NMP稀釋4.60g之DFA(0.038莫耳)的溶液，滴入後，在60℃持續攪拌1小時。之後，進行2次同樣的操作。之後，在室溫下添加16.96g之乙酸，攪拌1小時。攪拌結束後，將溶液倒入2L之水中，過濾聚合物固體之沉澱物後收集。進一步利用2L之水進行5次洗淨，利用50℃之乾燥機，進行所收集的聚合物固體之72小時乾燥，獲得聚醯胺酸酯粉末。 22.4 g of HFHA (0.037 mol) and 0.58 g of SiDA (0.0023 mol) were dissolved in 105 g of NMP under a stream of dry nitrogen. 5.75 g of ODPA (0.018 mol) was added together with 20 g of NMP, and stirred at 40 ° C for 1 hour. Thereafter, 6.23 g of PMDA-HH was added together with 20 g of NMP, and stirred at 80 ° C for 8 hours. Then, it was stirred at room temperature for 11 hours. Thereafter, 1.011 g of MAP was added together with 15 g of NMP, and stirred at 60 ° C for 1 hour. Thereafter, a solution of 4.60 g of DFA (0.038 mol) diluted with 10 g of NMP was added dropwise, and after dropwise addition, stirring was continued at 60 ° C for 1 hour. After that, the same operation was performed twice. Thereafter, 16.96 g of acetic acid was added at room temperature, and the mixture was stirred for 1 hour. After the completion of the stirring, the solution was poured into 2 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 2 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyphthalate powder.

於4g之所得之聚醯胺酸酯粉末中，添加0.455g之醌二疊氮化合物TP-250(東洋合成股份有限公司製)、0.455g之HAP-170(東洋合成股份有限公司製)、0.421g之溶解加速劑Tris-HAP(本州化學股份有限公司製)、0.682g之熱交聯劑HMOM(本州化學股份有限公司製)、0.182g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、9.3g之EL、6.9g之GBL而獲得感光性樹脂組成物之清漆。使用所得之清漆，利用上述(9)之方法製作起伏圖案且進行感光性評估後，顯影膜減少量減少至0.17μm，感度為300mJ/cm²。 To 4 g of the obtained polyphthalate powder, 0.455 g of a quinonediazide compound TP-250 (manufactured by Toyo Seisakusho Co., Ltd.) and 0.455 g of HAP-170 (manufactured by Toyo Seisakusho Co., Ltd.), 0.421 were added. g dissolution accelerator Tris-HAP (manufactured by Honshu Chemical Co., Ltd.), 0.682 g of thermal crosslinking agent HMOM (manufactured by Honshu Chemical Co., Ltd.), and 0.182 g of surfactant Active Flow 77 (trade name, Kyoeisha Chemical Co., Ltd.) A varnish of a photosensitive resin composition was obtained by 9.3 g of EL and 6.9 g of GBL. Using the obtained varnish, the undulating pattern was produced by the method of the above (9), and after the photosensitivity evaluation, the amount of development film reduction was reduced to 0.17 μm, and the sensitivity was 300 mJ/cm ² .

實施例31 Example 31

在4.646g之實施例12所得之聚醯亞胺粉末中，添加0.929g之醌二疊氮化合物HAP-170(東洋合成股份有限公司製)、0.664g之熱交聯劑HMOM(本州化學股份有限公司製)、0.011g之界面活性劑Polyflow 77(商品名、共榮社化學股份有限公司製)、18.75g之GBL而獲得感光性樹脂組成物之清漆。使用所得之清漆，利用上述(9)之方法製作起伏圖案而進行感光性評估後，顯影膜減少量為1.27μm，感度為125mJ/cm²。 To 4.646 g of the polyimine powder obtained in Example 12, 0.929 g of a quinonediazide compound HAP-170 (manufactured by Toyo Seisakusho Co., Ltd.) and 0.664 g of a thermal crosslinking agent HMOM (Honzhou Chemical Co., Ltd.) were added. A varnish of a photosensitive resin composition was obtained by using 0.011 g of a surfactant, Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and 18.75 g of GBL. Using the obtained varnish, the undulation pattern was produced by the method of the above (9), and after the photosensitivity evaluation, the amount of development film reduction was 1.27 μm, and the sensitivity was 125 mJ/cm ² .

[產業上之可利用性] [Industrial availability]

若根據本發明，能夠提供一種聚醯胺酸樹脂組成物、聚醯亞胺樹脂組成物及聚醯亞胺唑樹脂組成物，熱處理後之膜具有優異的耐熱性、光透射性、低雙折射性。熱處理後之膜能夠適用於平板顯示器、觸控面板、電子紙、彩色濾光片基板、太陽能電池等之可撓性基板、半導體元件之表面保護膜、層間絕緣膜、有機電致發光元件(有機EL元件)之絕緣層或間隙物層、薄膜電晶體基板之平坦化膜、有機電晶體之絕緣層、可撓性印刷基板等。 According to the present invention, it is possible to provide a polyamine resin composition, a polyimide composition, and a polyimine. The azole resin composition has excellent heat resistance, light transmittance, and low birefringence after heat treatment. The film after heat treatment can be applied to a flexible substrate such as a flat panel display, a touch panel, an electronic paper, a color filter substrate, a solar cell, a surface protective film of a semiconductor element, an interlayer insulating film, or an organic electroluminescence element (organic The insulating layer or the spacer layer of the EL element), the planarizing film of the thin film transistor substrate, the insulating layer of the organic transistor, the flexible printed circuit board, and the like.

Claims

一種聚醯胺酸樹脂組成物，其特徵為含有(a)以通式(1)所表示之構造單元作為主要成分之聚醯胺酸與(b)溶劑； (通式(1)中，X₁、X₂係各自獨立地表示氫原子或是碳數1至10之1價有機基；R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基；R₂係表示具有至少2個羥基的碳數2至40之2價有機基)。 A polyaminic acid resin composition characterized by comprising (a) a polyamic acid having a structural unit represented by the general formula (1) as a main component and (b) a solvent; (In the formula (1), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and R ₁ represents an alicyclic structure having a monocyclic or condensed polycyclic ring type; a tetravalent organic group having 4 to 40 carbon atoms, or an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 4 to 40 carbon atoms which are interlinked by a crosslinked structure; R ₂ represents a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups.

如申請專利範圍第1項之聚醯胺酸樹脂組成物，其中通式(1)中之R₁係由下列通式(4)至(10)所選出的1種以上； (通式(4)至(10)中，R₄至R₇₉係各自獨立地表示氫原子、鹵素原子或是氫原子亦可被鹵素原子所取代的碳數1至3之1價有機基；通式(7)中，X₃係氧原子、硫原子、磺醯基或氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基或是由此等2個以上連結構成之2價交聯結構；於通式(10)中，X₄係直接鍵結、氧原子、硫原子、磺醯基或氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基或是氫原子亦可被鹵素原子所取代的伸芳基或氧原子、硫原子、磺醯基、氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基與氫原子被鹵素原子所取代的伸芳基所選出的由2個以上連結構成之2價交聯結構)。 The polyamino acid resin composition according to claim 1, wherein R ₁ in the formula (1) is one or more selected from the following general formulae (4) to (10); (In the general formulae (4) to (10), R ₄ to R ₇₉ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom; In the formula (7), the X ₃ -based oxygen atom, the sulfur atom, the sulfonyl group or the hydrogen atom may be substituted by a halogen atom, and the divalent organic group having 1 to 3 carbon atoms may be substituted or two or more the divalent crosslinked structure; in the general formula (10), X ₄ based direct bond, an oxygen atom, a sulfur atom, a sulfonic acyl or a hydrogen atom may also be a halogen atom substituted with 1 to 3 carbon atoms of the divalent An organic group or a hydrogen atom may be substituted by a halogen atom, an aryl group or an oxygen atom, a sulfur atom, a sulfonyl group, or a hydrogen atom may be substituted by a halogen atom, and a carbon number of 1 to 3 may be substituted with a hydrogen atom and hydrogen. A divalent crosslinked structure composed of two or more bonds selected from an extended aryl group in which an atom is substituted by a halogen atom).

如申請專利範圍第1項之聚醯胺酸樹脂組成物，其中通式(1)中之R₂係由下式(14)所表示， The polyaminic acid resin composition of claim 1, wherein the R ₂ in the formula (1) is represented by the following formula (14),

如申請專利範圍第1項之聚醯胺酸樹脂組成物，其中以(a)通式(1)所表示之構造單元作為主要成分的聚醯胺酸含有10%至50%之以通式(36)所表示之構造單元； (通式(36)中，X₁、X₂係各自獨立地表示氫原子或是碳數1至10之1價有機基；R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基)。 The polyaminic acid resin composition according to the first aspect of the invention, wherein the polyamic acid having the structural unit represented by the formula (1) (1) as a main component contains 10% to 50% of the formula ( 36) the structural unit represented; (In the formula (36), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and R ₁ represents an alicyclic structure having a monocyclic or condensed polycyclic ring type; The tetravalent organic group having a carbon number of 4 to 40, or an organic group having a monocyclic alicyclic structure or a tetravalent organic group having a carbon number of 4 to 40 in which the crosslinked structure is interlinked therebetween.

如申請專利範圍第1至4項中任一項之聚醯胺酸樹脂組成物，其中藉由熱處理所得之膜面內/面外雙折射率為0.01以下。 The polyphthalic acid resin composition according to any one of claims 1 to 4, wherein the in-plane/out-of-plane birefringence obtained by the heat treatment is 0.01 or less.

一種聚醯亞胺樹脂組成物，其特徵為含有以(a’)通式(2)所表示之構造單元作為主要成分的聚醯亞胺與(b)溶劑； (通式(2)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基；R₂係表示具有至少2個羥基的碳數2至40之2價有機基)。 A polyimine resin composition characterized by comprising a polyimine and (b) a solvent having (a') a structural unit represented by the general formula (2) as a main component; (In the formula (2), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in the intermediate structure; and R ₂ means a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups.

如申請專利範圍第6項之聚醯亞胺樹脂組成物，其中通式(2)中之R₁係由下列通式(4)至(10)所選出的1種以上； (通式(4)至(10)中，R₄至R₇₉係各自獨立地表示氫原子、鹵素原子或是氫原子亦可被鹵素原子所取代的碳數1至3之1價有機基；通式(7)中，X₃係氧原子、硫原子、磺醯基或氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基或是由此等2個以上連結構成之2價交聯結構；於通式(10)中，X₄係直接鍵結、氧原子、硫原子、磺醯基或氫原子亦可被鹵素原子所取代的伸芳基或氧原子、硫原子、磺醯基、氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基或氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基與氫原子被鹵素原子所取代的伸芳基所選出的由2個以上連結構成之2價交聯結構)。 The polyimine resin composition of claim 6, wherein R ₁ in the formula (2) is one or more selected from the following general formulae (4) to (10); (In the general formulae (4) to (10), R ₄ to R ₇₉ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom; In the formula (7), the X ₃ -based oxygen atom, the sulfur atom, the sulfonyl group or the hydrogen atom may be substituted by a halogen atom, and the divalent organic group having 1 to 3 carbon atoms may be substituted or two or more a two-valent crosslinked structure; in the formula (10), X ₄ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group or a hydrogen atom which may be substituted by a halogen atom, an aryl group or an oxygen atom, sulfur a valent organic group having 1 to 3 carbon atoms or a hydrogen atom to which an atom, a sulfonyl group or a hydrogen atom may be substituted by a halogen atom may be substituted by a halogen atom, and a divalent organic group having 1 to 3 carbon atoms and a hydrogen atom. A divalent crosslinked structure composed of two or more linkages selected from an extended aryl group substituted by a halogen atom).

如申請專利範圍第6項之聚醯亞胺樹脂組成物，其中通式(2)中之R₂係由下式(14)所表示， The polyimine resin composition of claim 6, wherein the R ₂ in the formula (2) is represented by the following formula (14),

如申請專利範圍第6項之聚醯亞胺樹脂組成物，其中以(a’)通式(2)所表示之構造單元作為主要成分的聚醯亞胺含有10%至50%之以通式(37)所表示之構造單元； (通式(37)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基)。 The polyimine resin composition of claim 6, wherein the polyimine having the structural unit represented by the formula (2) (a) contains 10% to 50% of a general formula. (37) the structural unit represented; (In the formula (37), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure. Or a tetravalent organic group having 4 to 40 carbon atoms in which the crosslinked structure is interlinked.

如申請專利範圍第6至9項中任一項之聚醯亞胺樹脂組成物，其中藉由熱處理所得之膜面內/面外雙折射率為0.01以下。 The polyimine resin composition according to any one of claims 6 to 9, wherein the in-plane/out-of-plane birefringence obtained by the heat treatment is 0.01 or less.

一種聚醯亞胺唑樹脂組成物，其特徵為含有以(a”)通式(3)所表示之構造單元作為主要成分的聚醯亞胺唑與(b)溶劑； (通式(3)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基；R₃係表示碳數2至40之4價有機基)。 Polyimine An azole resin composition characterized by containing a polyimine which has a structural unit represented by the formula (3) (3) as a main component Oxazole and (b) solvent; (In the formula (3), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in a crosslinked structure; R ₃ means a tetravalent organic group having 2 to 40 carbon atoms.

如申請專利範圍第11項之聚醯亞胺唑樹脂組成物，其中通式(3)中之R₁係由下列通式(4)至(10)所選出的1種以上； (通式(4)至(10)中，R₄至R₇₉係各自獨立地表示氫原子、鹵素原子或是氫原子亦可被鹵素原子所取代的碳數1至3之1價有機基；通式(7)中，X₃係氧原子、硫原子、磺醯基或氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基或是由此等2個以上連結構成之2價交聯結構；於通式(10)中，X₄係直接鍵結、氧原子、硫原子、磺醯基或氫原子亦可被鹵素原子所取代的伸芳基或氧原子、硫原子、磺醯基、氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基或是氫原子亦可被鹵素原子所取代的碳數1至3之2價有機基與氫原子被鹵素原子所取代的伸芳基所選出的由2個以上連結構成之2價交聯結構)。 Such as the polyimine of claim 11 An azole resin composition in which R ₁ in the general formula (3) is one or more selected from the following general formulae (4) to (10); (In the general formulae (4) to (10), R ₄ to R ₇₉ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom; In the formula (7), the X ₃ -based oxygen atom, the sulfur atom, the sulfonyl group or the hydrogen atom may be substituted by a halogen atom, and the divalent organic group having 1 to 3 carbon atoms may be substituted or two or more a two-valent crosslinked structure; in the formula (10), X ₄ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group or a hydrogen atom which may be substituted by a halogen atom, an aryl group or an oxygen atom, sulfur A valent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom, or a hydrogen atom or a hydrogen atom may be substituted by a halogen atom, and a divalent organic group having 1 to 3 carbon atoms and hydrogen. A divalent crosslinked structure composed of two or more bonds selected from an extended aryl group in which an atom is substituted by a halogen atom).

如申請專利範圍第11項之聚醯亞胺唑樹脂組成物，其中通式(3)中之R₃係由下式(25)所表示， Such as the polyimine of claim 11 An azole resin composition in which R ₃ in the formula (3) is represented by the following formula (25),

如申請專利範圍第11項之聚醯亞胺唑樹脂組成物，其中以(a”)通式(3)所表示之構造單元作為主要成分的聚醯亞胺唑含有10%至50%之以通式(37)所表示之構造單元； (通式(37)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基)。 Such as the polyimine of claim 11 An azole resin composition in which a polyimine of (a") a structural unit represented by the formula (3) is used as a main component The azole contains 10% to 50% of the structural unit represented by the general formula (37); (In the formula (37), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure. Or a tetravalent organic group having 4 to 40 carbon atoms in which the crosslinked structure is interlinked.

如申請專利範圍第11至14項中任一項之聚醯亞胺唑樹脂組成物，其中藉由熱處理所得之膜面內/面外雙折射率為0.01以下。 Polyimine, as claimed in any one of claims 11 to 14 The azole resin composition in which the in-plane/out-of-plane birefringence obtained by heat treatment is 0.01 or less.

一種可撓性基板，其特徵為含有由以通式(2)所表示之聚醯亞胺結構的樹脂組成物； (通式(2)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基；R₂係表示具有至少2個羥基的碳數2至40之2價有機基)。 A flexible substrate characterized by containing a resin composition of a polyimine structure represented by the general formula (2); (In the formula (2), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in the intermediate structure; and R ₂ means a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups.

一種可撓性基板，其特徵為含有由以通式(3)所表示之聚醯亞胺唑構成之樹脂組成物； (通式(3)中，R₁係表示具有單環式或縮合多環式之脂環結構的碳數4至40之4價有機基、或是具有單環式脂環結構之有機基直接地或使交聯結構介於中間所相互連結的碳數4至40之4價有機基；R₃係表示碳數2至40之4價有機基)。 A flexible substrate characterized by containing a polyimine represented by the general formula (3) a resin composition composed of azole; (In the formula (3), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in a crosslinked structure; R ₃ means a tetravalent organic group having 2 to 40 carbon atoms.