TW201343722A - Polyimide precursor varnish, polyimide resin, electrical component, heat resistant tape, heat resistant coating and adhesive for aerospace - Google Patents

Polyimide precursor varnish, polyimide resin, electrical component, heat resistant tape, heat resistant coating and adhesive for aerospace Download PDF

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TW201343722A
TW201343722A TW102109066A TW102109066A TW201343722A TW 201343722 A TW201343722 A TW 201343722A TW 102109066 A TW102109066 A TW 102109066A TW 102109066 A TW102109066 A TW 102109066A TW 201343722 A TW201343722 A TW 201343722A
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polyimide
polyimine
acid dianhydride
precursor
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Kenji Iida
Shigeo Kiba
Kiyomi Imagawa
Yusuke Tomita
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Mitsui Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

A polyimide precursor varnish, polyimide resin and use thereof are provided. The polyimide precursor varnish can provide raw materials having excellent insulated property and mechanical strength, and satisfying both heat resistance and low water absorptivity. The polyimide precursor varnish of the invention includes a composition having a polyimide precursor and solvents. When a polyimide film obtained by coating the composition, rising temperature by 5 DEG C /min, and heating 1 hour under nitrogen atmosphere at 300 DEG C has a film thickness of 20 μ m-60 μ m after drying, it has glass transition temperature of 290 DEG C or more, water-absorbing ratio of 2.0% or less, and tearing fracture elongations of 55% or more.

Description

聚醯亞胺前驅物清漆、聚醯亞胺樹脂及其用途 Polyimine precursor varnish, polyimine resin and use thereof

本發明是有關於一種包含含有聚醯亞胺前驅物、及溶劑的組成物的聚醯亞胺前驅物清漆。並且是有關於一種藉由將由聚醯亞胺前驅物清漆而得的成形物進行醯亞胺化而形成的聚醯亞胺樹脂。而且是有關於一種使用上述聚醯亞胺前驅物清漆、或聚醯亞胺樹脂的用途。 The present invention relates to a polyamidene precursor varnish comprising a composition comprising a polyimide precursor and a solvent. Further, it relates to a polyimine resin which is formed by ruthenium imidating a molded article obtained by varnishing a polyimide precursor. Further, it relates to a use of the above polyimine precursor varnish or polyimine resin.

電線配線或電纜等成為金屬導體藉由絕緣被覆材塗佈，而保護導體部的構成。絕緣被覆材根據用途而開發了各種製品，作為電線或馬達捲線等的絕緣被覆材用途，可使用：聚醯胺、聚醯胺醯亞胺、聚酯醯亞胺、聚醯亞胺等工程塑膠。這些中，聚醯亞胺就耐熱性、電絕緣性、機械強度等的觀點而言表現出極優異的特性，因此特別是利用於使用環境嚴酷的馬達捲線等。 A wire harness, a cable, or the like is a structure in which a metal conductor is coated with an insulating coating material to protect the conductor portion. Insulation-coated materials have been developed for various applications. For use as insulating coatings for electric wires or motor windings, engineering plastics such as polyamides, polyamides, polyesters, polyimides, and polyimides can be used. . Among these, since the polyimine exhibits extremely excellent characteristics from the viewpoints of heat resistance, electrical insulating properties, mechanical strength, and the like, it is particularly used in a motor winding wire or the like which is severe in use environment.

作為商品化的聚醯亞胺，有：包含雙(4-胺基苯基)醚與均苯四甲酸二酐的KAPTON、VESPEL(註冊商標、杜邦(Dupont)公司製造)，作為包含雙(4-胺基苯基)醚與3,3',4,4'-聯苯四甲酸二酐的聚醯亞胺的Upilex(註冊商標、宇部興產公司製造)，AURUM (註冊商標、三井化學公司製造)等。 Commercially available polyimines include KAPTON and VESPEL (registered trademark, manufactured by DuPont), which contain bis(4-aminophenyl)ether and pyromellitic dianhydride, and contain bis (4). Upilex (registered trademark, manufactured by Ube Industries, Ltd.) of Amino-Aminophenyl)ether and 3,3',4,4'-biphenyltetracarboxylic dianhydride, AURUM (registered trademark, manufactured by Mitsui Chemicals, Inc.).

專利文獻1中記載如下的絕緣電線的製造方法：藉由擠出機於300℃以上、450℃以下的溫度範圍內，將具有下述通式(I)所示的重複結構單元的聚醯亞胺加熱熔融而被覆導體，進行冷卻固化而形成絕緣體。 Patent Document 1 describes a method for producing an insulated wire having a repeating structural unit represented by the following formula (I) in a temperature range of 300 ° C or higher and 450 ° C or lower by an extruder. The amine is heated and melted to coat the conductor, and is cooled and solidified to form an insulator.

式(I)中，R表示選自由碳數2以上的脂肪族基、環式脂肪族基、單環式芳香族基、縮合多環式芳香族基、芳香族基直接或藉由交聯員相互連結的非縮合多環式芳香族基所組成的組群的4價基團，X表示單鍵、硫原子、碸基、羰基、亞異丙基或六氟亞異丙基的2價基團。 In the formula (I), R represents an aliphatic group selected from a carbon number of 2 or more, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, an aromatic group, or directly by a crosslinker. a tetravalent group of a group of non-condensed polycyclic aromatic groups bonded to each other, and X represents a divalent group of a single bond, a sulfur atom, a thiol group, a carbonyl group, an isopropylidene group or a hexafluoroisopropylidene group. group.

專利文獻2揭示，使用對苯二胺及4,4'-二胺基二苯醚作為二胺、使用3,3',4,4'-聯苯四甲酸二酐作為酸二酐的絕緣電線。 Patent Document 2 discloses an insulated wire using p-phenylenediamine and 4,4'-diaminodiphenyl ether as a diamine and 3,3',4,4'-biphenyltetracarboxylic dianhydride as an acid dianhydride. .

專利文獻3中，為了獲得可形成具有耐熱性並且對導體的密接性高、介電常數低的絕緣被膜的絕緣塗料、絕緣電線，而提出包含具有下述通式(II)所示的重複單元、及下述通式(III)所示的重複單元的聚醯亞胺樹脂的絕緣塗料。 In order to obtain an insulating coating material or an insulated wire which can form an insulating film having heat resistance and high adhesion to a conductor and having a low dielectric constant, Patent Document 3 proposes to include a repeating unit having the following general formula (II). And an insulating coating of a polyimine resin of a repeating unit represented by the following formula (III).

通式(II)中，X1為具有下述式(IV)所示的芳香族醚結構的4價芳香族基，Y1為具有芳香族醚結構的2價芳香族基，通式(III)中，X2為4價脂環式基，Y2為包含脂環式結構的2價脂環式基，通式(II)及通式(III)中，m、n為重複數，且分別為正整數。 In the formula (II), X 1 is a tetravalent aromatic group having an aromatic ether structure represented by the following formula (IV), and Y 1 is a divalent aromatic group having an aromatic ether structure, and the formula (III) Wherein X 2 is a tetravalent alicyclic group, Y 2 is a divalent alicyclic group containing an alicyclic structure, and m, n are repeating numbers in the formula (II) and formula (III), and They are positive integers.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平2-210713號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2-210713

[專利文獻2]日本專利特開平7-37439號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 7-37439

[專利文獻3]日本專利特開2010-189510號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-189510

電子產業的顯著的發展受到各種電子零件、電子零件所用的原材料的開發的支撐。絕緣原材料中，如上述般，藉由銳意的研究開發而提出優異的原材料。然而，市場中作為更高性能的原材料，要求除了優異的絕緣特性、及機械強度外，還兼具耐熱性與低吸水性這兩者的原材料。若可提供滿足耐熱性與低吸水性這兩者的材料，則可提高高溫環境下的耐久性。另外，例如在用作絕緣電線的絕緣被覆材時，可期待實現低傳輸損失化。 The remarkable development of the electronics industry is supported by the development of raw materials for various electronic components and electronic components. Among the insulating raw materials, as described above, excellent raw materials have been proposed by intensive research and development. However, in the market, as a raw material of higher performance, in addition to excellent insulating properties and mechanical strength, it is required to have both heat resistance and low water absorption. If a material that satisfies both heat resistance and low water absorption can be provided, durability in a high temperature environment can be improved. Further, for example, when used as an insulating covering material for an insulated electric wire, it is expected to achieve low transmission loss.

另外，上述對絕緣被覆材的課題進行了敍述，但關於以耐熱膠帶、耐熱塗料、航空宇宙用黏接劑等為代表的各種用途，亦可產生同樣的課題。 In addition, although the above-mentioned problem of the insulating coating material has been described, the same problem can be caused by various applications such as heat-resistant tape, heat-resistant paint, and aerospace adhesive.

本發明是鑒於上述背景而完成，其目的是提供一種聚醯亞胺前驅物清漆、聚醯亞胺樹脂、及這些的用途，上述聚醯亞胺前驅物清漆可提供具有優異的絕緣特性及機械強度、而且滿足耐熱性與低吸水性這兩者的原材料。 The present invention has been made in view of the above background, and an object thereof is to provide a polyimide varnish precursor, a phthalimide resin, and the use thereof, which can provide excellent insulating properties and mechanical properties. A raw material that has both strength and heat resistance and low water absorption.

本發明者等人反覆進行銳意研究，結果發現在以下形態中可解決本發明的課題，從而完成了本發明。即，本發明的聚醯亞胺前驅物清漆包含含有聚醯亞胺前驅物、及溶劑的組成物，且將上述組成物進行塗膜，在以5℃/min進行升溫、於300℃於氮氣環境下加熱處理1小時而得的乾燥後的塗膜厚度為20 μm~60 μm的聚醯亞胺膜時，玻璃轉移溫度為290℃以上、吸水率為2.0%以 下、及拉伸斷裂伸長率為55%以上。 The present inventors have repeatedly conducted intensive studies, and as a result, have found that the subject of the present invention can be solved in the following aspects, and completed the present invention. That is, the polyimide precursor varnish of the present invention contains a composition containing a polyimide precursor and a solvent, and the composition is coated, and the temperature is raised at 5 ° C / min, and nitrogen is introduced at 300 ° C. When the polyimide film having a thickness of 20 μm to 60 μm after drying is heated for 1 hour in an environment, the glass transition temperature is 290 ° C or higher and the water absorption rate is 2.0%. The lower and tensile elongation at break are 55% or more.

此處所揭示的聚醯亞胺前驅物清漆的較佳的一個形態中，上述聚醯亞胺前驅物藉由將二胺、與酸二酐進行聚縮合而得，上述二胺是至少將相對於該二胺的總量而為19莫耳%以上、56莫耳%以下的化學式(1)所示的二胺成分A、及相對於該二胺的總量而為44莫耳%以上、81莫耳%以下的化學式(2)所示的二胺成分B作為構成成分，上述酸二酐是至少將相對於該酸二酐的總量而為60莫耳%以上、100莫耳%以下的化學式(3)所示的酸二酐成分C、及相對於該酸二酐的總量而為0莫耳%以上、40莫耳%以下的化學式(4)所示的酸二酐成分D作為構成成分。 In a preferred embodiment of the polyamidene precursor varnish disclosed herein, the polyimine precursor is obtained by polycondensing a diamine with an acid dianhydride, and the diamine is at least relative to The total amount of the diamine is 19 mol% or more and 56 mol% or less of the diamine component A represented by the chemical formula (1), and 44 mol% or more with respect to the total amount of the diamine, 81 The diamine component B represented by the chemical formula (2) having a molar ratio of 5% or less is a constituent component, and the acid dianhydride is at least 60 mol% or more and 100 mol% or less based on the total amount of the acid dianhydride. The acid dianhydride component C represented by the chemical formula (3) and the acid dianhydride component D represented by the chemical formula (4) of 0 mol% or more and 40 mol% or less with respect to the total amount of the acid dianhydride are used. Composition.

(式中，X表示單鍵、氧原子、硫原子、碸基、羰基、亞甲基、亞異丙基或六氟亞異丙基的2價基團) (wherein X represents a single bond, an oxygen atom, a sulfur atom, a thiol group, a carbonyl group, a methylene group, an isopropylidene group or a divalent group of a hexafluoroisopropylidene group)

(式中，Y表示單鍵、氧原子、硫原子、碸基、羰基、亞甲基、亞異丙基或六氟亞異丙基的2價基團) (wherein Y represents a single bond, an oxygen atom, a sulfur atom, a thiol group, a carbonyl group, a methylene group, an isopropylidene group or a divalent group of a hexafluoroisopropylidene group)

另外，此處所揭示的聚醯亞胺前驅物清漆的較佳的一個形態中，上述聚醯亞胺前驅物是相對於上述二胺與上述酸二酐的合計，而在上述二胺成分A與上述二胺成分B的合計滿足47.5 mol%~52.5 mol%、上述酸二酐成分C與上述酸二酐成分D的合計滿足47.5 mol%~52.5 mol%的範圍內進行共聚合者。 Further, in a preferred embodiment of the polyimine precursor varnish disclosed herein, the polyimine precursor is a total of the diamine component A and the diamine component and the acid dianhydride. The total of the diamine component B satisfies 47.5 mol% to 52.5 mol%, and the total of the acid dianhydride component C and the acid dianhydride component D satisfies the range of 47.5 mol% to 52.5 mol%.

另外，此處所揭示的聚醯亞胺前驅物清漆的較佳的一個形態中，上述二胺成分B是化學式(5)所記載的4,4'-雙(3-胺基苯氧基)聯苯。 Further, in a preferred embodiment of the polyimine precursor varnish disclosed herein, the diamine component B is a 4,4'-bis(3-aminophenoxy) group described in the chemical formula (5). benzene.

另外，此處所揭示的聚醯亞胺前驅物清漆的較佳的一個形態中，上述二胺成分A是化學式(6)所記載的4,4'-二胺基二苯醚。 Further, in a preferred embodiment of the polyimine precursor varnish disclosed herein, the diamine component A is a 4,4'-diaminodiphenyl ether of the formula (6).

另外，此處所揭示的聚醯亞胺前驅物清漆的較佳的一個形態中，上述酸二酐成分D是化學式(7)所記載的3,3',4,4'-聯苯四甲酸二酐。 Further, in a preferred embodiment of the polyimine precursor varnish disclosed herein, the acid dianhydride component D is 3,3',4,4'-biphenyltetracarboxylic acid described in the chemical formula (7). anhydride.

本發明的聚醯亞胺樹脂藉由將由上述形態的聚醯亞胺前驅物清漆而得的成形物進行醯亞胺化而形成。 The polyimine resin of the present invention is formed by ruthenium imidating a molded article obtained by varnishing a polyimine precursor precursor of the above aspect.

另外，此處所揭示的聚醯亞胺樹脂的較佳的一個形態中，有用作被覆導體的絕緣被覆材的形態。 Further, in a preferred embodiment of the polyimine resin disclosed herein, there is a form of an insulating coating material used as a coated conductor.

本發明的電子零件具備：導體、及被覆上述導體的絕緣被覆材，且上述絕緣被覆材的至少一部分具備聚醯亞胺樹脂，該聚醯亞胺樹脂藉由將由上述形態的聚醯亞胺前驅物清漆而得的成形物進行醯亞胺化而形成。作為電子零件的較佳例，有絕緣電線。 The electronic component of the present invention includes a conductor and an insulating covering material covering the conductor, and at least a part of the insulating covering material is provided with a polyimide resin, and the polyimide resin is preliminarily produced by the above-described form of polyimine The molded article obtained by the varnish is formed by hydrazine imidation. As a preferred example of the electronic component, there is an insulated wire.

本發明的耐熱膠帶具備：支撐基材、及形成於上述支撐基材上的接合層，上述支撐基材包含聚醯亞胺樹脂作為成分，該聚醯亞胺樹脂藉由將由上述形態的聚醯亞胺前驅物清漆而得的成形物進行醯亞胺化而形成。 The heat-resistant tape of the present invention comprises: a support substrate and a bonding layer formed on the support substrate, wherein the support substrate comprises a polyimide resin as a component, and the polyimide resin is obtained by the above-described form The molded article obtained from the imide precursor varnish is formed by hydrazine imidization.

本發明的耐熱塗料包含上述形態的聚醯亞胺前驅物清漆。 The heat resistant paint of the present invention comprises the polyimine precursor varnish of the above form.

本發明的航空宇宙用黏接劑包含上述形態的聚醯亞胺前驅物清漆、或包含由上述聚醯亞胺前驅物清漆形成的凝膠膜。 The aerospace adhesive of the present invention comprises the polyimine precursor varnish of the above form or a gel film formed of the above polyimine precursor varnish.

根據本發明，有可提供聚醯亞胺前驅物清漆、聚醯亞胺樹脂、及這些的用途的優異的效果，上述聚醯亞胺前驅物清漆可提供具有優異的絕緣特性及機械強度、而且兼具耐熱性與低吸水性這兩者的原材料。另外，根據本發明，有可提供低吸水性優異的原材料的優異的效果。 According to the present invention, there is provided an excellent effect of providing a polyimide varnish, a polyimide resin, and the use thereof, and the above-mentioned polyimide precursor varnish can provide excellent insulating properties and mechanical strength, and A raw material that combines both heat resistance and low water absorption. Further, according to the present invention, it is possible to provide an excellent effect of a raw material excellent in low water absorbability.

1‧‧‧絕緣電線 1‧‧‧insulated wire

2‧‧‧耐熱膠帶 2‧‧‧heat resistant tape

10‧‧‧導體 10‧‧‧Conductor

20‧‧‧絕緣被覆層 20‧‧‧Insulation coating

21‧‧‧第1絕緣被覆層 21‧‧‧1st insulation coating

22‧‧‧第2絕緣被覆層 22‧‧‧2nd insulation coating

30‧‧‧支撐基材 30‧‧‧Support substrate

31‧‧‧接合層 31‧‧‧ joint layer

圖1A是表示本實施形態的絕緣電線的一例的示意性剖面圖。 Fig. 1A is a schematic cross-sectional view showing an example of an insulated electric wire according to the embodiment.

圖1B是表示變形例的絕緣電線的一例的示意性剖面圖。 Fig. 1B is a schematic cross-sectional view showing an example of an insulated electric wire according to a modification.

圖2是表示本實施形態的耐熱膠帶的一例的示意性剖面圖。 Fig. 2 is a schematic cross-sectional view showing an example of the heat resistant tape of the embodiment.

以下，對應用本發明的實施形態的一例進行說明。另外，只要與本發明的宗旨一致，則當然其他的實施形態亦包含在本發明的範疇中。另外，以下的圖中的各構件的尺寸或比率，為了方便說明，未必與實際的尺寸或比率一致。另外，本說明書中，「任意的數A~任意的數B」的記載是指數A及大於數A的範圍、且數B及小於數B的範圍。 Hereinafter, an example of an embodiment to which the present invention is applied will be described. Further, other embodiments are also included in the scope of the present invention as long as they conform to the gist of the present invention. In addition, the size or ratio of each member in the following figures does not necessarily correspond to an actual size or ratio for convenience of description. In the present specification, the description of "arbitrary number A to any number B" is a range of the index A and the number A, and the number B and the range smaller than the number B.

[聚醯亞胺前驅物清漆、聚醯亞胺樹脂]本發明的聚醯亞胺前驅物清漆包含含有聚醯亞胺前驅物、及溶劑的組成物。更詳細而言，在將作為組成物的聚醯亞胺前驅物清漆進行塗膜，以5℃/min進行升溫、於300℃於氮氣環境下加熱處理1小時而得的乾燥後的塗膜厚度為20 μm以上、60 μm以下的範圍的聚醯亞胺膜(以下簡稱為「聚醯亞胺膜」)中，滿足(i)玻璃轉移溫度為290℃以上、(ii)吸水率為2.0%以下、及(iii)拉伸斷裂伸長率為55%以上的全部的條件。 [Polyimide precursor varnish, polyimine resin] The polyimine precursor varnish of the present invention contains a composition containing a polyimide precursor and a solvent. More specifically, the film thickness after drying is obtained by coating a polyimide film precursor varnish as a composition, heating at 5 ° C / min, and heat-treating at 300 ° C for 1 hour in a nitrogen atmosphere. In the polyimide film of 20 μm or more and 60 μm or less (hereinafter referred to as "polyimine film"), (i) the glass transition temperature is 290 ° C or higher, and (ii) the water absorption rate is 2.0%. Hereinafter, and (iii) all conditions of tensile elongation at break of 55% or more.

本發明的聚醯亞胺樹脂是藉由將由本發明的聚醯亞胺前驅物清漆而得的成形物進行醯亞胺化而形成者。此處，所謂成形物，是塗膜、膜、片、成形體、凝膠膜等。 The polyimine resin of the present invention is formed by ruthenium imidating a molded article obtained by varnishing the polyimine precursor of the present invention. Here, the molded article is a coating film, a film, a sheet, a molded body, a gel film, or the like.

為了使上述聚醯亞胺膜的乾燥後的塗膜厚度為20 μm~60 μm，例如將聚醯亞胺前驅物清漆塗成300 μm~400 μm的膜即可。上述聚醯亞胺膜的製作方法並無特別限定，作為一例，可列舉以下的方法。即，藉由300 μm~400 μm間隙的敷料器使用桌上塗敷機，在玻璃板上塗佈聚醯亞胺前驅物清漆。繼而，立即使用防爆型乾燥機，如上述般於氮氣環境中自常溫起以5℃/min升溫，於300℃保持1小時。然後，藉由自然冷卻而充分冷卻後，於溫水中漬水24小時，藉此自玻璃板剝離聚醯亞胺膜。並且，藉由充分地乾燥而以乾燥後的塗膜厚度為20 μm~60 μm的方式進行製作。 In order to make the thickness of the coating film after the drying of the above polyimide film is 20 μm to 60 μm, for example, a polyimide film precursor varnish may be applied to a film of 300 μm to 400 μm. The method for producing the polyimide film is not particularly limited, and examples thereof include the following methods. That is, the polyimine precursor varnish was coated on the glass plate using a table coater with an applicator having a gap of 300 μm to 400 μm. Then, an explosion-proof type dryer was used immediately, and the temperature was raised at 5 ° C / min from normal temperature in a nitrogen atmosphere as described above, and kept at 300 ° C for 1 hour. Then, after sufficiently cooling by natural cooling, water was sprayed in warm water for 24 hours, thereby peeling off the polyimide film from the glass plate. Further, it is produced by sufficiently drying the film thickness after drying to a thickness of 20 μm to 60 μm.

另外，本發明的聚醯亞胺前驅物清漆在製作上述膜厚的聚醯亞胺膜時，只要滿足上述(i)~(iii)的特性即可，並未規 定本發明的聚醯亞胺前驅物清漆的利用形態的膜厚。即，本發明的聚醯亞胺前驅物清漆可用於獲得各種膜厚的膜、片，及各種形態的成形物。 Further, in the polyimine precursor varnish of the present invention, when the polyimide film having the above film thickness is produced, the properties of the above (i) to (iii) are satisfied, and the composition is not regulated. The film thickness of the utilization form of the polyimine precursor varnish of the present invention is determined. That is, the polyimide precursor varnish of the present invention can be used for obtaining films, sheets, and molded articles of various forms having various film thicknesses.

本發明者等人反覆進行銳意研究，結果弄清，藉由使用在製作上述聚醯亞胺膜時，全部滿足上述(i)~(iii)的特性的聚醯亞胺前驅物清漆，而可提供具有優異的絕緣特性、及機械強度，而且兼具耐熱性與低吸水性的原材料。以下，進行詳細地說明。 The inventors of the present invention repeatedly conducted intensive studies, and as a result, it was found that by using the polyimine precursor varnish which satisfies the characteristics of the above (i) to (iii) in the production of the above polyimide film, It provides a raw material that has excellent insulation properties and mechanical strength, and has both heat resistance and low water absorption. Hereinafter, it demonstrates in detail.

上述聚醯亞胺膜中，就提供更優異的原材料的觀點而言，(i)的玻璃轉移溫度更佳為295℃以上，尤佳為300℃以上。另外，(ii)的吸水率更佳為設為1.9%以下，尤佳為設為1.8%以下。另外，(iii)的拉伸斷裂伸長率更佳為70%以上，特佳為100%以上。另外，作為絕緣體，就提高部分放電電壓耐性的觀點而言，聚醯亞胺樹脂的測定頻率為1 Hz時的介電常數，較佳為3.6以下，更佳為3.5以下，尤佳為3.4以下。 In the above polyimine film, the glass transition temperature of (i) is more preferably 295 ° C or higher, and particularly preferably 300 ° C or higher from the viewpoint of providing a more excellent raw material. Further, the water absorption rate of (ii) is more preferably 1.9% or less, and particularly preferably 1.8% or less. Further, the tensile elongation at break of (iii) is more preferably 70% or more, particularly preferably 100% or more. In addition, the dielectric constant of the polyimine resin at a measurement frequency of 1 Hz is preferably 3.6 or less, more preferably 3.5 or less, and particularly preferably 3.4 or less, from the viewpoint of improving partial discharge voltage resistance. .

另外，本說明書中玻璃轉移溫度是指藉由以下方法而測定的值。即，使用TA儀器(TA instruments)公司製造的RSA-II，藉由拉伸模式，於測定頻率1 Hz的條件下，進行上述聚醯亞胺膜的固體黏彈性的溫度分散測定，測定儲存彈性模數E'及損失彈性模數E"。並且，將由所得的損失正切tanδ=E"/E'的峰值導出的值設為「玻璃轉移溫度」。 In addition, the glass transition temperature in this specification is a value measured by the following method. Specifically, the RSA-II manufactured by TA Instruments (TA Instruments) was used to measure the storage viscosity of the solid viscoelasticity of the polyimide film by the tensile mode at a measurement frequency of 1 Hz. The modulus E' and the loss elastic modulus E" are added, and the value derived from the peak value of the obtained loss tangent tan δ = E" / E' is referred to as "glass transition temperature".

另外，本說明書的吸水率是指藉由以下方法而測定的 值。即，將上述聚醯亞胺膜切出為50 mm×50 mm尺寸，進行150℃×5分鐘乾燥後，立即測定質量。然後，於23℃的離子交換水中浸漬24小時。浸漬後，使用***等將自水槽取出的樣品的表面所附著的水分充分地吹散，然後測定質量，將根據下述數式(1)算出的值設為吸水率。 In addition, the water absorption rate of the present specification means the measurement by the following method. value. Namely, the above polyimide film was cut into a size of 50 mm × 50 mm, and dried at 150 ° C for 5 minutes, and the mass was measured immediately. Then, it was immersed in ion-exchange water at 23 ° C for 24 hours. After the immersion, the water adhering to the surface of the sample taken out from the water tank was sufficiently blown off using an air gun or the like, and then the mass was measured, and the value calculated according to the following formula (1) was taken as the water absorption rate.

<數式1>吸水率={(浸水後樣品的質量)-(浸水前樣品質量)}÷(浸水前樣品質量)．．數式(1) <Formula 1> Water absorption rate = {(mass of sample after immersion) - (sample quality before immersion)} ÷ (sample quality before immersion). . Number (1)

另外，拉伸斷裂伸長率是指藉由以下方法測定的值。即，將上述聚醯亞胺膜切出為長度140 mm×寬度10 mm尺寸，將實際的測定長度設為100 mm(其中兩端20 mm的部分為拉伸區域)，使用島津製作所公司製造的AUTOGRAPH AGS-100D於室溫(23℃)下、以速度50 mm/min將短條狀膜樣品拉伸。將根據此時的(斷裂時的聚醯亞胺膜的長度)/(聚醯亞胺膜的原來長度)算出的值設為拉伸斷裂伸長率。 Further, the tensile elongation at break means a value measured by the following method. That is, the above-mentioned polyimide film was cut into a length of 140 mm × a width of 10 mm, and the actual measurement length was set to 100 mm (the portion having 20 mm at both ends was a stretching region), and manufactured by Shimadzu Corporation. The AUTOGRAPH AGS-100D was stretched at room temperature (23 ° C) at a speed of 50 mm/min. The value calculated based on (the length of the polyimide film at the time of the fracture) / (the original length of the polyimide film) at this time was taken as the tensile elongation at break.

作為本發明的聚醯亞胺前驅物清漆的成分的聚醯亞胺前驅物，藉由將二胺與酸二酐進行聚縮合而得。以下，對用以滿足上述特性的較佳的聚醯亞胺前驅物的較佳實施形態進行說明。 The polyimine precursor which is a component of the polyimine precursor varnish of the present invention is obtained by polycondensing a diamine and an acid dianhydride. Hereinafter, a preferred embodiment of a preferred polyimide intermediate precursor which satisfies the above characteristics will be described.

本發明的聚醯亞胺前驅物若滿足上述(i)~(iii)的特性，則並無特別限定，作為較佳的單體，有以下形態。即，二胺有至少將相對於該二胺的總量而為19莫耳%以上、56莫耳%以下 的化學式(1)所示的二胺成分A、及相對於該二胺的總量而為44莫耳%以上、81莫耳%以下的化學式(2)所示的二胺成分B作為構成成分的形態。 The polyimine precursor of the present invention is not particularly limited as long as it satisfies the characteristics of the above (i) to (iii), and is preferably a monomer as follows. That is, the diamine is at least 19 mol% or more and 56 mol% or less based on the total amount of the diamine. The diamine component A represented by the chemical formula (1) and the diamine component B represented by the chemical formula (2) of 44 mol% or more and 81 mol% or less of the total amount of the diamine as a constituent component Shape.

化學式(2)中，X表示單鍵、氧原子、硫原子、碸基、羰基、亞甲基、亞異丙基或六氟亞異丙基的2價基團。 In the chemical formula (2), X represents a divalent group of a single bond, an oxygen atom, a sulfur atom, a thiol group, a carbonyl group, a methylene group, an isopropylidene group or a hexafluoroisopropylidene group.

酸二酐有至少將相對於該酸二酐的總量而為60莫耳%以上、100莫耳%以下的化學式(3)所示的均苯四甲酸二酐即酸二酐成分C、及相對於該酸二酐的總量而為0莫耳%以上、40莫耳%以下的化學式(4)所示的酸二酐成分D作為構成成分的形態。化學式(3)所示的均苯四甲酸二酐的下限值更佳為70莫耳%以上，尤佳為80莫耳%以上。另外，化學式(4)所示的酸二酐成分D的上限值更佳為30莫耳%以下，尤佳為20莫耳%以下。 The acid dianhydride is an acid dianhydride component C which is a pyromellitic dianhydride represented by the chemical formula (3) which is at least 60 mol% or more and 100 mol% or less with respect to the total amount of the acid dianhydride, and The acid dianhydride component D represented by the chemical formula (4) which is 0 mol% or more and 40 mol% or less of the total amount of the acid dianhydride is a component. The lower limit of the pyromellitic dianhydride represented by the chemical formula (3) is more preferably 70 mol% or more, and particularly preferably 80 mol% or more. Further, the upper limit of the acid dianhydride component D represented by the chemical formula (4) is more preferably 30 mol% or less, and particularly preferably 20 mol% or less.

化學式(4)中，Y表示單鍵、氧原子、硫原子、碸基、羰基、亞甲基、亞異丙基或六氟亞異丙基的2價基團。 In the chemical formula (4), Y represents a divalent group of a single bond, an oxygen atom, a sulfur atom, a thiol group, a carbonyl group, a methylene group, an isopropylidene group or a hexafluoroisopropylidene group.

上述化學式(1)、化學式(2)及化學式(4)在合成聚醯亞胺前驅物時，可分別獨立地使用單一或多種化合物。 In the above chemical formula (1), chemical formula (2), and chemical formula (4), when synthesizing a polyimide precursor, a single or a plurality of compounds may be used independently.

化學式(2)的二胺成分B的較佳例，可列舉：雙[4-(3-胺基苯氧基)苯基]硫醚、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]酮、4,4'-雙(3-胺基苯氧基)聯苯、4,4'-雙(4-胺基苯氧基)聯苯、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷等。 Preferred examples of the diamine component B of the chemical formula (2) include bis[4-(3-aminophenoxy)phenyl] sulfide and bis[4-(3-aminophenoxy)benzene.碸, bis[4-(3-aminophenoxy)phenyl]one, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-amine Phenoxy)biphenyl, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl] -1,1,1,3,3,3-hexafluoropropane, and the like.

作為二胺成分B的特佳例，可列舉：化學式(5)所記載的4,4'-雙(3-胺基苯氧基)聯苯。 As a particularly preferable example of the diamine component B, 4,4'-bis(3-aminophenoxy)biphenyl described by the chemical formula (5) is mentioned.

作為化學式(1)的二胺成分A的較佳例，可列舉：4,4'-二胺基二苯醚、3,4'-二胺基二苯醚、3,3'-二胺基二苯醚等。就結晶性提高的觀點而言，特佳為化學式(6)所示的4,4'-二胺基二苯醚。 Preferable examples of the diamine component A of the chemical formula (1) include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3'-diamino group. Diphenyl ether and the like. From the viewpoint of improving crystallinity, 4,4'-diaminodiphenyl ether represented by the chemical formula (6) is particularly preferred.

二胺較佳為將二胺成分A相對於二胺總量而設為19莫耳%~56莫耳%，將二胺成分B相對於二胺總量而設為44莫耳%~81莫耳%。藉由設為該範圍，而可更有效地兼具低吸水性與高Tg。相對於二胺總量的二胺成分A的下限值更佳為20莫耳%以上，尤佳為24莫耳%以上，特佳為30莫耳%以上，最佳為39莫耳%以上。另外，相對於二胺總量的二胺成分A的上限值更佳為設為51莫耳%以下，尤佳為設為50莫耳%以下。相對於二胺總量的二胺成分B的下限值更佳為49莫耳%以上，上限值更佳為80莫耳%以下，尤佳為76莫耳%以下，特佳為70莫耳%以下，最佳為61莫耳%以下。 The diamine preferably has a diamine component A of from 19 mol% to 56 mol% based on the total amount of the diamine, and a diamine component B of 44 mol% to 81 mol with respect to the total amount of the diamine. ear%. By setting it as this range, it is more effective to combine both low water absorption and high Tg. The lower limit of the diamine component A based on the total amount of the diamine is more preferably 20 mol% or more, particularly preferably 24 mol% or more, particularly preferably 30 mol% or more, and most preferably 39 mol% or more. . Further, the upper limit of the diamine component A with respect to the total amount of the diamine is more preferably 51 mol% or less, and particularly preferably 50 mol% or less. The lower limit of the diamine component B relative to the total amount of the diamine is more preferably 49 mol% or more, and the upper limit is more preferably 80 mol% or less, particularly preferably 76 mol% or less, and particularly preferably 70 mol%. Below the ear %, the best is below 61 mol%.

本實施形態中的二胺只要在上述聚醯亞胺膜中滿足上述(i)~(iii)的特性，則可使用上述化學式(1)、化學式(2)以外的二胺。就耐熱性的觀點而言，其他二胺較佳為芳香族二胺類。 In the diamine of the present embodiment, the diamines other than the above chemical formula (1) and chemical formula (2) can be used as long as the properties of the above (i) to (iii) are satisfied in the polyimide film. From the viewpoint of heat resistance, the other diamine is preferably an aromatic diamine.

其他芳香族二胺例如可列舉：對苯二胺、間苯二胺、間 胺基苄基胺、對胺基苄基胺、4,4'-二胺基聯苯、3,3'-二胺基聯苯、4,4'-二胺基二苯基甲烷、3,3'-二胺基二苯基甲烷、1,1-雙(4-胺基苯基)乙烷、1,1-雙(3-胺基苯基)乙烷、2,2-雙(4-胺基苯基)丙烷、2,2-雙(3-胺基苯基)丙烷、2,2-雙(4-胺基苯基)-1,1,1,3,3,3-六氟丙烷、2,2-雙-(3-胺基苯基)-1,1,1,3,3,3-六氟丙烷、3,3'-二胺基二苯硫醚、4,4'-二胺基二苯硫醚、3,3'-二胺基二苯基碸、3,3'-二胺基二苯甲酮、4,4'-二胺基二苯甲酮、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、2,2'-雙(4-(4-胺基苯氧基)苯基)丙烷、2,2'-二甲基-4,4'-二胺基聯苯、雙胺基苯基茀、雙甲苯胺茀、2,7-二胺基茀、2,2'-雙(三氟甲基)-1,1'-聯苯-4,4'-二胺、4,4'-亞甲基二苯胺、4,4'-(間苯二亞異丙基)二苯胺等。 Examples of the other aromatic diamines include p-phenylenediamine, m-phenylenediamine, and Aminobenzylamine, p-aminobenzylamine, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3, 3'-Diaminodiphenylmethane, 1,1-bis(4-aminophenyl)ethane, 1,1-bis(3-aminophenyl)ethane, 2,2-bis (4 -aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexa Fluoropropane, 2,2-bis-(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl hydrazine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1 , 3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2'-bis(4-(4-aminophenoxy)benzene Propane, 2,2'-dimethyl-4,4'-diaminobiphenyl, bisaminophenyl hydrazine, bis-toluidine oxime, 2,7-diamino hydrazine, 2,2'- Bis(trifluoromethyl)-1,1'-biphenyl-4,4'-diamine, 4,4'-methylenediphenylamine, 4,4'-(m-phenyleneisopropylene) Aniline and the like.

作為上述化學式(4)所示的酸二酐成分D的較佳例，可列舉：3,3',4,4'-聯苯四甲酸二酐、2,2',3,3'-聯苯四甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、2,2',3,3'-二苯甲酮四甲酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、雙(3,4-二羧基苯基)醚二酐、雙(2,3-二羧基苯基)醚二酐、雙(3,4-二羧基苯基)碸二酐、雙(2,3-二羧基苯基)碸二酐、2,2-雙(3,4-二羧基苯基)1,1,1,3,3,3-六氟丙烷二酐、2,2-雙(3,4-二羧基苯基)1,1,1,3,3,3-六氯丙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)甲烷二酐、4,4'-(對苯二氧)二鄰苯二甲酸二酐、4,4'-(間苯二氧)二鄰苯二甲酸二酐等化合物。 Preferred examples of the acid dianhydride component D represented by the above chemical formula (4) include 3,3',4,4'-biphenyltetracarboxylic dianhydride and 2,2',3,3'-linked. Pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-dual ( 3,4-Dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis(3,4-di Carboxyphenyl)ruthenic anhydride, bis(2,3-dicarboxyphenyl)ruthenium anhydride, 2,2-bis(3,4-dicarboxyphenyl) 1,1,1,3,3,3- Hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) 1,1,1,3,3,3-hexachloropropane dianhydride, 1,1-bis(2,3-di Carboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylene oxide) A compound such as diphthalic dianhydride or 4,4'-(m-phenylenedioxy)diphthalic dianhydride.

這些中，更佳為3,3',4,4'-聯苯四甲酸二酐、3,3',4,4'-二 苯甲酮四甲酸二酐、3,3',4,4'-二苯醚四甲酸二酐、對苯二氧二(4-鄰苯二甲酸)二酐。 Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-two are more preferred. Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, p-phenylenedioxybis(4-phthalic acid) dianhydride.

特佳為可列舉：化學式(7)所記載的3,3',4,4'-聯苯四甲酸二酐。 Particularly preferred is 3,3',4,4'-biphenyltetracarboxylic dianhydride described in Chemical Formula (7).

酸二酐可單獨使用酸二酐成分C，除了酸二酐成分C外亦可添加酸二酐成分D。酸二酐成分D可使用1種化合物，亦可混合使用2種以上。本實施形態中的酸二酐只要滿足上述(i)~(iii)的特性，則可使用上述化學式(3)、化學式(4)以外的酸二酐。就耐熱性的觀點而言，其他酸二酐較佳為芳香族酸二酐。 The acid dianhydride component C can be used alone as the acid dianhydride, and the acid dianhydride component D can be added in addition to the acid dianhydride component C. The acid dianhydride component D may be used alone or in combination of two or more. The acid dianhydride in the present embodiment can use an acid dianhydride other than the above chemical formula (3) or chemical formula (4) as long as the characteristics of the above (i) to (iii) are satisfied. From the viewpoint of heat resistance, the other acid dianhydride is preferably an aromatic acid dianhydride.

作為其他芳香族酸二酐的較佳例，可列舉：1,2,3,4-苯四甲酸二酐、2,3,6,7-萘四甲酸二酐、1,4,5,8-萘四甲酸二酐、1,2,5,6-萘四甲酸二酐、3,4,9,10-苝四甲酸二酐、2,3,6,7-蒽四甲酸二酐、1,2,7,8-菲四甲酸二酐等。 Preferable examples of the other aromatic acid dianhydride include 1,2,3,4-benzenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8. -naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 2,3,6,7-decanetetracarboxylic dianhydride, 1 , 2,7,8-phenanthrenecarboxylic acid dianhydride and the like.

本實施形態的聚醯亞胺前驅物的數量平均分子量並無特別限定，例如可設為5,000~100萬的範圍。作為較佳的範圍，為5,000~50,000。聚醯亞胺前驅物的數量平均分子量可藉由凝膠滲透層析法(gel permeation chromatography，GPC)而測定。 The number average molecular weight of the polyimine precursor of the present embodiment is not particularly limited, and may be, for example, in the range of 5,000 to 1,000,000. As a preferred range, it is 5,000 to 50,000. The number average molecular weight of the polyimine precursor can be determined by gel permeation chromatography (GPC).

繼而，對聚醯亞胺前驅物清漆的製造方法進行說明。首先，使上述特定的二胺與特定的四甲酸二酐反應而獲得聚醯胺酸。聚醯亞胺前驅物的酸二酐與二胺在合成時的比例並無特別限定，較佳為相對於二胺與酸二酐的合計，而在二胺成分A與二胺成分B的合計滿足47.5莫耳%~52.5莫耳%，且酸二酐成分C與酸二酐成分D的合計滿足47.5莫耳%~52.5莫耳%的範圍內進行共聚合。 Next, a method of producing a polyimide precursor varnish will be described. First, the specific diamine described above is reacted with a specific tetracarboxylic dianhydride to obtain a poly-proline. The ratio of the acid dianhydride to the diamine of the polyimine precursor is not particularly limited, and is preferably a total of the diamine component A and the diamine component B with respect to the total of the diamine and the acid dianhydride. The copolymerization of 47.5 mol% to 52.5 mol% is satisfied, and the total of the acid dianhydride component C and the acid dianhydride component D satisfies the range of 47.5 mol% to 52.5 mol%.

聚合亦可藉由固相系進行，但較佳為藉由液相系進行。液相系中，聚合濃度例如設為20質量%~30質量%左右。反應溶劑並無特別限定，較佳為沸點為100℃以上者。通常，可較佳地利用聚醯亞胺前驅物的聚合時所用的溶劑。例如將至少一種反應物質、較佳為酸二酐類與二胺類這兩種溶解者。具體而言，可列舉：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、甲酚、二甲基亞碸、N-甲基-2-吡咯烷酮、四甲基脲等。這些溶劑類可單獨使用，或者亦可藉由與苯甲腈、二噁烷、二甲苯或甲苯等其他溶劑的組合而使用。 The polymerization can also be carried out by a solid phase system, but is preferably carried out by a liquid phase system. In the liquid phase system, the polymerization concentration is, for example, about 20% by mass to 30% by mass. The reaction solvent is not particularly limited, and is preferably one having a boiling point of 100 ° C or higher. In general, a solvent used in the polymerization of the polyimide precursor is preferably used. For example, at least one of the reactants, preferably an acid dianhydride and a diamine, is dissolved. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, cresol, dimethyl hydrazine, N-methyl-2-pyrrolidone, tetramethyl Urea, etc. These solvents may be used singly or in combination with other solvents such as benzonitrile, dioxane, xylene or toluene.

聚醯亞胺前驅物的製造中，可不使用觸媒而進行，但亦可適當使用觸媒。觸媒只要不脫離本發明的宗旨，則並無特別限制。另外，觸媒的使用量考慮觸媒的揮散性或酸強度等觸媒自身的性質、反應條件，進行適當調整即可。 In the production of the polyimide precursor, the catalyst may be used without using a catalyst, but a catalyst may be suitably used. The catalyst is not particularly limited as long as it does not deviate from the gist of the present invention. In addition, the amount of the catalyst to be used may be appropriately adjusted in consideration of the properties of the catalyst itself such as the dispersibility of the catalyst or the acid strength, and the reaction conditions.

液相反應步驟中，原料、溶劑及根據需要而添加的其他觸媒等的投入順序、方法並無特別限定。反應溫度只要可獲得必 需的數量平均分子量(Mn)即可，並無特別限制，但將作為聚醯亞胺前驅物的聚醯胺酸進行聚合時，通常為20℃以上、100℃以下。反應時間只要為對獲得必需的聚合度而言充分的範圍內，則並無特別限定。另外，反應時較佳為於氮氣等惰性氣體環境下進行。反應系內(反應機內)的固體成分濃度並無特別限定，通常為5質量%以上~50質量%以下。 In the liquid phase reaction step, the order and method of introducing the raw materials, the solvent, and other catalysts added as needed are not particularly limited. As long as the reaction temperature is available The number average molecular weight (Mn) to be used is not particularly limited, but when the polyamic acid which is a polyimide precursor is polymerized, it is usually 20° C. or higher and 100° C. or lower. The reaction time is not particularly limited as long as it is within a range sufficient to obtain a necessary degree of polymerization. Further, the reaction is preferably carried out under an inert gas atmosphere such as nitrogen. The solid content concentration in the reaction system (in the reactor) is not particularly limited, but is usually 5% by mass or more and 50% by mass or less.

反應裝置並無特別限定，可列舉：高速混合機(住友重機械工業公司製造)、愛工化學混合機(愛工舍製作所公司製造)、行星式混合機(井上製作所公司製造)、氦氮氧混合機(trimix)(井上製作所公司製造)等混練機。 The reaction apparatus is not particularly limited, and examples thereof include a high-speed mixer (manufactured by Sumitomo Heavy Industries, Ltd.), a AI chemical mixer (manufactured by Aijo Co., Ltd.), a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.), and a nitrogen-oxygen mixer. (trimix) (manufactured by Inoue Co., Ltd.) and other kneading machines.

就提高塗敷性的觀點等而言，聚醯亞胺前驅物清漆中的樹脂固體成分的濃度較佳為5質量%~50質量%，更佳為10質量%~30質量%。溶劑並無特別限定，較佳為極性溶劑。極性溶劑的例子除了N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基甲醯胺、N,N-二乙基乙醯胺、N,N-二甲基甲氧基乙醯胺、二甲基亞碸、六甲基磷醯胺、N-甲基-2-吡咯烷酮、二甲基碸等外，亦包括：這些的2種以上的混合溶劑，或這些溶劑與作為非極性溶劑的苯、甲苯、二甲苯、苯甲腈、二噁烷、環己烷、1,3,5-三甲基苯、1,2,4-三甲基苯等的混合溶劑等。 The concentration of the resin solid content in the polyimide intermediate varnish is preferably from 5% by mass to 50% by mass, and more preferably from 10% by mass to 30% by mass, from the viewpoint of improving the coating property. The solvent is not particularly limited, and is preferably a polar solvent. Examples of polar solvents other than N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N , N-dimethylmethoxyacetamide, dimethyl hydrazine, hexamethylphosphoniumamine, N-methyl-2-pyrrolidone, dimethyl hydrazine, etc., including: two or more of these Mixed solvent, or these solvents and benzene, toluene, xylene, benzonitrile, dioxane, cyclohexane, 1,3,5-trimethylbenzene, 1,2,4-tris as a non-polar solvent a mixed solvent such as methylbenzene.

本發明的聚醯亞胺前驅物清漆在不脫離本發明的宗旨的範圍內，可添加任意的添加劑。例如可添加黏接助劑、黏接劑、抗氧化劑、紫外線吸收劑、著色劑等。另外，亦可添加矽烷偶合 劑等表面改質劑等。作為較佳的添加劑，可例示環氧、雙順丁烯二醯亞胺、耐地醯亞胺。就耐熱性與反應性的觀點而言，較佳為添加分子量為600以下的雙順丁烯二醯亞胺。本發明的聚醯亞胺前驅物可為單一種類，亦可混合使用多種。而且，本發明的聚醯亞胺前驅物清漆在不脫離本發明的宗旨的範圍內，可混合與本發明的聚醯亞胺前驅物不同的聚合物。即，在由聚醯亞胺前驅物清漆而得的聚醯亞胺樹脂中，在不脫離本發明的宗旨的範圍內，可包含其他聚合物。另外，在聚醯亞胺前驅物清漆中，亦可包含經部分醯亞胺化者。 The polyamidene precursor varnish of the present invention may be added with any additives without departing from the gist of the present invention. For example, an adhesion aid, an adhesive, an antioxidant, an ultraviolet absorber, a colorant, or the like can be added. In addition, decane coupling can also be added. Surface modifiers such as agents. Preferred examples of the additive include epoxy, bis-methyleneimine, and ruthenium imide. From the viewpoint of heat resistance and reactivity, it is preferred to add a bis-n-butyleneimine having a molecular weight of 600 or less. The polyimine precursor of the present invention may be used in a single type or in combination of a plurality of types. Further, the polyamidene precursor varnish of the present invention may be blended with a polymer different from the polyimine precursor of the present invention within the range not departing from the gist of the present invention. That is, in the polyimine resin obtained from the polyimide varnish varnish, other polymers may be contained within a range not departing from the gist of the present invention. In addition, in the polyamidene precursor varnish, a part of the ruthenium iodide may also be included.

先前的聚醯亞胺樹脂中，通常源自醯亞胺基，因此吸水率超過2.0%。因此，例如在應用聚醯亞胺樹脂作為絕緣電線的導體的絕緣被覆材時，存在因絕緣被覆材導致傳輸損失變大的問題。另外，先前的聚醯亞胺樹脂中，存在於高濕熱下因吸水而容易產生絕緣性不良的問題。 In the prior polyimine resin, it is usually derived from a quinone imine group, and thus the water absorption rate exceeds 2.0%. Therefore, for example, when an insulating covering material of a conductor of an insulated electric wire is used as the conductor of the insulated electric wire, there is a problem that the transmission loss increases due to the insulating covering material. Further, in the conventional polyimide resin, there is a problem in that it is likely to cause poor insulation due to water absorption under high-humidity heat.

藉由採用如上述專利文獻1的聚醯亞胺結構體，而可相 對降低醯亞胺基密度而改善吸水率。然而，由此會導致玻璃轉移溫度變低，因此在耐熱性方面存在課題。如此，聚醯亞胺樹脂中於低吸水性與耐熱性具有折衷(trade off)的關係，而難以滿足低吸水性與耐熱性這兩者。另外，如專利文獻1般藉由熔融擠出成形法進行成形加工時，通常需要在400℃以上的高溫下成形，而與樹脂的熱分解溫度接近，因此需要精密地控制成形條件。 By using the polyimine structure of Patent Document 1 as described above, the phase can be phased Improves water absorption by reducing the density of quinone imine groups. However, this causes the glass transition temperature to become low, and thus there is a problem in heat resistance. As described above, in the polyimide resin, there is a trade off relationship between low water absorbability and heat resistance, and it is difficult to satisfy both of low water absorbability and heat resistance. Further, when molding is performed by a melt extrusion molding method as in Patent Document 1, it is usually necessary to form at a high temperature of 400 ° C or higher, and the thermal decomposition temperature of the resin is close to each other. Therefore, it is necessary to precisely control the molding conditions.

根據本發明的聚醯亞胺前驅物清漆，可藉由在上述的聚 醯亞胺膜中將玻璃轉移溫度設為290℃以上、吸水率設為2.0%以下、拉伸斷裂伸長率設為55%以上，而提供兼具低吸水性與高玻璃轉移溫度、高機械強度且平衡優異的聚醯亞胺樹脂。更詳細而言，藉由將玻璃轉移溫度設為290℃以上，而可實現高溫環境下亦優異的可靠性、及耐久性。例如即便在250℃左右的環境中亦可長期使用。另外，藉由將吸水率設為2.0%以下，而可在用作被覆導體的絕緣被覆材時實現低傳輸損失化。另外，可改善在高濕度下容易產生絕緣不良的問題。而且，藉由將拉伸斷裂伸長率設為55%以上，而可實現優異的機械強度，並實現優異的可靠性、耐久性。另外，藉由將拉伸斷裂伸長率設為55%以上，而撓性優異。另外，根據塗佈本發明的聚醯亞胺前驅物清漆的方法，而具有可於400℃以下加熱乾燥，而且容易薄膜化的優異的優點。 Polyimine precursor varnish according to the present invention, which can be polymerized by the above The yttrium imide film has a glass transition temperature of 290° C. or higher, a water absorption ratio of 2.0% or less, and a tensile elongation at break of 55% or more, thereby providing both low water absorption, high glass transition temperature, and high mechanical strength. And a well-balanced polyimide resin. More specifically, by setting the glass transition temperature to 290 ° C or higher, it is possible to achieve excellent reliability and durability in a high-temperature environment. For example, it can be used for a long time even in an environment of about 250 °C. In addition, by setting the water absorption rate to 2.0% or less, it is possible to achieve low transmission loss when used as an insulating coating material for a coated conductor. In addition, the problem of easily causing poor insulation under high humidity can be improved. Further, by setting the tensile elongation at break to 55% or more, excellent mechanical strength can be achieved, and excellent reliability and durability can be achieved. Moreover, it is excellent in flexibility by setting the tensile elongation at break to 55% or more. Moreover, according to the method of applying the polyimine precursor varnish of the present invention, it has an excellent advantage that it can be dried by heating at 400 ° C or lower and is easily thinned.

作為聚醯亞胺前驅物，使用上述特定結構的二胺、且使用上述特定結構的酸二酐，藉此可容易提供具有兼具低吸水性與高玻璃轉移溫度、高機械強度且平衡優異的上述效果的聚醯亞胺樹脂。作為酸二酐，導入化學式(3)的均苯四甲酸二酐、或均苯四甲酸二酐與化學式(4)，且使用化學式(1)、化學式(2)的二胺，藉此在製成聚醯亞胺樹脂時，可實現剛直化並降低醯亞胺基密度，且提高結晶性。作為其結果，考察認為成功取得了低吸水性與高玻璃轉移溫度、高機械強度的平衡。且，根據所得的聚醯亞胺樹脂，亦有可實現低介電常數性的優異的優點。 As the polyimine precursor, the diamine of the above specific structure is used, and the acid dianhydride of the above specific structure is used, whereby it is easy to provide the balance of low water absorption, high glass transition temperature, high mechanical strength, and excellent balance. The above effect of the polyimide resin. The acid dianhydride is introduced into the pyromellitic dianhydride of the chemical formula (3) or the pyromellitic dianhydride and the chemical formula (4), and the diamine of the chemical formula (1) or the chemical formula (2) is used. When it is incorporated into a quinone imine resin, it is possible to achieve straightening and reduce the density of the quinone imine group, and to improve crystallinity. As a result, it was considered that the balance between low water absorption, high glass transition temperature, and high mechanical strength was successfully obtained. Further, according to the obtained polyimine resin, there is an advantage that it is excellent in low dielectric constant.

另外，若在聚醯亞胺骨架中導入以4,4'-雙(3-胺基苯氧 基)聯苯(以下為mBP)、及3,3',4,4'-聯苯四甲酸二酐(以下為s-BPDA)等聯苯結構為主體的結構，則可更有效地實現低醯亞胺基密度化、結晶性提高的效果，而且可實現因導入4,4'-二胺基二苯醚、及均苯四甲酸二酐而帶來的剛直化。因此，可更有效地取得低吸水性與高玻璃轉移溫度、高機械強度的平衡。藉此，例如作為電線被覆材時，可更有效地實現低傳輸損失化。 In addition, if 4,4'-bis(3-aminophenoxyl) is introduced into the polyimine skeleton A structure in which a biphenyl structure such as biphenyl (hereinafter referred to as mBP) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as s-BPDA) is the main component can be more effectively realized. The effect of increasing the density and crystallinity of the quinone imine group, and the straightening by the introduction of 4,4'-diaminodiphenyl ether and pyromellitic dianhydride. Therefore, the balance between low water absorption and high glass transition temperature and high mechanical strength can be more effectively achieved. Thereby, for example, when it is used as a wire covering material, it is possible to achieve low transmission loss more effectively.

另外，聚醯亞胺樹脂具有耐藥品性優異的特性。因此，具有在高溫、多濕等嚴酷的條件、或要求耐藥品性的用途中亦可使用的優異的優點。根據本發明的聚醯亞胺前驅物清漆，可提供具有優異的絕緣特性及機械強度，並兼具耐熱性與低吸水性的原材料，因此可較佳地利用於以絕緣電線等各種電子零件、耐熱膠帶、耐熱性塗料、航空宇宙用黏接劑為代表的寬廣範圍的用途。以下，對使用本發明的聚醯亞胺前驅物清漆而形成的實施形態的一例進行說明。 Further, the polyimide resin has characteristics excellent in chemical resistance. Therefore, it has an excellent advantage which can be used also in the severe conditions, such as a high temperature, and a wet, and the application which requires the chemical-resistance. According to the polyamidene precursor varnish of the present invention, it is possible to provide a raw material having excellent insulating properties and mechanical strength and having both heat resistance and low water absorption. Therefore, it can be preferably used for various electronic parts such as insulated wires. A wide range of applications represented by heat-resistant tapes, heat-resistant coatings, and aerospace adhesives. Hereinafter, an example of an embodiment formed by using the polyimine precursor varnish of the present invention will be described.

[絕緣電線]圖1A是表示本發明的絕緣電線的一例的示意性剖面圖。絕緣電線1具有導體10、及藉由絕緣被覆材而形成的絕緣被覆層20。導體10只要可發揮出作為電線的功能即可，並無特別限定，例如包含：無氧銅、銅、鋁、鋁合金、或這些的組合等金屬等導電材料。絕緣被覆層20被覆導體10，包含使用聚醯亞胺前驅物清漆而形成的聚醯亞胺樹脂。在導體10與絕緣被覆層20之間，可設置使這些的接合變得良好的密接層。在圖1A的例子中，表示絕緣被覆層20由1層聚醯亞胺樹脂形成的例子，但如 圖1B所示般，可為包含第1絕緣被覆層21、第2絕緣被覆層22等2層的積層結構的絕緣被覆層20，亦可為3層以上的積層結構。在進行多層積層時，可積層多層的使用本發明的聚醯亞胺前驅物清漆而形成的聚醯亞胺樹脂，亦可製成其他絕緣層與本發明的聚醯亞胺樹脂的積層體。其他絕緣層並無特別限定，例如可根據需求適當設計與導體10的密接性提高的材料、或柔軟性高的材料等。 [Insulated Wire] FIG. 1A is a schematic cross-sectional view showing an example of an insulated wire of the present invention. The insulated wire 1 has a conductor 10 and an insulating coating layer 20 formed by insulating a covering material. The conductor 10 is not particularly limited as long as it can function as an electric wire, and includes, for example, a conductive material such as oxygen-free copper, copper, aluminum, an aluminum alloy, or a combination of these. The insulating coating layer 20 covers the conductor 10 and contains a polyimide resin formed using a polyimide varnish. An adhesion layer for facilitating the bonding between the conductor 10 and the insulating coating layer 20 can be provided. In the example of Fig. 1A, an example in which the insulating coating layer 20 is formed of one layer of polyimide resin is shown, but As shown in FIG. 1B, the insulating coating layer 20 having a laminated structure including two layers of the first insulating coating layer 21 and the second insulating coating layer 22 may have a laminated structure of three or more layers. In the case of multi-layer lamination, a multilayered polyimine resin formed using the polyimine precursor varnish of the present invention may be a laminate of another insulating layer and the polyimine resin of the present invention. The other insulating layer is not particularly limited. For example, a material having improved adhesion to the conductor 10 or a material having high flexibility can be appropriately designed according to requirements.

絕緣被覆層20的厚度可根據用途進行任意設定，並無特別限定，例如可設為1 μm~100 μm左右。絕緣被覆層20的更佳的下限值為10 μm以上，尤佳的範圍為20 μm以上。絕緣被覆層20可藉由在導體10上塗佈聚醯亞胺前驅物清漆進行乾燥、燒接而得。塗佈方法並無特別限定，可例示直接或間地接塗佈於導體10的外周的方法。藉由燒接，而自聚醯亞胺前驅物轉變為聚醯亞胺。在積層多層絕緣被覆層時，可藉由重複進行塗佈、燒接步驟而形成。在積層聚醯亞胺樹脂層以外的絕緣被覆層時，可適當利用公知的形成方法。 The thickness of the insulating coating layer 20 can be arbitrarily set according to the use, and is not particularly limited, and can be, for example, about 1 μm to 100 μm. A more preferable lower limit value of the insulating coating layer 20 is 10 μm or more, and a more preferable range is 20 μm or more. The insulating coating layer 20 can be obtained by drying and baking by coating a polyimide 10 on a conductor 10 with a polyimide varnish. The coating method is not particularly limited, and a method of applying directly or indirectly to the outer periphery of the conductor 10 can be exemplified. By polycondensation, the polyimine precursor is converted to polyimine. When the multilayer insulating coating layer is laminated, it can be formed by repeating the coating and baking steps. In the case of laminating an insulating coating layer other than the polyimide layer, a known forming method can be suitably employed.

燒接步驟並無特別限定，較佳為在惰性氣體中進行，例如可在氮氣環境化進行。加熱條件若為可自聚醯亞胺前驅物轉變為聚醯亞胺的條件，則並無特別限定，例如可列舉：於200℃~400℃左右加熱1分鐘~10小時的範圍的例子。另外，上述導體10、絕緣被覆層20表示剖面具有圓形狀剖面的例子，並無特別限定，亦可分別獨立為矩形形狀、橢圓形狀等。 The calcination step is not particularly limited, and it is preferably carried out in an inert gas, for example, it can be carried out under nitrogen atmosphere. The heating condition is not particularly limited as long as it can be converted from a polyimine precursor to a polyimine. For example, an example of heating at a temperature of from 200 ° C to 400 ° C for 1 minute to 10 hours is exemplified. In addition, the conductor 10 and the insulating coating layer 20 are examples in which the cross section has a circular cross section, and are not particularly limited, and may be independently a rectangular shape, an elliptical shape, or the like.

根據本發明的絕緣電線，由於絕緣被覆層20的至少一 層使用由本發明的聚醯亞胺前驅物清漆而得的聚醯亞胺樹脂，因此機械強度優異。因此，即便受到強外力作用，亦可恰當保護內部的導體10。另外，本發明的聚醯亞胺樹脂由於低吸水性優異，因此在用作絕緣電線1時，可實現低傳輸損失化。而且，本發明的聚醯亞胺樹脂由於耐藥品性、耐熱性亦優異，因此亦可於高溫、高濕度下等嚴酷的條件下較佳地利用。 The insulated wire according to the present invention is at least one of the insulating coating layer 20 The layer is a polyimine resin obtained from the phthalocyanine precursor varnish of the present invention, and thus is excellent in mechanical strength. Therefore, even if it is subjected to a strong external force, the inner conductor 10 can be properly protected. Further, since the polyimide resin of the present invention is excellent in low water absorbability, when used as the insulated electric wire 1, low transmission loss can be achieved. Further, since the polyimide resin of the present invention is excellent in chemical resistance and heat resistance, it can be preferably used under severe conditions such as high temperature and high humidity.

[耐熱膠帶]圖2是表示本發明的耐熱膠帶的一例的示意性剖面圖。耐熱膠帶2具備：支撐基材30、及接合層31。在支撐基材30與接合層31之間可設置將這些的接合強化的中間層等。耐熱膠帶2例如為了確保在200℃左右的高溫區域亦可使用的耐熱性，而支撐基材30、接合層31使用具有耐熱性者。 [Heat-Resistant Tape] FIG. 2 is a schematic cross-sectional view showing an example of the heat-resistant tape of the present invention. The heat resistant tape 2 includes a support base material 30 and a bonding layer 31. An intermediate layer or the like which strengthens the bonding of these may be provided between the support substrate 30 and the bonding layer 31. For example, in order to ensure heat resistance which can be used in a high temperature region of about 200 ° C, the heat-resistant tape 2 is used for the support substrate 30 and the bonding layer 31 to have heat resistance.

支撐基材30至少具備：由本發明的聚醯亞胺前驅物清漆形成的聚醯亞胺樹脂層。支撐基材30可包含單層或多層的聚醯亞胺樹脂層，亦可為包含其他材料的層與聚醯亞胺樹脂層的積層體。其他材料只要不脫離本發明的宗旨，則並無特別限定，例如可列舉：鋁箔等金屬箔或金屬層、塑膠膜等。較佳為與由本發明的聚醯亞胺前驅物清漆形成的聚醯亞胺樹脂層的接合性優異、且耐熱性亦優異者。 The support substrate 30 is provided with at least a polyimide film having a polyamidene precursor varnish of the present invention. The support substrate 30 may include a single layer or a plurality of layers of a polyimide resin layer, or may be a laminate of a layer containing another material and a polyimide layer. Other materials are not particularly limited as long as they do not deviate from the gist of the present invention, and examples thereof include a metal foil such as an aluminum foil, a metal layer, and a plastic film. It is preferable that the polyimide polyimide resin layer formed of the polyamidene precursor varnish of the present invention is excellent in adhesion and excellent in heat resistance.

接合層31可與被黏接體接合，若為不脫離本發明的宗旨者，則並無特別限定，通常使用黏著層。作為接合層31的較佳的例子，可列舉：矽酮系黏著劑、橡膠系黏著劑、及丙烯酸系黏著劑。就提高接合層31的耐熱性的觀點而言，較佳為熱硬化性。 The bonding layer 31 can be bonded to the adherend, and is not particularly limited as long as it does not deviate from the gist of the present invention, and an adhesive layer is usually used. Preferable examples of the bonding layer 31 include an anthrone-based adhesive, a rubber-based adhesive, and an acrylic adhesive. From the viewpoint of improving the heat resistance of the bonding layer 31, it is preferably thermosetting.

耐熱膠帶2的厚度或尺寸可根據各種用途進行適當設計。例如支撐基材30的厚度較佳為2 μm~100 μm左右。支撐基材30的下限值更佳為5 μm以上，尤佳為10 μm以上。另外，支撐基材30的上限值更佳為50 μm以下，尤佳為30 μm以下。接合層31的厚度例如可設為3 μm~100 μm左右。藉由調整支撐基材30與接合層31的厚度，而可調整黏著力。根據所要求的用途，而適當選擇厚度或接合層的材料、積層形態，從而可提供追隨性優異的耐熱膠帶、或剛性高的耐熱膠帶。 The thickness or size of the heat-resistant tape 2 can be appropriately designed according to various uses. For example, the thickness of the support substrate 30 is preferably about 2 μm to 100 μm. The lower limit of the support substrate 30 is more preferably 5 μm or more, and particularly preferably 10 μm or more. Further, the upper limit of the support base material 30 is more preferably 50 μm or less, and particularly preferably 30 μm or less. The thickness of the bonding layer 31 can be, for example, about 3 μm to 100 μm. The adhesion can be adjusted by adjusting the thickness of the support substrate 30 and the bonding layer 31. Depending on the intended use, the thickness or the material of the bonding layer or the laminated form can be appropriately selected to provide a heat-resistant tape excellent in followability or a heat-resistant tape having high rigidity.

耐熱膠帶2可藉由各種方法製造，可例示以下的方法。即，藉由在進行旋轉的支撐體上成膜狀地連續擠出或塗佈聚醯亞胺前驅物清漆而獲得凝膠膜。繼而，藉由自上述支撐體剝離凝膠膜，並進行延伸、乾燥、熱處理，而進行醯亞胺化而獲得支撐基材30。然後，於其上藉由先前公知的塗佈方法形成接合層31。塗敷方法並無特別限定，例如可例示：輥塗法、逆輥塗佈法、凹版輥法、棒塗法、缺角輪塗佈法、模塗法等。經塗敷的黏著劑的乾燥條件根據所用的黏著劑進行適當調整即可，通常在80℃~200℃的溫度範圍內乾燥10秒~10分鐘。 The heat-resistant tape 2 can be produced by various methods, and the following methods can be exemplified. That is, a gel film is obtained by continuously extruding or coating a polyimide film precursor varnish in a film form on a rotating support. Then, the support substrate 30 is obtained by exfoliating the gel film from the support, stretching, drying, and heat treatment to carry out hydrazine imidization. Then, the bonding layer 31 is formed thereon by a previously known coating method. The coating method is not particularly limited, and examples thereof include a roll coating method, a reverse roll coating method, a gravure roll method, a bar coating method, a notch wheel coating method, and a die coating method. The drying conditions of the applied adhesive may be appropriately adjusted depending on the adhesive to be used, and are usually dried in a temperature range of 80 ° C to 200 ° C for 10 seconds to 10 minutes.

另外，本發明中所謂的凝膠膜，是包含將聚醯亞胺前驅物及/或經部分醯亞胺化的聚醯亞胺樹脂混合而成的聚醯亞胺前驅物、與溶劑的膜。凝膠膜例如有膜厚為1 μm~100 μm左右、溶劑含量為1質量%~70質量%左右者。 Further, the gel film in the present invention is a film comprising a polyimine imine precursor obtained by mixing a polyimide precursor and/or a partially fluorinated polyimine resin, and a solvent. . The gel film has, for example, a film thickness of about 1 μm to 100 μm and a solvent content of about 1% by mass to 70% by mass.

另外，耐熱膠帶2並不限定於圖2的例子，可取各種形 態。例如可製成在支撐基材30的雙面設置接合層的雙面膠帶。另外，亦可設為在接合層31的上層積層剝離膜、在使用時將剝離膜剝離的構成。另外，亦可製成輥狀耐熱膠帶。另外，本發明的耐熱膠帶2的尺寸並無特別限定，除了細帶狀的所謂膠帶狀的形態外，亦包括片狀者。另外，亦可不設置接合層31而將由聚醯亞胺前驅物清漆而得的凝膠膜自身用作耐熱膠帶2。 In addition, the heat-resistant tape 2 is not limited to the example of FIG. 2, and various shapes are available. state. For example, a double-sided tape in which a bonding layer is provided on both sides of the support substrate 30 can be produced. In addition, it is also possible to adopt a configuration in which a release film is laminated on the upper layer of the bonding layer 31 and the release film is peeled off during use. In addition, a roll-shaped heat-resistant tape can also be produced. Further, the size of the heat-resistant tape 2 of the present invention is not particularly limited, and includes a sheet-like shape in addition to a tape-like shape in the form of a thin strip. Further, the gel film obtained by varnishing the polyimide film precursor may be used as the heat-resistant tape 2 without providing the bonding layer 31.

根據本發明的耐熱膠帶，由於使用由本發明的聚醯亞胺前驅物清漆而得的聚醯亞胺樹脂，因此絕緣特性及機械強度優異，而且兼具耐熱性與低吸水性這兩者。此外，耐藥品性、耐候性亦優異。另外，由於撓性亦優異，因此可應用於各種各樣的形狀的被黏接體。因此，例如適合作為在熱輥或加熱器等熱設備中所用的遮蔽、加溫加壓條件下所用的構件的電絕緣、半導體製造製程領域中印刷基板等的保護膠帶。 According to the heat-resistant adhesive tape of the present invention, since the polyimide resin obtained from the polyimide varnish of the present invention is used, it is excellent in insulating properties and mechanical strength, and has both heat resistance and low water absorbability. In addition, it is excellent in chemical resistance and weather resistance. Moreover, since it is excellent in flexibility, it can be applied to the to-be-bonded body of various shapes. For this reason, for example, it is suitable as a protective tape for a member used for shielding, heating and pressurizing conditions used in a thermal device such as a heat roller or a heater, and a printed circuit board for printing a substrate or the like in the field of semiconductor manufacturing processes.

[耐熱塗料]對使用本發明的聚醯亞胺前驅物清漆作為耐熱塗料的例子進行說明。本發明的耐熱塗料根據需要可包含顏料。顏料的種類在不脫離本發明的宗旨的範圍內並無特別限定，作為一例，可列舉：碳黑、磷酸鋅、磷酸鋁、磷酸鈣、磷酸鎂、鉬酸鋅、鉬酸鈣、矽砂、碳酸鈣、滑石、黏土、高嶺土、沈積性硫酸鋇等。較佳為具有耐熱性、耐蝕性的防蝕顏料。另外，本發明的耐熱塗料中，在不脫離本發明的宗旨的範圍內，可添加任意其他的添加劑。例如可例示：加強材、硬化劑、瀝青乳劑、造膜助劑、消泡劑、分散劑、增黏劑、塑化劑、防腐劑、防菌劑、防 銹劑、著色劑等。 [Heat Resistant Coating] An example in which the polyamidene precursor varnish of the present invention is used as a heat resistant coating will be described. The heat resistant coating of the present invention may contain a pigment as needed. The type of the pigment is not particularly limited as long as it does not deviate from the gist of the present invention, and examples thereof include carbon black, zinc phosphate, aluminum phosphate, calcium phosphate, magnesium phosphate, zinc molybdate, calcium molybdate, and strontium sand. Calcium carbonate, talc, clay, kaolin, sedimentary barium sulfate, and the like. An anticorrosive pigment having heat resistance and corrosion resistance is preferred. Further, in the heat-resistant paint of the present invention, any other additives may be added without departing from the gist of the present invention. For example, reinforcing materials, hardeners, asphalt emulsions, film forming aids, defoamers, dispersants, tackifiers, plasticizers, preservatives, antibacterial agents, and anti-bacterial agents can be exemplified. Rust, coloring agent, etc.

耐熱塗料中，在不脫離本發明的宗旨的範圍內，可添加聚醯亞胺前驅物以外的樹脂。聚醯亞胺前驅物以外的樹脂可為熱塑性樹脂、熱硬化性樹脂的任一種，但就耐熱性的觀點而言，較佳為熱硬化性樹脂。 In the heat-resistant paint, a resin other than the polyimide precursor may be added without departing from the gist of the present invention. The resin other than the polyimide precursor may be either a thermoplastic resin or a thermosetting resin, but from the viewpoint of heat resistance, a thermosetting resin is preferred.

本發明的耐熱塗料的固體成分濃度若可形成塗膜，則並無特別限定，較佳為10質量%~70質量%左右。在固體成分濃度小於10質量%時，厚膜塗裝性降低，若固體成分濃度超過70質量%，則在調配時作業性、或儲存穩定性等方面容易產生問題。 The solid content concentration of the heat-resistant paint of the present invention is not particularly limited as long as it can form a coating film, and is preferably about 10% by mass to 70% by mass. When the solid content concentration is less than 10% by mass, the thick film coating property is lowered, and when the solid content concentration is more than 70% by mass, workability, storage stability, and the like are likely to cause problems in preparation.

本發明的耐熱塗料的塗裝方法例如可例示：將上述聚醯亞胺前驅物清漆塗敷於被塗裝面，在可自聚醯亞胺前驅物轉變為聚醯亞胺的條件下進行加熱處理的方法。作為被塗裝面，可應用金屬材料、陶瓷材料、塑膠材料等各種材料。為了提高與被塗裝面的密接性，可預先對被塗裝面實施電漿處理、噴射處理等表面處理，或形成底塗層。 The coating method of the heat-resistant paint of the present invention can be exemplified by applying the above-mentioned polyimide pigment precursor varnish to the surface to be coated, and heating it under the condition that the polyimide precursor can be converted into a polyimide. The method of processing. As the coated surface, various materials such as a metal material, a ceramic material, and a plastic material can be applied. In order to improve the adhesion to the surface to be coated, the surface to be coated may be subjected to surface treatment such as plasma treatment or blast treatment in advance, or an undercoat layer may be formed.

耐熱塗料的皮膜可藉由利用加熱處理進行醯亞胺化的方法而得，塗敷方法可不受限地利用公知的方法。例如可例示：藉由塗佈法、浸漬法、噴霧法、刷毛塗佈法等而形成塗膜的方法。加熱處理條件若可自聚醯亞胺前驅物轉變為聚醯亞胺，則並無特別限定，例如可藉由在200℃~400℃左右加熱1分鐘~10小時的範圍而得。可於大氣中進行，亦可於氮氣環境化等進行。經過這些步驟而可獲得耐熱皮膜。皮膜厚度根據用途進行適當設計即可。 The film of the heat-resistant paint can be obtained by a method of imidization by heat treatment, and the coating method can be carried out by any known method without limitation. For example, a method of forming a coating film by a coating method, a dipping method, a spray method, a brush coating method, or the like can be exemplified. The heat treatment conditions are not particularly limited as long as they can be converted from a polyimide precursor to a polyimide, and can be obtained, for example, by heating at a temperature of from 200 ° C to 400 ° C for a period of from 1 minute to 10 hours. It can be carried out in the atmosphere or in a nitrogenous environment. Through these steps, a heat resistant film can be obtained. The film thickness can be appropriately designed according to the use.

根據本發明的耐熱塗料，由於含有由本發明的聚醯亞胺前驅物清漆而得的聚醯亞胺樹脂作為主成分，因此可提供具有優異的絕緣特性及機械強度、且兼具耐熱性與低吸水性的耐熱皮膜。此外，耐藥品性、耐候性亦優異。另外，由於撓性亦優異，因此可用作各種各樣的形狀的被塗裝面的耐熱皮膜。具體而言，適合於電氣、電子設備，機械，汽車，航空、宇宙設備，一般產業用設備等。亦適合於暴露於高溫環境的用途。 According to the heat-resistant paint of the present invention, since the polyimine resin obtained from the polyimide varnish of the present invention is contained as a main component, it can provide excellent insulating properties and mechanical strength, and has both heat resistance and low heat resistance. Water-absorbing heat-resistant film. In addition, it is excellent in chemical resistance and weather resistance. Moreover, since it is excellent in flexibility, it can be used as a heat-resistant film of the coated surface of various shapes. Specifically, it is suitable for electrical, electronic equipment, machinery, automobiles, aviation, space equipment, general industrial equipment, and the like. Also suitable for exposure to high temperature environments.

[航空宇宙用黏接劑]對本發明的聚醯亞胺前驅物清漆、或包含本發明的聚醯亞胺樹脂的航空宇宙用黏接劑進行說明。本發明的航空宇宙黏接劑可僅包含本發明的聚醯亞胺前驅物清漆，亦可在使用二液型等其他黏接成分時進行混合。另外，航空宇宙用黏接劑還可包含將聚醯亞胺前驅物清漆的塗膜進行醯亞胺化而得的聚醯亞胺樹脂膜。 [Aerospace Cohesive Agent] The polyiminoimine precursor varnish of the present invention or the aerospace adhesive containing the polyimine resin of the present invention will be described. The aerospace adhesive of the present invention may contain only the polyimide precursor varnish of the present invention, or may be mixed when other bonding components such as a two-liquid type are used. Further, the aerospace adhesive may further comprise a polyimide film obtained by subjecting a coating film of a polyimide precursor varnish to ruthenium imidization.

航空宇宙用黏接劑的一個形態是包含聚醯亞胺前驅物清漆者。作為樹脂，在不脫離本發明的宗旨的範圍內，可添加聚醯亞胺前驅物以外的樹脂。聚醯亞胺前驅物以外的樹脂可為熱塑性樹脂、熱硬化性樹脂的任一種，但較佳為至少部分地與聚醯亞胺前驅物相溶者，就耐熱性的觀點而言，較佳為熱硬化性樹脂。作為較佳的樹脂，可列舉：環氧樹脂、雙順丁烯二醯亞胺樹脂、丙烯酸系樹脂、苯并噁唑樹脂等。 One form of aerospace adhesive is a varnish containing a polyimide precursor. As the resin, a resin other than the polyimide precursor can be added without departing from the gist of the invention. The resin other than the polyimide precursor may be any of a thermoplastic resin and a thermosetting resin, but is preferably at least partially compatible with the polyimide precursor, and is preferably heat resistance. It is a thermosetting resin. Preferred examples of the resin include an epoxy resin, a bis-xenylenediamine resin, an acrylic resin, and a benzoxazole resin.

就耐熱性優異、黏接時的流動性亦適當、膜形成性變佳的方面而言，較理想為熱硬化性樹脂的量相對於聚醯亞胺樹脂100 質量份，在較佳為1質量份~200質量份、更佳為5質量份~100質量份的範圍內使用。 The amount of the thermosetting resin is preferably relative to the polyimide resin 100 in terms of excellent heat resistance, appropriate fluidity at the time of bonding, and improved film formability. The mass part is preferably used in the range of 1 part by mass to 200 parts by mass, more preferably 5 parts by mass to 100 parts by mass.

這些熱硬化性樹脂中，市售有各種結構者，就產業上的利用範圍廣、可實現適度的硬化、交聯密度等亦可藉由調配比例進行控制的方面而言，較佳為環氧樹脂。作為環氧樹脂，若為分子內包含至少2個環氧基者，則並無特別限定。例如作為酚的縮水甘油醚型環氧樹脂，可列舉：雙酚A、雙酚AD、雙酚S、雙酚F或鹵化雙酚A與表氯醇的縮合物、苯酚酚醛清漆樹脂的縮水甘油醚、甲酚酚醛清漆樹脂的縮水甘油醚、雙酚A酚醛清漆樹脂的縮水甘油醚、二環戊二烯改質苯酚酚醛清漆樹脂的縮水甘油醚、聯苯型環氧樹脂等。 Among these thermosetting resins, those having various structures are commercially available, and it is preferably an epoxy resin in terms of industrial use, moderate hardening, crosslink density, etc., which can be controlled by blending ratio. Resin. The epoxy resin is not particularly limited as long as it contains at least two epoxy groups in the molecule. For example, as the glycidyl ether type epoxy resin of phenol, bisphenol A, bisphenol AD, bisphenol S, bisphenol F or a condensate of halogenated bisphenol A and epichlorohydrin, and glycidol of a phenol novolak resin can be mentioned. An ether, a glycidyl ether of a cresol novolak resin, a glycidyl ether of a bisphenol A novolac resin, a glycidyl ether of a dicyclopentadiene modified phenol novolak resin, a biphenyl type epoxy resin, or the like.

另外，根據需要可含有硬化劑，可列舉：酚系硬化劑、胺系硬化劑、酸酐系硬化劑、咪唑類等。而且，亦可調配無機物質填料。填料是為了對黏接劑賦予低熱膨脹性、低吸濕性、高彈性、高導熱性等而調配，並且亦有助於膜狀黏接劑的強度提高。作為無機物質填料，例如可列舉：二氧化矽、氧化鋁、氮化矽、氮化鋁、氮化硼、二氧化鈦、玻璃、氧化鐵、陶瓷等無機絕緣體。這些可單獨使用或混合使用2種以上。而且，在黏接劑中，根據需要在不損及本發明的目的的範圍內，可適當添加矽烷偶合劑、鈦系偶合劑等偶合劑。偶合劑有助於提高與被黏接體或填料的黏接界面的黏接強度。 In addition, a curing agent may be contained as needed, and examples thereof include a phenol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, and an imidazole. Moreover, an inorganic material filler can also be formulated. The filler is formulated to impart low thermal expansion, low moisture absorption, high elasticity, high thermal conductivity, etc. to the adhesive, and also contributes to an increase in the strength of the film adhesive. Examples of the inorganic material filler include inorganic insulators such as cerium oxide, aluminum oxide, cerium nitride, aluminum nitride, boron nitride, titanium oxide, glass, iron oxide, and ceramics. These can be used individually or in mixture of 2 or more types. Further, in the adhesive, a coupling agent such as a decane coupling agent or a titanium coupling agent may be appropriately added as needed within the range not impairing the object of the present invention. The coupling agent helps to improve the bonding strength to the bonding interface of the bonded body or the filler.

作為本發明的航空宇宙用黏接劑的溶劑量，並無特別限 制，通常以成為清漆具有流動性的程度的黏度的方式進行調整。通常若清漆所含的聚醯亞胺前驅物成分量為1質量%~40質量%、較佳為5質量%~35質量%、更佳為10質量%~30質量%的範圍，則於流動性或加工性、成膜性、塗敷性等方面而言為理想。另外，清漆的黏度並無特別限制，可在容易操作的範圍內進行適當選擇，而且根據需要可包含黏度調節劑等。 The amount of solvent used as the aerospace adhesive of the present invention is not particularly limited. The system is usually adjusted so as to have a viscosity at which the varnish has fluidity. Usually, if the amount of the polyimide component contained in the varnish is from 1% by mass to 40% by mass, preferably from 5% by mass to 35% by mass, more preferably from 10% by mass to 30% by mass, the flow is in the flow. It is ideal in terms of properties, workability, film formability, and coating properties. Further, the viscosity of the varnish is not particularly limited, and may be appropriately selected within a range that is easy to handle, and may include a viscosity modifier or the like as needed.

本發明的航空宇宙用黏接劑的被塗敷面並無特別限定，作為一例，可列舉：金屬材料、陶瓷材料、塑膠材料等。為了提高與被塗敷面的密接性，而可預先對被塗敷面實施電漿處理、噴射處理等表面處理、或形成底塗層。另外，航空宇宙用黏接劑可直接塗佈，並且亦可於基材膜上成形。塗膜形成方法、加熱處理方法等並無特別限定。例如可列舉：耐熱塗料的塗裝方法中所說明的例子。 The coated surface of the aerospace adhesive of the present invention is not particularly limited, and examples thereof include a metal material, a ceramic material, and a plastic material. In order to improve the adhesion to the surface to be coated, the surface to be coated may be subjected to surface treatment such as plasma treatment or blast treatment in advance or an undercoat layer may be formed. In addition, aerospace adhesives can be applied directly and can also be formed on a substrate film. The coating film forming method, the heat treatment method, and the like are not particularly limited. For example, the example demonstrated by the coating method of a heat resistant coating is mentioned.

另外，作為本發明的航空宇宙用黏接劑的其他形態，有膜狀者。在製成膜狀黏接劑時，較佳為使用上述的凝膠膜的方法。即，較佳為藉由以下方式而製造的方法：藉由在進行旋轉的支撐體上成膜狀地連續擠出或塗佈聚醯亞胺前驅物清漆而獲得凝膠膜，自上述支撐體剝離凝膠膜，並進行延伸、乾燥、熱處理。另外，亦可例示：藉由在玻璃基板上或脫模性高的聚醯亞胺膜上形成塗膜而在熱處理後進行剝離而得的方法；或者藉由將塗佈於實施了脫模處理的聚對苯二甲酸乙二酯(polyethylene terephthalate，PET)膜上的凝膠膜剝離，然後進行延伸、乾燥、 熱處理而製造的方法等。 Further, as another form of the aerospace adhesive of the present invention, there is a film shape. In the case of forming a film-like adhesive, a method of using the above-described gel film is preferred. That is, a method produced by continuously extruding or coating a polyimide film precursor varnish in a film form on a rotating support body to obtain a gel film from the support body is preferable. The gel film is peeled off, and stretched, dried, and heat-treated. In addition, a method of forming a coating film on a glass substrate or a polyimide film having a high release property and peeling it after heat treatment may be exemplified; or by applying a release treatment to the coating. The gel film on the polyethylene terephthalate (PET) film is peeled off, then stretched, dried, A method of manufacturing by heat treatment or the like.

膜狀黏接劑層的厚度亦取決於用途，例如可設為1 μm~200 μm左右。在使用膜狀黏接劑時，可夾持於被黏接物之間並進行熱壓接。壓接時的溫度較佳為高於樹脂組成物的玻璃轉移溫度，通常設為300℃~450℃、較佳為設為350℃~400℃。若為此種範圍，則聚醯亞胺組成物不會熱分解，且可進行充分的黏接。 The thickness of the film-like adhesive layer depends on the application, and can be, for example, about 1 μm to 200 μm. When a film-like adhesive is used, it can be sandwiched between the adherends and thermocompression bonded. The temperature at the time of pressure bonding is preferably higher than the glass transition temperature of the resin composition, and is usually 300 ° C to 450 ° C, preferably 350 ° C to 400 ° C. If it is such a range, a polyimide composition will not thermally decompose, and it can fully bond.

根據本發明的航空宇宙用黏接劑，由於包含由本發明的聚醯亞胺前驅物清漆而得的聚醯亞胺樹脂作為主成分，因此具有優異的絕緣特性及機械強度，並且兼具耐熱性與低吸水性。此外，耐藥品性、耐候性亦優異。另外，由於撓性亦優異，因此適合作為在嚴酷的高溫環境下、高濕度環境下使用的航空宇宙用黏接劑。 The aerospace adhesive according to the present invention has excellent insulating properties and mechanical strength and heat resistance because it contains a polyimine resin obtained from the polyamidene precursor varnish of the present invention as a main component. With low water absorption. In addition, it is excellent in chemical resistance and weather resistance. In addition, since it is excellent in flexibility, it is suitable as an aerospace adhesive for use in a severe high-temperature environment and a high-humidity environment.

≪實施例≫ ≪Example≫

以下，藉由實施例對本發明進行更詳細地說明，但本發明不受以下實施例的任何限定。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

[實施例1](聚醯亞胺前驅物清漆的製備)在二甲基乙醯胺溶劑中，將4,4'-二胺基二苯醚(和歌山精化公司製造)(以下稱為「4,4'-ODA」)、4,4'-雙(3-胺基苯氧基)聯苯(三井化學公司製造)(以下稱為「m-BP」)這2種二胺、與均苯四甲酸二酐(三菱瓦斯化學公司製造)(以下稱為「PMDA」)的酸二酐，以4,4'-ODA：mBP：PMDA=20：30：49.5的莫耳比進行調配。繼而，將混合物攪拌4小時以上而獲得樹脂固體成分比例為20質量%~25質量%的聚醯亞胺前驅物清漆。 [Example 1] (Preparation of polyimine precursor varnish) 4,4'-diaminodiphenyl ether (manufactured by Wakayama Seiki Co., Ltd.) in a solvent of dimethylacetamide (hereinafter referred to as " 4,4'-ODA"), 4,4'-bis(3-aminophenoxy)biphenyl (manufactured by Mitsui Chemicals, Inc.) (hereinafter referred to as "m-BP") The acid dianhydride of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) (hereinafter referred to as "PMDA") was formulated at a molar ratio of 4,4'-ODA:mBP:PMDA=20:30:49.5. Then, the mixture was stirred for 4 hours or more to obtain a polyimide varnish varnish having a resin solid content ratio of 20% by mass to 25% by mass.

(聚醯亞胺膜的製作)在玻璃板上藉由360 μm間隙的敷料器使用桌上塗敷機塗佈上述聚醯亞胺前驅物清漆。塗佈後，立即使用防爆型乾燥機在氮氣環境中進行乾燥。乾燥是自常溫起以5℃/min升溫，於300℃下保持1小時。然後進行自然冷卻。經充分冷卻後，在溫水中浸水24小時，藉此自玻璃板剝離聚醯亞胺膜，而獲得所期望的聚醯亞胺膜樣品。所得的聚醯亞胺膜在乾燥後的膜厚為30 μm。 (Production of Polyimine Film) The above polyimide precursor varnish was coated on a glass plate by a spreader of 360 μm gap using a table coater. Immediately after coating, it was dried in a nitrogen atmosphere using an explosion-proof dryer. The drying was carried out at a temperature of 5 ° C / min from normal temperature, and kept at 300 ° C for 1 hour. Then carry out natural cooling. After sufficiently cooling, water was immersed in warm water for 24 hours, whereby the polyimide film was peeled off from the glass plate to obtain a desired polyimide film sample. The obtained polyimide film had a film thickness of 30 μm after drying.

(吸水性評價)藉由吸水率評價所製作的膜樣品的吸水性。將對象樣品切出為50 mm×50 mm尺寸，進行150℃×5分鐘乾燥後，立即測定質量。然後，在23℃的離子交換水中浸漬24小時。浸漬後，藉由***將自水槽取出的樣品的表面所附著的水分充分地吹散後，測定質量，根據上述數式(1)算出吸水率。將吸水率為2.0%以下者設為○，將吸水率超過2.0%者設為×。 (Evaluation of Water Absorption) The water absorption of the film sample produced was evaluated by water absorption. The sample of the object was cut out to a size of 50 mm × 50 mm, and the mass was measured immediately after drying at 150 ° C for 5 minutes. Then, it was immersed in ion-exchange water at 23 ° C for 24 hours. After the immersion, the moisture adhering to the surface of the sample taken out from the water tank was sufficiently blown off by an air gun, and the mass was measured, and the water absorption rate was calculated from the above formula (1). The case where the water absorption rate is 2.0% or less is ○, and the case where the water absorption rate exceeds 2.0% is ×.

(玻璃轉移溫度評價(耐熱性評價))對藉由上述方法而製作的聚醯亞胺膜評價玻璃轉移溫度。測定是藉由固體黏彈性的溫度分散測定(拉伸模式)，評價儲存彈性模數E'與損失彈性模數E"，由損失正切tanδ=E"/E'的峰值導出玻璃轉移溫度。測定裝置是使用TA儀器公司製造的RSA-III。將玻璃轉移溫度為290℃以上者設為○，將小於290℃者設為×。 (Evaluation of Glass Transition Temperature (Evaluation of Heat Resistance)) The glass transition temperature of the polyimide film produced by the above method was evaluated. The measurement was carried out by temperature dispersion measurement (stretching mode) of solid viscoelasticity, and the storage elastic modulus E' and the loss elastic modulus E" were evaluated, and the glass transition temperature was derived from the peak of the loss tangent tan δ = E"/E'. The measuring device was an RSA-III manufactured by TA Instruments. When the glass transition temperature is 290 ° C or higher, it is ○, and when it is less than 290 ° C, it is ×.

(機械強度評價)測定所製作的聚醯亞胺膜的拉伸機械強度。將樣品切出為140 mm長度×10 mm寬度尺寸，使用兩端20 mm部分作為拉伸區域(實際的測定長度為100 mm)。以速度50 mm/min拉伸短條狀膜樣品，藉此測定拉伸斷裂伸長率。測定裝置是使用島津製作所公司製造的AUTOGRAPH AGS-100D。將拉伸斷裂伸長率(亦簡稱為「斷裂伸長率」)為55%以上者設為○，將小於55%者設為×。 (Mechanical strength evaluation) The tensile mechanical strength of the produced polyimide film was measured. The sample was cut to a width of 140 mm length × 10 mm width, and a 20 mm portion at both ends was used as the stretching area (actual measurement length was 100 mm). At speed 50 The short strip film sample was stretched by mm/min, whereby the tensile elongation at break was measured. The measuring device was an AUTOGRAPH AGS-100D manufactured by Shimadzu Corporation. The tensile elongation at break (also referred to simply as "elongation at break") is 55% or more, and is ○, and less than 55% is ×.

(介電常數評價)對藉由上述方法而製作的聚醯亞胺膜，藉由依據JIS K6911的方法，評價介電常數。使用安捷倫科技(Agilent Technology)公司製造的LCR計HP4284A，於頻率1 MHz、主電極=18 mmφ、保護電極=26 mmφ、對電極=28 mmφ的條件下，使用於22℃×60%RH下放置24小時的聚醯亞胺膜樣品，於22℃×60%RH環境下實施評價。 (Evaluation of Dielectric Constant) The dielectric constant of the polyimide film produced by the above method was evaluated by the method according to JIS K6911. Using an LCR meter HP4284A manufactured by Agilent Technologies, at a frequency of 1 MHz, a main electrode = 18 mmφ, a guard electrode = 26 mmφ, and a counter electrode = 28 mmφ, placed at 22 ° C × 60% RH A 24-hour polyimide film sample was evaluated in an environment of 22 ° C × 60% RH.

[實施例2]將作為二胺的4,4'-ODA、m-BP這2種、與作為酸二酐的PMDA，以4,4'-ODA：mBP：PMDA=25：25：49.5的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。膜厚調整為30 μm(以下的實施例、比較例中亦同樣地調整為30 μm)。 [Example 2] Two kinds of 4,4'-ODA and m-BP which are diamines, and PMDA which is an acid dianhydride, 4,4'-ODA:mBP:PMDA=25:25:49.5 A polyamidene precursor varnish was produced and evaluated in the same manner as in Example 1 except that the molar ratio was adjusted. The film thickness was adjusted to 30 μm (the same applies to the following examples and comparative examples, and was adjusted to 30 μm in the same manner).

[實施例3]將作為二胺的4,4'-ODA、m-BP這2種、與作為酸二酐的PMDA，以4,4'-ODA：mBP：PMDA=12.5：37.5：49.5的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Example 3] Two kinds of 4,4'-ODA and m-BP which are diamines, and PMDA which is an acid dianhydride, 4,4'-ODA:mBP:PMDA=12.5:37.5:49.5 A polyamidene precursor varnish was produced and evaluated in the same manner as in Example 1 except that the molar ratio was adjusted.

[實施例4]將作為二胺的4,4'-ODA、m-BP這2種、與作為酸二酐的PMDA、3,3',4,4'-聯苯四甲酸二酐(JFE化學(JFE Chemical)公司製造)(以下稱為「s-BPDA」)這2種，以4,4'-ODA： mBP：PMDA：s-BPDA=25：25：44.55：4.95的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Example 4] Two kinds of 4,4'-ODA and m-BP as diamines, and PMDA, 3,3',4,4'-biphenyltetracarboxylic dianhydride (JFE) as acid dianhydride Chemical (JFE Chemical) company (hereinafter referred to as "s-BPDA"), 2, 4'-ODA: A polyimine precursor varnish was prepared and evaluated in the same manner as in Example 1 except that the molar ratio of mBP:PMDA:s-BPDA=25:25:44.55:4.95 was adjusted.

[實施例5]將作為二胺的4,4'-ODA、m-BP這2種、與作為酸二酐的PMDA、s-BPDA這2種，以4,4'-ODA：mBP：PMDA：s-BPDA=25：25：35：14.5的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Example 5] Two kinds of 4,4'-ODA and m-BP which are diamines, and two types of PMDA and s-BPDA which are acid dianhydrides, 4,4'-ODA:mBP:PMDA A polyamidene precursor varnish was prepared and evaluated in the same manner as in Example 1 except that the molar ratio of s-BPDA=25:25:35:14.5 was adjusted.

[實施例6]將作為二胺的4,4'-ODA、m-BP、1,3-雙(4-胺基苯氧基)苯(日本純良藥品公司製造、以下稱為4-APB)這3種、與作為酸二酐的PMDA、s-BPDA這2種，以4,4'-ODA：mBP：4-APB：PMDA：s-BPDA=10：25：15：35：14.5的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Example 6] 4,4'-ODA, m-BP, and 1,3-bis(4-aminophenoxy)benzene as a diamine (manufactured by Nippon Pure Pharmaceutical Co., Ltd., hereinafter referred to as 4-APB) These three kinds, with PMDA and s-BPDA as acid dianhydride, are 4,4'-ODA:mBP:4-APB:PMDA:s-BPDA=10:25:15:35:14.5 A polyimide polyimide precursor varnish was produced and evaluated in the same manner as in Example 1 except that the ear ratio was adjusted.

[比較例1]將作為二胺的4,4'-ODA、與作為酸二酐的PMDA，以4,4'-ODA：PMDA=50：49.5的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Comparative Example 1] 4,4'-ODA as a diamine and PMDA as an acid dianhydride were blended at a molar ratio of 4,4'-ODA:PMDA=50:49.5, and In the same manner as in Example 1, a polyimide varnish precursor varnish was produced and evaluated.

[比較例2]將作為二胺的m-BP、與作為酸二酐的PMDA，以m-BP：PMDA=50：49.5的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Comparative Example 2] The same procedure as in Example 1 except that m-BP as a diamine and PMDA as an acid dianhydride were blended in a molar ratio of m-BP:PMDA=50:49.5. In a manner, a polyamidene precursor varnish was produced and evaluated.

[比較例3]將作為二胺的4,4'-ODA、m-BP這2種、與作為酸二酐的PMDA、s-BPDA這2種，以4,4'-ODA：mBP：PMDA： s-BPDA=25：25：24.5：25的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Comparative Example 3] Two kinds of 4,4'-ODA and m-BP which are diamines, and two types of PMDA and s-BPDA which are acid dianhydrides, 4,4'-ODA:mBP:PMDA : A polyamidene precursor varnish was prepared and evaluated in the same manner as in Example 1 except that the molar ratio of s-BPDA=25:25:24.5:25 was adjusted.

[比較例4]將作為二胺的4,4'-(間苯二亞異丙基)二苯胺(三井精細化學(Mitsui Fine Chemicals)公司製造)(以下稱為「雙苯胺M」)、m-BP這2種、與作為酸二酐的PMDA，以雙苯胺M：mBP：PMDA=25：25：49.5的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Comparative Example 4] 4,4'-(m-phenylene isopropylidene)diphenylamine (manufactured by Mitsui Fine Chemicals Co., Ltd.) (hereinafter referred to as "diphenylamine M") as a diamine, m In the same manner as in Example 1, except that the two types of -BP were mixed with PMDA as an acid dianhydride in a molar ratio of bisaniline M:mBP:PMDA=25:25:49.5. The quinone imine precursor varnish was evaluated.

[比較例5]將2,2'-二甲基-4,4'-二胺基聯苯(和歌山精化公司製造)(以下稱為「間聯甲苯胺」)、m-BP這2種、與作為酸二酐的PMDA，以間聯甲苯胺：mBP：PMDA=25：25：49.5的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Comparative Example 5] 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seiki Co., Ltd.) (hereinafter referred to as "m-toluidine") and m-BP A polyimine precursor was produced in the same manner as in Example 1 except that PMDA as an acid dianhydride was blended with a molar ratio of m-toluidine:mBP:PMDA=25:25:49.5. Varnish and evaluation.

[比較例6]將作為二胺的4,4'-ODA、m-BP這2種、與作為酸二酐的PMDA這1種，以4,4'-ODA：mBP：PMDA=7.5：42.5：49.5的莫耳比進行調配，除此以外，以與實施例1相同的方式，製作聚醯亞胺前驅物清漆，並評價。 [Comparative Example 6] 4 kinds of 4,4'-ODA and m-BP which are diamines, and PMDA which is an acid dianhydride, 4,4'-ODA:mBP:PMDA=7.5:42.5 A polyamidene precursor varnish was prepared and evaluated in the same manner as in Example 1 except that the molar ratio of 49.5 was adjusted.

表1表示聚醯亞胺酸清漆的製備比率，表2表示物性值的結果。 Table 1 shows the preparation ratio of the polyamido acid varnish, and Table 2 shows the results of the physical property values.

本實施例的聚醯亞胺膜確認到低介電常數性優異。例如比較例1的聚醯亞胺膜的介電常數為3.61，相對於此，實施例2的聚醯亞胺膜的介電常數為3.35、實施例5的聚醯亞胺膜的介電常數為3.33。 The polyimide film of this example was confirmed to have excellent low dielectric constant. For example, the dielectric constant of the polyimide film of Comparative Example 1 is 3.61, whereas the dielectric constant of the polyimide film of Example 2 is 3.35, and the dielectric constant of the polyimide film of Example 5. Is 3.33.

根據本實施例可知，在任一種聚醯亞胺膜中，玻璃轉移 溫度均為290℃以上、吸水率均為2.0%以下、及拉伸斷裂伸長率均為55%以上，除了優異的機械強度外，在耐熱性與低吸水性這兩者中亦可提供必需的充分的特性。 According to the present embodiment, in any of the polyimide membranes, glass transfer The temperature is 290 ° C or higher, the water absorption rate is 2.0% or less, and the tensile elongation at break is 55% or more. In addition to excellent mechanical strength, it is also required to provide both heat resistance and low water absorption. Fully versatile.

該申請案主張以2012年3月14日申請的日本專利申請特願2012-57315為基礎的優先權，其揭示的全部內容併入於此。 The present application claims priority based on Japanese Patent Application No. 2012-57315, filed on Mar.

[產業上之可利用性] [Industrial availability]

由本發明的聚醯亞胺前驅物清漆而得的聚醯亞胺樹脂，具有優異的絕緣特性、及機械特性，且兼具優異的低吸水性、耐熱性，因此可廣泛地用於要求這些特性的所有用途。作為較佳的用途例，可列舉：絕緣電線等各種電子零件、耐熱膠帶、耐熱塗料、航空宇宙用黏接劑。另外，例如適合作為以耐熱膜、印刷配線板用基材、汽車、航空宇宙為代表的各種產業用滑動零件，辦公室自動化(office automation，OA)設備用無縫帶、散熱構件、電磁波屏蔽構件、電池用黏合劑、太陽電池用構件、牙科用構件、透明導體的絕緣保護材。另外，由於可實現低傳輸損失化、低介電常數化，因此特別適合於絕緣電線、或捲線等用途。 The polyimine resin obtained from the polyamidene precursor varnish of the present invention has excellent insulating properties and mechanical properties, and has excellent low water absorption and heat resistance, and thus can be widely used for requiring these properties. All uses. Examples of preferred applications include various electronic parts such as insulated wires, heat-resistant tapes, heat-resistant coatings, and aerospace adhesives. In addition, for example, it is suitable as various industrial sliding parts represented by heat-resistant films, substrates for printed wiring boards, automobiles, and aerospace, office belts, office heating (OA) equipment, seamless belts, heat-dissipating members, and electromagnetic wave shielding members. A battery adhesive, a member for a solar cell, a dental member, and an insulating protective material for a transparent conductor. In addition, since it can achieve low transmission loss and low dielectric constant, it is particularly suitable for applications such as insulated wires or coils.

1‧‧‧絕緣電線 1‧‧‧insulated wire

10‧‧‧導體 10‧‧‧Conductor

20‧‧‧絕緣被覆層 20‧‧‧Insulation coating

Claims (12)

一種聚醯亞胺前驅物清漆，其包含含有聚醯亞胺前驅物、及溶劑的組成物，且在將上述組成物進行塗膜，以5℃/min進行升溫、於300℃於氮氣環境下加熱處理1小時而得的乾燥後的塗膜厚度為20 μm~60 μm的聚醯亞胺膜時，玻璃轉移溫度為290℃以上，吸水率為2.0%以下，及拉伸斷裂伸長率為55%以上。 A polyamidene precursor varnish comprising a composition comprising a polyimide precursor and a solvent, wherein the composition is coated, heated at 5 ° C/min, and subjected to a nitrogen atmosphere at 300 ° C When the polyimine film having a thickness of 20 μm to 60 μm after drying is obtained by heat treatment for 1 hour, the glass transition temperature is 290 ° C or higher, the water absorption rate is 2.0% or less, and the tensile elongation at break is 55. %the above. 如申請專利範圍第1項所述的聚醯亞胺前驅物清漆，其中上述聚醯亞胺前驅物是藉由將二胺、與酸二酐進行聚縮合而得者，上述二胺是至少將相對於上述二胺的總量而為19莫耳%以上、56莫耳%以下的化學式(1)所示的二胺成分A、及相對於上述二胺的總量而為44莫耳%以上、81莫耳%以下的化學式(2)所示的二胺成分B作為構成成分，上述酸二酐是至少將相對於上述酸二酐的總量而為60莫耳%以上、100莫耳%以下的化學式(3)所示的酸二酐成分C、及相對於上述酸二酐的總量而為0莫耳%以上、40莫耳%以下的化學式(4)所示的酸二酐成分D作為構成成分； (式中，X表示單鍵、氧原子、硫原子、碸基、羰基、亞甲基、亞異丙基或六氟亞異丙基的2價基團) (式中，Y表示單鍵、氧原子、硫原子、碸基、羰基、亞甲基、亞異丙基或六氟亞異丙基的2價基團)。 The polyamidiene precursor varnish according to claim 1, wherein the polyimine precursor is obtained by polycondensing a diamine with an acid dianhydride, and the diamine is at least The diamine component A represented by the chemical formula (1) in an amount of 19 mol% or more and 56 mol% or less based on the total amount of the diamine, and 44 mol% or more based on the total amount of the diamine The diamine component B represented by the chemical formula (2) of 81 mol% or less is a constituent component, and the acid dianhydride is at least 60 mol% or more and 100 mol% based on the total amount of the acid dianhydride. The acid dianhydride component C represented by the following chemical formula (3) and the acid dianhydride component represented by the chemical formula (4) of 0 mol% or more and 40 mol% or less with respect to the total amount of the acid dianhydride. D as a constituent; (wherein X represents a single bond, an oxygen atom, a sulfur atom, a thiol group, a carbonyl group, a methylene group, an isopropylidene group or a divalent group of a hexafluoroisopropylidene group) (wherein Y represents a single bond, an oxygen atom, a sulfur atom, a thiol group, a carbonyl group, a methylene group, an isopropylidene group or a divalent group of hexafluoroisopropylidene group). 如申請專利範圍第2項所述的聚醯亞胺前驅物清漆，其中上述聚醯亞胺前驅物是 相對於上述二胺與上述酸二酐的合計，而在上述二胺成分A與上述二胺成分B的合計滿足47.5莫耳%~52.5莫耳%、上述酸二酐成分C與上述酸二酐成分D的合計滿足47.5莫耳%~52.5莫耳%的範圍內進行共聚合者。 The polyamidiene precursor varnish according to claim 2, wherein the polyimine precursor is The total of the diamine component A and the diamine component B is 47.5 mol% to 52.5 mol%, and the acid dianhydride component C and the acid dianhydride are added to the total of the diamine and the acid dianhydride. The total of the components D satisfies the range of 47.5 mol% to 52.5 mol%. 如申請專利範圍第2項或第3項所述的聚醯亞胺前驅物清漆，其中上述二胺成分B是化學式(5)所記載的4,4'-雙(3-胺基苯氧基)聯苯： The polyamidiamine precursor varnish according to claim 2, wherein the diamine component B is a 4,4'-bis(3-aminophenoxy group) of the formula (5). Biphenyl: 如申請專利範圍第2項或第3項所述的聚醯亞胺前驅物清漆，其中上述二胺成分A是化學式(6)所記載的4,4'-二胺基二苯醚： The polyimine precursor varnish according to claim 2, wherein the diamine component A is 4,4'-diaminodiphenyl ether of the formula (6): 如申請專利範圍第2項或第3項所述的聚醯亞胺前驅物清漆，其中上述酸二酐成分D是化學式(7)所記載的3,3',4,4'-聯苯四甲酸二酐： The polyamidiamine precursor varnish according to claim 2, wherein the acid dianhydride component D is 3,3',4,4'-biphenyl four according to the formula (7). Formic acid dianhydride: 一種聚醯亞胺樹脂，其藉由將由如申請專利範圍第1項至第6項中任一項所述的聚醯亞胺前驅物清漆而得的成形物進行醯亞胺化而形成。 A polyimine resin which is obtained by ruthenium imidating a molded article obtained by varnishing a polyimide precursor precursor according to any one of claims 1 to 6. 如申請專利範圍第7項所述的聚醯亞胺樹脂，其用作被覆導體的絕緣被覆材。 The polyimine resin described in claim 7 is used as an insulating covering material for a coated conductor. 一種電子零件，其具備：導體、及被覆上述導體的絕緣被覆材，上述絕緣被覆材的至少一部分包含聚醯亞胺樹脂，上述聚醯亞胺樹脂是藉由將由如申請專利範圍第1項至第6項中任一項所述的聚醯亞胺前驅物清漆而得的成形物進行醯亞胺化而形成。 An electronic component comprising: a conductor; and an insulating covering material covering the conductor; wherein at least a part of the insulating covering material comprises a polyimide resin, and the polyimine resin is obtained by the first aspect of the patent application The molded article obtained from the polyamidene precursor varnish according to any one of the items 6 is obtained by imidization. 一種耐熱膠帶，其具備：支撐基材、及形成於上述支撐基材上的接合層，上述支撐基材包含聚醯亞胺樹脂作為成分，上述聚醯亞胺樹脂是藉由將由如申請專利範圍第1項至第6項中任一項所述的聚醯亞胺前驅物清漆而得的成形物進行醯亞胺化而形成。 A heat resistant tape comprising: a support substrate and a bonding layer formed on the support substrate, wherein the support substrate comprises a polyimide resin as a component, and the polyimine resin is used as claimed in the patent application The molded article obtained from the polyamidene precursor varnish according to any one of the items 1 to 6 is obtained by imidization. 一種耐熱塗料，其包含如申請專利範圍第1項至第6項中任一項所述的聚醯亞胺前驅物清漆。 A heat-resistant coating comprising the polyimine precursor varnish as described in any one of claims 1 to 6. 一種航空宇宙用黏接劑，其包含如申請專利範圍第1項 至第6項中任一項所述的聚醯亞胺前驅物清漆、或者包含由上述聚醯亞胺前驅物清漆形成的凝膠膜。 An aerospace adhesive comprising the first item of the patent application scope The polyamidene precursor varnish according to any one of the above items, or the gel film formed of the above polyimine precursor varnish.
TW102109066A 2012-03-14 2013-03-14 Polyimide precursor varnish, polyimide resin, electrical component, heat resistant tape, heat resistant coating and adhesive for aerospace TW201343722A (en)

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