TWI529215B - Flexible device substrate and flexible device - Google Patents

Flexible device substrate and flexible device Download PDF

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TWI529215B
TWI529215B TW102140739A TW102140739A TWI529215B TW I529215 B TWI529215 B TW I529215B TW 102140739 A TW102140739 A TW 102140739A TW 102140739 A TW102140739 A TW 102140739A TW I529215 B TWI529215 B TW I529215B
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substrate
amino
polyimide
bis
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TW201431955A (en
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Yamato Saito
Akihiro Izumi
Shozo Takada
Ichiro Doi
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Asahi Kasei E Materials Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1259—Multistep manufacturing methods
    • H01L27/1262—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate
    • H01L27/1266—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate the substrate on which the devices are formed not being the final device substrate, e.g. using a temporary substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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    • 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
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    • 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
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1218—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or structure of the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78603—Thin film transistors, i.e. transistors with a channel being at least partly a thin film characterised by the insulating substrate or support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides
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Description

可撓性裝置用基板及可撓性裝置 Substrate for flexible device and flexible device

本發明特別係關於可撓性裝置及於其製造中有用之樹脂組合物、積層體及積層體之製造方法、與使用積層體之可撓性裝置之製造方法。又，本發明係關於適宜地用於可撓性裝置之可撓性裝置用基板、及使用其之可撓性裝置。 In particular, the present invention relates to a flexible device, a resin composition useful in the production thereof, a method for producing a laminate, a laminate, and a method for producing a flexible device using the laminate. Moreover, the present invention relates to a substrate for a flexible device that is suitably used in a flexible device, and a flexible device using the same.

目前，太陽電池模組、平板顯示器等裝置之基板主要使用包含玻璃之基板，但為了輕量化、薄型化而進行樹脂基板之研究。所研究之樹脂基板需要對於使用矽系半導體之裝置之製造步驟所需之400℃以上之熱處理步驟、使用金屬氧化物半導體之裝置之製造步驟所需之300℃以上的熱處理步驟的耐受性；又，為了抑制由於樹脂基板與矽系半導體、或金屬氧化物半導體之熱膨脹係數差所產生的熱處理步驟時的尺寸差，使用樹脂基板與無機基板之積層體，於製造裝置後需要將樹脂基板自無機基板剝離之加工。 At present, a substrate including a glass is mainly used for a substrate such as a solar cell module or a flat panel display, but a resin substrate is studied for weight reduction and thinning. The resin substrate to be studied needs to be resistant to a heat treatment step of 400 ° C or more required for the production step of the apparatus using the lanthanide semiconductor, or a heat treatment step of 300 ° C or more required for the production step of the apparatus using the metal oxide semiconductor; Further, in order to suppress the dimensional difference in the heat treatment step caused by the difference in thermal expansion coefficient between the resin substrate and the lanthanide semiconductor or the metal oxide semiconductor, a laminate of the resin substrate and the inorganic substrate is used, and the resin substrate needs to be self-made after the device is manufactured. Processing of inorganic substrate peeling.

一般而言，熱膨脹係數接近矽系半導體且具有400℃以上之耐熱性的聚醯亞胺可藉由分子配向而使之低熱膨脹化，因此不具有對無機基板之密接性。因此，於無機基板表面形成樹脂接著用無機層，例如氮化矽層及非晶形矽層。於此情形時，為了自無機基板剝離樹脂基板，可採用如下的方法：如專利文獻1般在製造裝置後藉由雷射使聚醯亞胺分解；如專利文獻2般藉由自氫化非晶形矽層產生氫而自無機基板剝離樹脂基板之剝離方法等。 In general, a polyimide having a thermal expansion coefficient close to that of a lanthanoid semiconductor and having heat resistance of 400 ° C or higher can be thermally expanded by molecular alignment, and thus does not have adhesion to an inorganic substrate. Therefore, a resin is formed on the surface of the inorganic substrate, followed by an inorganic layer such as a tantalum nitride layer and an amorphous tantalum layer. In this case, in order to peel the resin substrate from the inorganic substrate, a method may be employed in which the polyimine is decomposed by laser after manufacturing the device as in Patent Document 1, and the self-hydrogenated amorphous form is used as in Patent Document 2. A method of peeling off a resin substrate from an inorganic substrate by generating hydrogen in the ruthenium layer.

另一方面，於半導體元件之層間絕緣膜(鈍化膜)、表面保護膜(保護層膜)之領域中，已知有含有聚醯亞胺、矽烷偶合劑、溶劑之樹脂組合物(參照專利文獻3)。 On the other hand, in the field of an interlayer insulating film (passivation film) and a surface protective film (protective layer film) of a semiconductor element, a resin composition containing a polyimide, a decane coupling agent, or a solvent is known (refer to the patent literature). 3).

又，於半導體裝置等各種電子零件之表面保護膜或層間絕緣膜等領域中，已知有於有機溶劑中溶解特定之二胺與特定之羧酸及/或其衍生物作為溶質，包含特定量之包含聚矽氧油之界面活性劑的聚醯亞胺前驅物溶液(參照專利文獻4)。 Further, in the field of a surface protective film or an interlayer insulating film of various electronic components such as a semiconductor device, it is known to dissolve a specific diamine and a specific carboxylic acid and/or a derivative thereof as a solute in an organic solvent, and to contain a specific amount. A polyimine precursor solution containing a surfactant of a polyoxygenated oil (see Patent Document 4).

又，作為半導體裝置之表面保護膜或層間絕緣膜，已知有包含鹼可溶性樹脂、光酸產生劑、脂肪酸醇化合物及有機矽化物而成之感光性樹脂組合物(參照專利文獻5)。 In addition, as the surface protective film or the interlayer insulating film of the semiconductor device, a photosensitive resin composition containing an alkali-soluble resin, a photoacid generator, a fatty acid alcohol compound, and an organic telluride is known (see Patent Document 5).

又，已知有一種正型感光性樹脂組合物，其成為可用作半導體元件等電子零件之表面保護膜、層間絕緣膜等的聚苯并唑系耐熱性高分子(參照專利文獻6)。 Further, a positive-type photosensitive resin composition which is used as a surface protective film for an electronic component such as a semiconductor element, an interlayer insulating film, or the like, is known. An azole-based heat-resistant polymer (see Patent Document 6).

又，已知有一種可撓性光接收元件，其具有可撓性之透明塑膠製之基板、電極層、半導體層，並且基板係藉由以聚醯亞胺為主成分之聚醯亞胺膜所形成(參照專利文獻7)。 Further, a flexible light-receiving element having a flexible transparent plastic substrate, an electrode layer, and a semiconductor layer is known, and the substrate is made of a polyimide film mainly composed of polyimine. It is formed (refer to Patent Document 7).

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

[專利文獻1]日本專利特表2012-511173號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-511173

[專利文獻2]國際公開第2009/037797號說明書 [Patent Document 2] International Publication No. 2009/037797

[專利文獻3]日本專利特開2009-102505號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-102505

[專利文獻4]日本專利特開2001-139808號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2001-139808

[專利文獻5]日本專利特開2008-216569號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-216569

[專利文獻6]日本專利特開2004-170611號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2004-170611

[專利文獻7]日本專利特開昭64-774號公報 [Patent Document 7] Japanese Patent Laid-Open No. 64-774

然而，於專利文獻1及專利文獻2中所記載之剝離方法中，存在於該等剝離步驟時產生源自接著層(樹脂接著用無機層等)之缺陷的現象。又，存在因雷射而於樹脂基板上產生缺陷之現象。其結果為，樹脂基板之耐久性或機械強度降低，且膜厚不均容易增大。 However, in the peeling methods described in Patent Document 1 and Patent Document 2, there is a phenomenon in which defects due to the adhesive layer (resin is followed by an inorganic layer or the like) occur in the peeling step. Further, there is a phenomenon in which defects are generated on the resin substrate due to laser irradiation. As a result, the durability or mechanical strength of the resin substrate is lowered, and the film thickness unevenness is likely to increase.

而且，於使用如上所述而形成之樹脂基板而製造的可撓性裝置中，存在產生裝置之動作不良、例如薄膜電晶體之臨界電壓之變動或不均等。基於該等原因，裝置製造之良率降低，於成本降低或生產性提高之方面亦成為較大障礙。 Further, in the flexible device manufactured by using the resin substrate formed as described above, there is a malfunction of the device, for example, fluctuation or unevenness of the threshold voltage of the thin film transistor. For these reasons, the yield of the device is reduced, which also becomes a major obstacle in terms of cost reduction or productivity improvement.

又，於藉由專利文獻3及專利文獻4中所記載之樹脂組合物而製成之樹脂基板中，未必可謂充分地同時實現對無機基板之密接性及剝離性，具有實現進一步改良之必要性。 Further, in the resin substrate produced by the resin compositions described in Patent Document 3 and Patent Document 4, it is not necessary to sufficiently achieve the adhesion and peelability to the inorganic substrate at the same time, and the necessity for further improvement is required. .

又，於專利文獻5、專利文獻6及專利文獻7中，除了對無機基板之密接性以外，關於剝離性並未提及。專利文獻5係藉由樹脂組合物而形成半導體裝置之表面保護膜或層間絕緣層者，於實施例中，僅進行感度及接著性之實驗，於專利文獻5中並未設想包含用以對無機基板同時實現密接性與剝離性之組成的樹脂組合物。 Further, in Patent Document 5, Patent Document 6, and Patent Document 7, the peeling property is not mentioned except for the adhesion to the inorganic substrate. Patent Document 5 is a method of forming a surface protective film or an interlayer insulating layer of a semiconductor device by a resin composition. In the examples, only experiments for sensitivity and adhesion are performed, and Patent Document 5 does not contemplate inclusion of inorganic materials. A resin composition in which the substrate simultaneously has a composition of adhesion and releasability.

於專利文獻6中，為了使正型感光性樹脂組合物與基板之密接性提高，而添加矽烷偶合劑，但並未設想自基板之剝離，因此與專利文獻5同樣地，專利文獻6中並未設想包含用以對無機基板同時實現密接性與剝離性之組成的樹脂組合物。 In Patent Document 6, in order to improve the adhesion between the positive photosensitive resin composition and the substrate, a decane coupling agent is added. However, since the peeling from the substrate is not assumed, the patent document 6 is similar to Patent Document 5. A resin composition containing a composition for simultaneously achieving adhesion and releasability to an inorganic substrate is not contemplated.

又，於專利文獻7中，記載了包含聚醯亞胺膜之基板，但並未設想自無機基板剝離包含聚醯亞胺膜之基板，且未設想包含用以對無機基板同時實現密接性與剝離性之組成的聚醯亞胺膜。 Further, Patent Document 7 describes a substrate including a polyimide film, but it is not assumed that the substrate including the polyimide film is peeled off from the inorganic substrate, and it is not assumed to include the adhesion between the inorganic substrate and the inorganic substrate. A polyimide film having a peeling composition.

又，任意專利文獻中並未揭示於以聚醯亞胺為主體之可撓性裝 置用基板中可使膜厚不均變小之組成。如下述之比較例所示：先前以聚醯亞胺為主體之可撓性裝置用基板之膜厚不均容易增大。又，任意專利文獻中並未揭示於電氣特性等特性之評價中顯示出良好之面內均一性的以聚醯亞胺為主體之可撓性裝置用基板、或包含聚醯亞胺樹脂層之可撓性裝置。 Moreover, in any patent document, it is not disclosed in a flexible device mainly composed of polyimide. A composition in which the film thickness unevenness is reduced in the substrate is used. As shown in the comparative example below, the film thickness unevenness of the substrate for a flexible device mainly composed of polyimine is likely to increase. Further, in any of the patent documents, a substrate for a flexible device mainly comprising polyimide, which exhibits good in-plane uniformity in the evaluation of characteristics such as electrical characteristics, or a layer containing a polyimide resin layer is not disclosed. Flexible device.

本發明係鑒於該方面而成者，其目的在於提供於可撓性裝置之製造過程中在樹脂層及無機基板之間具有充分之密接性，且於最終階段可容易地自樹脂層僅剝離無機基板之樹脂組合物、積層體及積層體之製造方法與可撓性裝置之製造方法。而且，本發明之目的在於提供膜厚不均較小、於構成裝置時難以產生裝置之動作不良的可撓性裝置用基板、及使用其之可撓性裝置。 The present invention has been made in view of the above aspects, and an object thereof is to provide sufficient adhesion between a resin layer and an inorganic substrate in a manufacturing process of a flexible device, and to easily peel only inorganic from a resin layer in a final stage. A resin composition for a substrate, a method for producing a laminate, a laminate, and a method for producing a flexible device. Further, an object of the present invention is to provide a substrate for a flexible device which is less likely to have a film thickness unevenness and which is less likely to cause malfunction of the device when the device is formed, and a flexible device using the same.

本發明之可撓性裝置用基板之特徵在於含有：(α)5%熱分解溫度為350℃以上之聚醯亞胺、(β)具有下述通式(1)所表示之化學結構及/或下述通式(2)所表示之化學結構之化合物、(γ)具有由下述通式(3)所表示之化學結構、羥基、羧基及磺基所組成之群中之1種以上之化合物、(δ)具有下述通式(4)所表示之化學結構之化合物。 The substrate for a flexible device of the present invention is characterized by comprising: (α) 5% of a polyamidene having a thermal decomposition temperature of 350 ° C or higher, (β) having a chemical structure represented by the following formula (1) and/or Or a compound having a chemical structure represented by the following formula (2), and (γ) having one or more of a group consisting of a chemical structure represented by the following formula (3), a hydroxyl group, a carboxyl group, and a sulfo group; The compound (δ) has a chemical structure represented by the following formula (4).

[化3]通式(3)-(CH2)nO- [Chemical Formula 3] General formula (3)-(CH 2 ) n O-

(n表示1以上5以下之整數) (n represents an integer of 1 or more and 5 or less)

[化4]通式(4)-Si(OH)3 [4]-(Si)-Si(OH) 3

本發明之可撓性裝置之特徵在於：於上述所記載之可撓性裝置用基板上形成有半導體裝置。 A flexible device according to the present invention is characterized in that the semiconductor device is formed on the substrate for a flexible device described above.

本發明之可撓性裝置之特徵在於：上述半導體裝置為薄膜電晶體。 The flexible device of the present invention is characterized in that the semiconductor device is a thin film transistor.

本發明之上述可撓性裝置為多晶矽半導體或金屬氧化物半導體驅動型可撓性顯示器。 The above flexible device of the present invention is a polycrystalline germanium semiconductor or a metal oxide semiconductor driven flexible display.

本發明之可撓性裝置之特徵在於包含聚醯亞胺樹脂層，該聚醯亞胺樹脂層含有：(α)5%熱分解溫度為350℃以上之聚醯亞胺、(β)具有下述通式(1)所表示之化學結構及/或下述通式(2)所表示之化學結構之化合物、(γ)具有由下述通式(3)所表示之化學結構、羥基、羧基及磺基所組成之群中之1種以上之化合物、(δ)具有下述通式(4)所表示之化學結構之化合物。 The flexible device of the present invention is characterized by comprising a polyimine resin layer containing: (α) 5% polypyridinium having a thermal decomposition temperature of 350 ° C or higher, (β) having a lower layer The chemical structure represented by the general formula (1) and/or the chemical structure represented by the following general formula (2), (γ) has a chemical structure represented by the following general formula (3), a hydroxyl group, a carboxyl group. And one or more compounds of the group consisting of a sulfo group, and (δ) a compound having a chemical structure represented by the following formula (4).

[化7]通式(3)-(CH2)nO- General formula (3)-(CH 2 ) n O-

(n表示1以上5以下之整數) (n represents an integer of 1 or more and 5 or less)

[化8]通式(4)-Si(OH)3 [Chemical Formula 8] General formula (4)-Si(OH) 3

本發明之積層體之特徵在於：具備無機基板、與設置在上述無機基板之表面上的包含(a)5%熱分解溫度為350℃以上之聚醯亞胺之聚醯亞胺樹脂層，並且上述聚醯亞胺樹脂層與上述無機基板之180°剝離強度為0.004~0.250N/cm。 The laminate of the present invention is characterized by comprising an inorganic substrate and a polyimine resin layer comprising (a) a polyamidimide having a thermal decomposition temperature of 350 ° C or higher, which is provided on the surface of the inorganic substrate, and The 180° peel strength of the polyimine resin layer and the inorganic substrate is 0.004 to 0.250 N/cm.

本發明之積層體之特徵在於上述聚醯亞胺樹脂層進而包含：(b)聚矽氧界面活性劑或氟系界面活性劑、及(c)具有選自由醯胺基、胺基、胺基甲酸酯基、羧基、芳基、酸酐基及聚合性環狀醚基所組成之群中之至少1種官能基的烷氧基矽烷化合物。 The laminate of the present invention is characterized in that the polyimine resin layer further comprises: (b) a polyfluorene surfactant or a fluorine-based surfactant, and (c) having a selected from the group consisting of a mercapto group, an amine group, and an amine group. An alkoxydecane compound having at least one functional group of a group consisting of a formate group, a carboxyl group, an aryl group, an acid anhydride group, and a polymerizable cyclic ether group.

本發明之積層體之特徵在於：上述無機基板為玻璃基板。 The laminated body of the present invention is characterized in that the inorganic substrate is a glass substrate.

本發明之可撓性裝置之製造方法之特徵在於包括：於上述所記載之積層體上形成半導體裝置之步驟；其後自無機基板剝離之步驟。 A method of manufacturing a flexible device according to the present invention includes the step of forming a semiconductor device on the laminated body described above, and thereafter removing the inorganic substrate.

本發明之可撓性裝置之製造方法之特徵在於進而包括：將上述積層體加熱至250℃以上之步驟。 The method for producing a flexible device of the present invention is characterized by further comprising the step of heating the laminate to 250 ° C or higher.

本發明之可撓性裝置之製造方法之特徵在於：上述半導體裝置為薄膜電晶體。 A method of manufacturing a flexible device according to the present invention is characterized in that the semiconductor device is a thin film transistor.

本發明之可撓性裝置之製造方法之特徵在於：上述可撓性裝置為多晶矽半導體或金屬氧化物半導體驅動型可撓性顯示器。 A method of manufacturing a flexible device according to the present invention is characterized in that the flexible device is a polycrystalline germanium semiconductor or a metal oxide semiconductor-driven flexible display.

本發明之樹脂組合物之特徵在於包括：(a)5%熱分解溫度為350℃以上之聚醯亞胺、或藉由醯亞胺化處理而成為5%熱分解溫度為350℃ 以上之聚醯亞胺的聚醯亞胺前驅物、(b)聚矽氧系界面活性劑或氟系界面活性劑、(c)具有選自由胺基、胺基甲酸酯基、羧基、芳基、酸酐基、醯胺基及聚合性環狀醚基所組成之群中之至少1種官能基的烷氧基矽烷化合物。 The resin composition of the present invention is characterized in that it comprises: (a) a polyamidimide having a 5% thermal decomposition temperature of 350 ° C or higher, or a 5% thermal decomposition temperature of 350 ° C by hydrazine imidization treatment. The polyimine precursor of the above polyimine, (b) a polyoxyn surfactant or a fluorine surfactant, (c) having a group selected from the group consisting of an amine group, a urethane group, a carboxyl group, and a aryl group An alkoxydecane compound having at least one functional group in the group consisting of a group, an acid anhydride group, a guanamine group, and a polymerizable cyclic ether group.

本發明之樹脂組合物之特徵在於：上述(b)成分係於分子內具有2個以上1000個以下之Si-O鍵作為非極性部位，且於分子內具有1個以上100個以下之聚醚基、羥基、羧基或磺基作為極性部位的聚矽氧系界面活性劑。 The resin composition of the present invention is characterized in that the component (b) is a non-polar moiety having two or more and 1,000 or less Si-O bonds in the molecule, and one or more polyethers having one or more and less than 100 in the molecule. A polyfluorene-based surfactant having a base, a hydroxyl group, a carboxyl group or a sulfo group as a polar moiety.

本發明之樹脂組合物之特徵在於：上述(b)成分係於分子內具有3個以上100個以下之C-F鍵作為非極性部位，且於分子內具有1個以上100個以下之聚醚基、羥基、羧基或磺基作為極性部位的氟系界面活性劑。 In the resin composition of the present invention, the component (b) is a non-polar site having three or more and 100 or less CF bonds in the molecule, and one or more polyether groups of one or more and 100 or less in the molecule. A hydroxyl group, a carboxyl group or a sulfo group is a fluorine-based surfactant of a polar site.

本發明之樹脂組合物之特徵在於：相對於上述(a)成分100質量份，包含0.001質量份~10質量份之上述(b)成分。 The resin composition of the present invention is characterized in that it contains 0.001 parts by mass to 10 parts by mass of the above component (b) per 100 parts by mass of the component (a).

本發明之樹脂組合物之特徵在於：上述(c)成分係具有選自由胺基甲酸酯基、羧基、醯胺基及芳基所組成之群中之至少1種官能基的烷氧基矽烷化合物。 The resin composition of the present invention is characterized in that the component (c) is an alkoxydecane having at least one functional group selected from the group consisting of a urethane group, a carboxyl group, a guanamine group, and an aryl group. Compound.

本發明之樹脂組合物之特徵在於：相對於上述(a)成分100質量份，包含0.001質量份~9質量份之上述(c)成分。 The resin composition of the present invention is characterized in that it contains 0.001 parts by mass to 9 parts by mass of the above component (c) per 100 parts by mass of the component (a).

本發明之樹脂組合物之特徵在於：進而包含(d)溶劑。於此情形時，上述(d)成分為非質子性極性溶劑。 The resin composition of the present invention is characterized by further comprising (d) a solvent. In this case, the component (d) is an aprotic polar solvent.

本發明之積層體之製造方法之特徵在於包括：於無機基板上展開上述所記載之樹脂組合物的步驟；形成包含上述樹脂組合物之聚醯亞胺樹脂層，而獲得具備上述無機基板及上述聚醯亞胺樹脂層之積層體的步驟。 The method for producing a laminate according to the present invention includes the steps of: developing the resin composition described above on an inorganic substrate; forming a polyimine resin layer containing the resin composition, and obtaining the inorganic substrate and the above A step of laminating a layer of a polyimide resin layer.

本發明之積層體之製造方法之特徵在於：上述無機基板為玻璃 基板。 The method for producing a laminate of the present invention is characterized in that the inorganic substrate is glass Substrate.

本發明之可撓性裝置之製造方法之特徵在於包括：於藉由上述所記載之積層體之製造方法而獲得之積層體上形成半導體裝置的步驟，其後自無機基板剝離之步驟。 The method for producing a flexible device according to the present invention includes the step of forming a semiconductor device on a laminate obtained by the method for producing a laminate according to the above-described method, and thereafter removing the film from the inorganic substrate.

本發明之可撓性裝置之製造方法之特徵在於進而包括：將上述積層體加熱至250℃以上之步驟。 The method for producing a flexible device of the present invention is characterized by further comprising the step of heating the laminate to 250 ° C or higher.

本發明之可撓性裝置之製造方法之特徵在於：上述半導體裝置為薄膜電晶體。 A method of manufacturing a flexible device according to the present invention is characterized in that the semiconductor device is a thin film transistor.

本發明之可撓性裝置之製造方法之特徵在於：上述可撓性裝置為多晶矽半導體或金屬氧化物半導體驅動型可撓性顯示器。 A method of manufacturing a flexible device according to the present invention is characterized in that the flexible device is a polycrystalline germanium semiconductor or a metal oxide semiconductor-driven flexible display.

根據本發明，可提供於可撓性裝置之製造過程中在樹脂層及無機基板之間具有充分之密接性，且於最終階段可容易地自樹脂層僅剝離無機基板之樹脂組合物、積層體及積層體之製造方法與可撓性裝置之製造方法。又，可提供膜厚不均較小，於構成裝置時難以產生裝置之動作不良之可撓性裝置用基板、及使用其之可撓性裝置。 According to the present invention, it is possible to provide a resin composition and a laminate which can have sufficient adhesion between the resin layer and the inorganic substrate in the manufacturing process of the flexible device, and which can easily peel only the inorganic substrate from the resin layer in the final stage. And a method of manufacturing a laminate and a method of manufacturing the flexible device. Further, it is possible to provide a substrate for a flexible device which is less likely to cause a malfunction of the device when the device is formed, and a flexible device using the same.

11‧‧‧第1基板 11‧‧‧1st substrate

12‧‧‧第1聚醯亞胺樹脂層 12‧‧‧1st polyimide resin layer

100‧‧‧可撓性顯示器 100‧‧‧Flexible display

101‧‧‧第1障壁層 101‧‧‧1st barrier layer

102‧‧‧半導體層 102‧‧‧Semiconductor layer

103‧‧‧閘極絕緣膜 103‧‧‧Gate insulation film

104‧‧‧閘極電極 104‧‧‧gate electrode

105‧‧‧層間絕緣膜 105‧‧‧Interlayer insulating film

106‧‧‧接觸孔 106‧‧‧Contact hole

107a‧‧‧源極-汲極電極 107a‧‧‧Source-drain electrodes

107b‧‧‧源極-汲極電極 107b‧‧‧Source-drain electrodes

108‧‧‧TFT 108‧‧‧TFT

109‧‧‧平坦化層 109‧‧‧flattening layer

110‧‧‧接觸孔 110‧‧‧Contact hole

111‧‧‧第1電極 111‧‧‧1st electrode

112‧‧‧像素定義膜 112‧‧‧ pixel definition film

113‧‧‧中間層 113‧‧‧Intermediate

114‧‧‧第2電極 114‧‧‧2nd electrode

201‧‧‧密封構件 201‧‧‧ Sealing members

202‧‧‧第2基板 202‧‧‧2nd substrate

203‧‧‧第2聚醯亞胺樹脂層 203‧‧‧2nd polyimide resin layer

204‧‧‧第2障壁層 204‧‧‧2nd barrier layer

210‧‧‧有機發光元件 210‧‧‧Organic light-emitting elements

圖1A、B係表示使用本實施形態之樹脂組合物的可撓性顯示器之製造步驟的剖面模式圖。 1A and 1B are cross-sectional schematic views showing a manufacturing procedure of a flexible display using the resin composition of the embodiment.

圖2係表示使用本實施形態之樹脂組合物的可撓性顯示器之製造步驟的剖面模式圖。 Fig. 2 is a schematic cross-sectional view showing a manufacturing step of a flexible display using the resin composition of the embodiment.

圖3係表示使用本實施形態之樹脂組合物的可撓性顯示器之製造步驟的剖面模式圖。 Fig. 3 is a schematic cross-sectional view showing a manufacturing step of a flexible display using the resin composition of the embodiment.

圖4係表示使用本實施形態之樹脂組合物的可撓性顯示器之製造步驟的剖面模式圖。 Fig. 4 is a schematic cross-sectional view showing a manufacturing step of a flexible display using the resin composition of the embodiment.

圖5係表示使用本實施形態之樹脂組合物的可撓性顯示器之製造 步驟的剖面模式圖。 Figure 5 is a view showing the manufacture of a flexible display using the resin composition of the present embodiment. The section pattern diagram of the step.

圖6係表示使用本實施形態之樹脂組合物的可撓性顯示器之製造步驟的剖面模式圖。 Fig. 6 is a schematic cross-sectional view showing a manufacturing step of a flexible display using the resin composition of the embodiment.

圖7係表示使用本實施形態之樹脂組合物的可撓性顯示器之製造步驟的剖面模式圖。 Fig. 7 is a schematic cross-sectional view showing a manufacturing step of a flexible display using the resin composition of the embodiment.

圖8係表示將提高密接性之添加劑添加至聚醯亞胺中時之密接性變化的概念圖。 Fig. 8 is a conceptual diagram showing changes in adhesion when an additive for improving adhesion is added to a polyimide.

圖9係表示實施例27、比較例5、比較例7中之TOF-SIMS之m/z=78.7-79.3之結果。 Fig. 9 shows the results of m/z = 78.7-79.3 of TOF-SIMS in Example 27, Comparative Example 5, and Comparative Example 7.

圖10係表示實施例27、比較例5、比較例7中之TOF-SIMS之m/z=58.4-59.5之結果。 Fig. 10 shows the results of m/z = 58.4 - 59.5 of TOF-SIMS in Example 27, Comparative Example 5, and Comparative Example 7.

圖11係表示實施例27、比較例5、比較例7中之TOF-SIMS之m/z=44.5-45.5之結果。 Fig. 11 shows the results of m/z = 44.5 - 45.5 of TOF-SIMS in Example 27, Comparative Example 5, and Comparative Example 7.

本發明者等人為了解決上述課題而反覆進行努力研究，結果發現藉由控制聚醯亞胺樹脂層與無機基板之180°剝離強度，可同時實現聚醯亞胺樹脂層與無機基板之密接性及剝離性；又，發現使用包含特定界面活性劑與特定烷氧基矽烷化合物之含有聚醯亞胺或聚醯亞胺前驅物的樹脂組合物所形成之聚醯亞胺樹脂層對於無機基板顯示出優異之密接性及易剝離性，基於該發現而完成本發明。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the adhesion between the polyimide film and the inorganic substrate can be simultaneously achieved by controlling the 180° peel strength of the polyimide film and the inorganic substrate. And peelability; further, it was found that a polyimide resin layer formed using a resin composition containing a specific surfactant and a specific alkoxydecane compound containing a polyimide or a polyimide precursor is displayed on an inorganic substrate. The present invention has been completed based on this finding because of excellent adhesion and easy peelability.

本發明之聚醯亞胺樹脂層係具有可撓性之成為例如較薄之膜狀者，於可撓性記憶體、感測器、RF-ID等可撓性裝置中使用。代表性而言，可用於可撓性顯示器。 The polyimine resin layer of the present invention is flexible, for example, a thin film, and is used in a flexible device such as a flexible memory, a sensor, or an RF-ID. Typically, it can be used in flexible displays.

為了成形如此薄之膜狀之聚醯亞胺樹脂層，進而於聚醯亞胺樹脂層上適宜地形成構成裝置之各功能層，必須首先於剛性基板上將聚醯亞胺樹脂層成形，於使聚醯亞胺樹脂層密接於剛性基板上之狀態 下，於聚醯亞胺樹脂層上依序形成構成裝置之各功能層，其後自剛性基板上剝離所完成之可撓性裝置。 In order to form such a thin film-like polyimide layer and further form the functional layers constituting the device on the polyimide layer, it is necessary to first form the polyimide layer on the rigid substrate. a state in which the polyimide layer is adhered to a rigid substrate Next, each functional layer constituting the device is sequentially formed on the polyimide film layer, and thereafter the completed flexible device is peeled off from the rigid substrate.

聚醯亞胺樹脂層之優點為對裝置形成製程中所實施之固化步驟(包括乾燥步驟)具有良好之耐熱性。因此，於裝置形成製程中對聚醯亞胺樹脂層實施固化步驟，於聚醯亞胺樹脂層中亦不產生缺陷。 The polyimine resin layer has the advantage of having good heat resistance to the curing step (including the drying step) carried out in the device forming process. Therefore, the polyimide resin layer is subjected to a curing step in the device formation process, and no defects are generated in the polyimide layer.

於使用聚醯亞胺樹脂層之裝置形成製程中，重要的是如上所述般聚醯亞胺樹脂層對作為剛性基板之無機基板具有適度之密接性與剝離性。 In the apparatus forming process using the polyimide resin layer, it is important that the polyimide resin layer has moderate adhesion and peelability to the inorganic substrate as a rigid substrate as described above.

圖8係表示將提高密接性之添加劑添加至聚醯亞胺中時之密接性變化的概念圖。 Fig. 8 is a conceptual diagram showing changes in adhesion when an additive for improving adhesion is added to a polyimide.

圖8中所示之(1)表示於聚醯亞胺中未添加提高剝離性之添加劑之狀態下，加入提高密接性之添加劑之情形時之與無機基板之密接性。 (1) shown in FIG. 8 shows the adhesion to the inorganic substrate in the case where an additive for improving adhesion is added to the polyimide without adding an additive which improves the releasability.

於(1)之情形時，可知藉由僅少量加入提高密接性之添加劑，密接性急遽上升。因此，於(1)之狀態下，無法控制密接性，無法適度地控制聚醯亞胺樹脂層與無機基板之180°剝離強度。 In the case of (1), it is understood that the adhesion is rapidly increased by adding only a small amount of the additive which improves the adhesion. Therefore, in the state of (1), the adhesion cannot be controlled, and the 180° peel strength of the polyimide film and the inorganic substrate cannot be appropriately controlled.

另一方面，圖8中所示之(2)表示於聚醯亞胺中添加有提高剝離性之添加劑之狀態下，加入提高密接性之添加劑之情形時之與無機基板之密接性。 On the other hand, (2) shown in FIG. 8 shows the adhesion to the inorganic substrate when the additive for improving the adhesion is added to the polyimine in which the additive for improving the releasability is added.

於(2)中，可知若加入提高密接性之添加劑，則密接性緩慢地上升。藉由(2)之情形，可適度地控制聚醯亞胺樹脂層與無機基板之180°剝離強度，可獲得良好之密接性與剝離性。本發明係基於圖8中所示之(2)之概念而成者。 In (2), it is understood that when an additive for improving adhesion is added, the adhesion is gradually increased. In the case of (2), the 180° peel strength of the polyimide film and the inorganic substrate can be appropriately controlled, and good adhesion and peelability can be obtained. The present invention has been developed based on the concept of (2) shown in FIG.

以下，對本發明之一實施形態(以下簡稱為「實施形態」)加以詳細說明。另外，本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變形而實施。 Hereinafter, an embodiment (hereinafter simply referred to as "embodiment") of the present invention will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

<積層體> <Laminated body>

本實施形態之積層體具備無機基板、與設置在上述無機基板之表面上的包含(a)5%熱分解溫度為350℃以上之聚醯亞胺的聚醯亞胺樹脂層，上述聚醯亞胺樹脂層與上述無機基板之180°剝離強度為0.004~0.250N/cm。 The laminate of the present embodiment includes an inorganic substrate and a polyimine resin layer containing (a) a polyamidimide having a 5% thermal decomposition temperature of 350 ° C or higher, which is provided on the surface of the inorganic substrate, The 180° peel strength of the amine resin layer and the above inorganic substrate is 0.004 to 0.250 N/cm.

此處，所謂「180°剝離強度」係日本工業標準(JIS手冊接著、K-6854)中所規定之評價藉由黏著層而貼合之積層膜或黏著帶之剝離強度的試驗法，此處表示與無機基板之表面所形成之聚醯亞胺樹脂層的密接性。 Here, the "180° peel strength" is a test method for evaluating the peeling strength of a laminated film or an adhesive tape which is bonded by an adhesive layer as defined in Japanese Industrial Standards (JIS Handbook, K-6854). It indicates the adhesion to the polyimide film layer formed on the surface of the inorganic substrate.

於本實施形態之積層體中，聚醯亞胺樹脂層與無機基板之180°剝離強度為0.004N/cm以上，藉此聚醯亞胺樹脂層(聚醯亞胺膜)與無機基板之耐熱密接性變得充分。180°剝離強度更佳為0.010N/cm以上，進而較佳為0.015N/cm以上。另一方面，180°剝離強度為0.250N/cm以下，藉此可控制自無機基板剝離聚醯亞胺樹脂層之剝離性。180°剝離強度更佳為0.075N/cm以下，進而較佳為0.050N/cm以下。 In the laminate of the present embodiment, the 180° peel strength of the polyimide layer and the inorganic substrate is 0.004 N/cm or more, whereby the heat resistance of the polyimide film (polyimine film) and the inorganic substrate is high. The adhesion becomes sufficient. The 180° peel strength is more preferably 0.010 N/cm or more, and still more preferably 0.015 N/cm or more. On the other hand, the 180° peel strength is 0.250 N/cm or less, whereby the peeling property of the polyimide film from the inorganic substrate can be controlled. The 180° peel strength is more preferably 0.075 N/cm or less, further preferably 0.050 N/cm or less.

180°剝離強度之控制例如如下所述般進而包含(b)聚矽氧系界面活性劑或氟系界面活性劑、及(c)具有選自由胺基、胺基甲酸酯基、羧基、芳基、酸酐基、醯胺基及聚合性環狀醚基所組成之群中之至少1種官能基的烷氧基矽烷化合物之情形時，可藉由調整該等之種類或量而進行。 The control of the 180° peel strength further includes, as described below, (b) a polyfluorene-based surfactant or a fluorine-based surfactant, and (c) having an amine group, a urethane group, a carboxyl group, and an aromatic group. In the case of an alkoxydecane compound having at least one functional group in the group consisting of a group, an acid anhydride group, a guanamine group, and a polymerizable cyclic ether group, it can be carried out by adjusting the kind or amount of these.

本實施形態之積層體較佳為聚醯亞胺樹脂層之厚度為5μm~200μm。尤佳為10μm~30μm。若為5μm以上，則樹脂層之機械強度優異；若為200μm以下，則樹脂層之彎曲性、輕量性優異。又，無機基板之厚度較佳為0.2mm~5mm。 The laminate of the present embodiment preferably has a thickness of the polyimide layer of 5 μm to 200 μm. It is preferably 10 μm to 30 μm. When it is 5 μm or more, the resin layer is excellent in mechanical strength, and when it is 200 μm or less, the resin layer is excellent in flexibility and lightness. Further, the thickness of the inorganic substrate is preferably 0.2 mm to 5 mm.

<樹脂組合物> <Resin composition>

本實施形態之樹脂組合物包含：(a)5%熱分解溫度為350℃以上之聚醯亞胺或成為5%熱分解溫度為350℃以上之聚醯亞胺的聚醯亞胺前 驅物、(b)聚矽氧系界面活性劑或氟系界面活性劑、(c)具有選自由胺基、胺基甲酸酯基、羧基、芳基、酸酐基、醯胺基及聚合性環狀醚基所組成之群中之至少1種官能基的烷氧基矽烷化合物。 The resin composition of the present embodiment comprises: (a) a polyethylenimine having a 5% thermal decomposition temperature of 350 ° C or higher or a polyiminimide having a polyethylenimine having a 5% thermal decomposition temperature of 350 ° C or higher. a precursor, (b) a polyoxyn surfactant or a fluorine-based surfactant, (c) having an amine group, a urethane group, a carboxyl group, an aryl group, an acid anhydride group, a guanamine group, and a polymerizable group. An alkoxydecane compound having at least one functional group in the group consisting of a cyclic ether group.

根據此種構成，首先包含5%熱分解溫度為350℃以上之聚醯亞胺、或對聚醯亞胺前驅物進行聚醯亞胺化而形成之聚醯亞胺樹脂層之5%熱分解溫度為350℃以上，因此可形成可耐受在可撓性顯示器製造中所需之例如超過300℃之熱處理步驟的聚醯亞胺樹脂層。 According to such a configuration, first, a 5% thermal decomposition of a polyfluorene imine resin having a 5% thermal decomposition temperature of 350 ° C or higher or a polyamidimide resin layer formed by polyimidization of a polyfluorene imine precursor is included. The temperature is 350 ° C or more, so that a polyimide film which can withstand a heat treatment step of, for example, more than 300 ° C required in the manufacture of a flexible display can be formed.

此處，所謂熱分解溫度係指藉由TG/DTA測定而獲得之熱分解溫度。所謂5%熱分解溫度係指於TG/DTA測定中，於氮氣環境下、40℃下保持1小時後，以10℃/min之速度進行升溫時由熱分解所引起之重量變化達到5%時之溫度。 Here, the thermal decomposition temperature means a thermal decomposition temperature obtained by measurement by TG/DTA. The 5% thermal decomposition temperature refers to the TG/DTA measurement, which is maintained at 40 ° C for 1 hour in a nitrogen atmosphere, and the temperature change caused by thermal decomposition at a temperature of 10 ° C / min reaches 5%. The temperature.

又，藉由添加聚矽氧系界面活性劑或氟系界面活性劑，於將清漆狀組合物塗佈於無機基板上時之膜厚均一性提高。於可撓性裝置之製造中，膜厚均一性良好之情況具有如下優點：可於無機基板上穩定地形成聚醯亞胺樹脂層，於熱處理時難以產生外觀異常。 Moreover, by adding a polyoxymethylene-based surfactant or a fluorine-based surfactant, the film thickness uniformity is improved when the varnish-like composition is applied onto an inorganic substrate. In the production of the flexible device, when the film thickness uniformity is good, there is an advantage that the polyimide film can be stably formed on the inorganic substrate, and it is difficult to cause an appearance abnormality at the time of heat treatment.

又，具有選自由胺基、胺基甲酸酯基、羧基、芳基、酸酐基、醯胺基及聚合性環狀醚基所組成之群中之至少1種官能基的烷氧基矽烷化合物由於該化合物之官能基與聚合物之直接鍵結或分子間相互作用，於對樹脂組合物進行加熱時難以揮發。又，烷氧基矽烷化合物由於醯亞胺化、配向時之熱處理而有效地取入至聚醯亞胺樹脂層中，因此相對於無機基板，聚醯亞胺樹脂層保持為所期望之厚度，例如聚醯亞胺樹脂層表現出於惰性環境下之超過300℃之耐熱密接性(初始密接性及長期密接性)。 Further, an alkoxydecane compound having at least one functional group selected from the group consisting of an amine group, a urethane group, a carboxyl group, an aryl group, an acid anhydride group, a guanamine group, and a polymerizable cyclic ether group Due to the direct bonding or intermolecular interaction of the functional group of the compound with the polymer, it is difficult to volatilize when heating the resin composition. Further, since the alkoxydecane compound is efficiently taken into the polyimine resin layer by heat treatment during hydrazine imidation or alignment, the polyimide layer is maintained to have a desired thickness with respect to the inorganic substrate. For example, the polyimide film exhibits heat-resistant adhesion (initial adhesion and long-term adhesion) of more than 300 ° C in an inert environment.

另一方面，不具有該等官能基之烷氧基矽烷化合物於進行醯亞胺化之前的加熱過程中，除了附著、鍵結於無機基板表面之化合物以外均揮發，並不有效地殘留於組合物中，因此密接於無機基板上之聚 醯亞胺樹脂層變薄，耐熱密接性差。 On the other hand, the alkoxydecane compound having no such functional group volatilizes in addition to the compound adhered to and bonded to the surface of the inorganic substrate during the heating process prior to the imidization, and does not effectively remain in the combination. Therefore, the aggregation in close contact with the inorganic substrate The yttrium imide resin layer is thinned, and the heat-resistant adhesiveness is poor.

耐熱密接性包含對積層體進行操作時之初始密接性、裝置形成時之熱處理時之長期密接性。初始密接性係指於無機基板上塗佈藉由醯亞胺化處理而成為5%熱分解溫度為350℃以上之聚醯亞胺的聚醯亞胺前驅物樹脂組合物，繼而藉由熱處理進行聚醯亞胺化而形成聚醯亞胺樹脂層不久後之聚醯亞胺樹脂層與無機基板於高溫條件下之密接性，或者係指於無機基板上塗佈5%熱分解溫度為350℃以上之聚醯亞胺樹脂組合物，繼而藉由熱處理而除去溶劑不久後之聚醯亞胺樹脂層與無機基板於高溫條件下之密接性，具體而言係指300℃以上之溫度下之密接性。另一方面，所謂長期密接性係指進而於高溫條件下長時間、具體而言例如於300℃~500℃下繼續6分鐘~5小時而對包含無機基板及聚醯亞胺樹脂層之積層體實施熱處理後之密接性。於可撓性裝置之製造中，初始密接性及長期密接性良好之情況具有於熱處理時抑制剝離、鼓出等外觀異常之優點。 The heat-resistant adhesiveness includes the initial adhesiveness when the laminated body is operated and the long-term adhesiveness at the time of heat treatment at the time of device formation. The initial adhesiveness refers to a polyimine precursor resin composition which is coated with a polyimide having a 5% thermal decomposition temperature of 350 ° C or higher by imidization treatment on an inorganic substrate, followed by heat treatment. The adhesion of the polyimide layer of the polyimide film to the inorganic substrate at a high temperature after the polyimidization to form a polyimide film, or the coating of 5% on the inorganic substrate is 350 ° C. The above polyimine resin composition, followed by heat treatment to remove the solvent, and the adhesion of the polyimide film to the inorganic substrate under high temperature conditions, specifically, the adhesion at a temperature of 300 ° C or higher Sex. On the other hand, the term "long-term adhesion" refers to a laminate comprising an inorganic substrate and a polyimide resin layer for a long period of time, specifically, for example, at 300 ° C to 500 ° C for 6 minutes to 5 hours. The adhesion after heat treatment is performed. In the production of the flexible device, the initial adhesion and the long-term adhesion are excellent, and there is an advantage in that appearance abnormality such as peeling or bulging is suppressed during heat treatment.

另一方面，藉由熱處理，利用所添加之聚矽氧系界面活性劑或氟系界面活性劑之界面活性效果，結果表現出聚醯亞胺樹脂層對無機基板之易剝離性。藉此，可藉由形成裝置時之熱處理而在不會自無機基板剝離聚醯亞胺樹脂層之情況下良好地形成裝置，於形成裝置後可容易地在無缺陷之情況下自無機基板剝離聚醯亞胺樹脂層，而獲得良好之可撓性裝置。 On the other hand, by the heat treatment, the interfacial activity of the polyfluorene-based surfactant or the fluorine-based surfactant to be added is used to exhibit the easy peelability of the polyimide film to the inorganic substrate. Thereby, the device can be favorably formed without peeling off the polyimide layer from the inorganic substrate by heat treatment at the time of forming the device, and can be easily peeled off from the inorganic substrate without defects after the device is formed. A layer of polyimide resin is obtained to obtain a good flexible device.

此處，所謂易剝離性係指可自無機基板容易地剝離聚醯亞胺樹脂層。易剝離性優異之情況具有如下優點：於可撓性裝置之製造中，最終可容易地將無機基板自聚醯亞胺樹脂層剝離。又，於本實施形態中，可將聚醯亞胺樹脂層自無機基板乾淨地剝去，可獲得於剝離面無缺陷而成為平坦化面之聚醯亞胺樹脂層。 Here, the easy peelability means that the polyimide film can be easily peeled off from the inorganic substrate. The case where the easy peelability is excellent has an advantage that in the manufacture of the flexible device, the inorganic substrate can be easily peeled off from the polyimide film layer. Further, in the present embodiment, the polyimine resin layer can be cleanly peeled off from the inorganic substrate, and a polyimide film having a flat surface on which the release surface is free from defects can be obtained.

以下，對本實施形態之樹脂組合物之各構成要素加以詳細說 明。 Hereinafter, each component of the resin composition of the present embodiment will be described in detail. Bright.

(a)聚醯亞胺或聚醯亞胺前驅物 (a) Polyimine or polyimine precursor

本實施形態之聚醯亞胺或聚醯亞胺前驅物可藉由使四羧酸二酐與二胺反應而獲得。再者，所謂聚醯亞胺前驅物係表示藉由醯亞胺化而成為聚醯亞胺者，不僅表示聚醯胺酸，亦包含聚醯胺酸之一部分醯亞胺化而成者、或聚醯胺酸酯。其中，就於所使用之溶劑中之溶解性與聚醯亞胺化後之耐熱性之觀點而言，較佳為聚醯胺酸。 The polyimine or polyimine precursor of the present embodiment can be obtained by reacting a tetracarboxylic dianhydride with a diamine. Further, the term "polyimine precursor" means a polyimine which is obtained by ruthenium imidization, and includes not only poly-proline but also a part of the polyamid acid, or Polyphthalate. Among them, polylysine is preferred from the viewpoint of solubility in the solvent to be used and heat resistance after polyamidation.

就耐熱性、機械強度之方面而言，聚醯亞胺或聚醯亞胺前驅物較佳為使選自由均苯四甲酸二酐、3,3',4,4'-聯苯四羧酸二酐、2,3,3',4'-聯苯四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、對伸苯基雙(偏苯三甲酸單酯酸酐)、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、3,3'-氧雙鄰苯二甲酸二酐、及4,4'-氧雙鄰苯二甲酸二酐所組成之群中之至少1種為全部四羧酸二酐之80mol%以上，且使選自由對苯二胺、間苯二胺、聯苯胺、4,4'-(或3,4'-、3,3'-、2,4'-)二胺基-二苯醚、5-胺基-2-(對胺基-苯基)苯并唑、6-胺基-2-(對胺基-苯基)苯并唑、5-胺基-2-(間胺基苯基)苯并唑、及6-胺基-2-(間胺基苯基)苯并唑所組成之群中之至少1種為全部二胺之80mol%以上，進行反應而獲得之聚醯亞胺或聚醯胺酸。 In terms of heat resistance and mechanical strength, the polyimide or polyimine precursor is preferably selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic acid. Dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, p-phenylene bis(trimellitic acid) Ester anhydride), 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-oxydiphthalic dianhydride, and 4 At least one of the group consisting of 4'-oxydiphthalic dianhydride is 80 mol% or more of all tetracarboxylic dianhydrides, and is selected from p-phenylenediamine, m-phenylenediamine, benzidine, 4,4'-(or 3,4'-,3,3'-,2,4'-)diamino-diphenyl ether, 5-amino-2-(p-amino-phenyl)benzo Azole, 6-amino-2-(p-amino-phenyl)benzo Azole, 5-amino-2-(m-aminophenyl)benzo Azole and 6-amino-2-(m-aminophenyl)benzo At least one of the group consisting of azoles is a polyimine or a polyamine obtained by reacting at least 80 mol% of all diamines.

就透明性、耐熱性之觀點而言，聚醯亞胺或聚醯亞胺前驅物較佳為使作為四羧酸二酐之選自由含氟基之芳香族酸二酐、脂環式酸二酐、含硫之酸二酐所組成之群中之至少1種、或作為二胺之選自由含氟基之芳香族二胺、脂環式二胺、含硫二胺所組成之群中之至少1種反應而獲得之聚醯亞胺或聚醯胺酸。 From the viewpoint of transparency and heat resistance, the polyimide or polyimine precursor is preferably a tetracarboxylic dianhydride selected from a fluorine-containing aromatic acid dianhydride and an alicyclic acid At least one of a group consisting of an anhydride and a sulfuric acid dianhydride, or a group of a diamine selected from the group consisting of a fluorine-containing aromatic diamine, an alicyclic diamine, and a sulfur-containing diamine Polyimine or polylysine obtained by at least one reaction.

含氟基之芳香族酸二酐可列舉2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、2,2-雙(4-(3,4-二羧基苯氧基)苯基)六氟丙烷二酐、2,2-雙(4-(3,4-二羧基苯甲醯氧基)苯基)六氟丙烷二酐、及2,2'-雙(三氟甲基)-4,4'-雙 (3,4-二羧基苯氧基)聯苯二酐等。 Examples of the fluorine-containing aromatic acid dianhydride include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and 2,2-bis(4-(3,4-dicarboxyphenoxy) group. Phenyl) hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane dianhydride, and 2,2'-bis(trifluoro Methyl)-4,4'-double (3,4-dicarboxyphenoxy)biphenyl dianhydride and the like.

脂環式酸二酐可列舉雙環[2,2,2]辛-7-烯-2,3,5,6-四羧酸二酐、2,3,5,6-環己烷四羧酸二酐、3,3',4,4'-聯環己烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、環丁烷四羧酸二酐等。 Examples of the alicyclic acid dianhydride include bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and 2,3,5,6-cyclohexanetetracarboxylic acid. Diacetic anhydride, 3,3',4,4'-bicyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and the like.

含硫之酸二酐可列舉雙(3,4-二羧基苯基)碸二酐等。 Examples of the sulfur-containing acid dianhydride include bis(3,4-dicarboxyphenyl)ruthenium anhydride.

含氟基之芳香族二胺可列舉1,1,1,3,3,3-六氟-2,2-雙(4-胺基-苯基)丙烷、2,2'-雙(三氟甲基)聯苯胺、2,2-雙(3-胺基-4-羥基苯基)六氟丙烷、2,2'-雙(3-胺基-2,4-二羥基苯基)六氟丙烷、2,2'-雙(4-胺基-3,5-二羥基苯基)六氟丙烷、2,2-雙[4-(3-胺基-苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、2,2-雙[4-(4-胺基-苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷等。 Examples of the fluorine-containing aromatic diamine include 1,1,1,3,3,3-hexafluoro-2,2-bis(4-amino-phenyl)propane and 2,2'-bis(trifluoro). Methyl)benzidine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-2,4-dihydroxyphenyl)hexafluoro Propane, 2,2'-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 2,2-bis[4-(3-amino-phenoxy)phenyl]-1 1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-amino-phenoxy)phenyl]-1,1,1,3,3,3-hexa Fluoropropane, etc.

脂環式二胺可列舉1,4-二胺基環己烷、1,3-二胺基環己烷、4,4'-二胺基二環己基甲烷、4,4'-二胺基二環己基丙烷、2,3-二胺基雙環[2.2.1]庚烷、2,5-二胺基雙環[2.2.1]庚烷、2,6-二胺基雙環[2.2.1]庚烷、2,7-二胺基雙環[2.2.1]庚烷、2,5-雙(胺基甲基)-雙環[2.2.1]庚烷、2,6-雙(胺基甲基)-雙環[2.2.1]庚烷、2,3-雙(胺基甲基)-雙環[2.2.1]庚烷等。 Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, and 4,4'-diamino group. Dicyclohexylpropane, 2,3-diaminobicyclo[2.2.1]heptane, 2,5-diaminobicyclo[2.2.1]heptane, 2,6-diaminobicyclo[2.2.1] Heptane, 2,7-diaminobicyclo[2.2.1]heptane, 2,5-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl) )-bicyclo[2.2.1]heptane, 2,3-bis(aminomethyl)-bicyclo[2.2.1]heptane, and the like.

含硫二胺可列舉4,4'-(或3,4'-、3,3'-、2,4'-)二胺基-二苯基碸、4,4'-(或3,4'-、3,3'-、2,4'-)二胺基-二苯基硫醚、4,4'-二(4-胺基-苯氧基)苯基碸、4,4'-二(3-胺基-苯氧基)苯基碸、3,3'-二胺基-二苯基碸、3,3'-二甲基-4,4'-二胺基-聯苯-6,6'-二碸、雙(3-胺基-苯基)硫醚、雙(4-胺基-苯基)硫醚、雙(3-胺基-苯基)亞碸、雙(4-胺基-苯基)亞碸、雙(3-胺基-苯基)碸、雙(4-胺基-苯基)碸等。 Examples of the sulfur-containing diamine include 4,4'-(or 3,4'-, 3,3'-, 2,4'-)diamino-diphenylanthracene, 4,4'- (or 3,4). '-, 3,3'-, 2,4'-)diamino-diphenyl sulfide, 4,4'-bis(4-amino-phenoxy)phenylhydrazine, 4,4'- Bis(3-Amino-phenoxy)phenylindole, 3,3'-diamino-diphenylanthracene, 3,3'-dimethyl-4,4'-diamino-biphenyl- 6,6'-diindole, bis(3-amino-phenyl) sulfide, bis(4-amino-phenyl) sulfide, bis(3-amino-phenyl) anthracene, double (4 -Amino-phenyl) anthracene, bis(3-amino-phenyl)anthracene, bis(4-amino-phenyl)anthracene, and the like.

其他可使用之四羧酸二酐可列舉3,3',4,4'-二苯甲酮四羧酸二酐、2,3,3',4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐等。該等四羧酸二酐可單獨或將2種以上混合使用。 Other tetracarboxylic dianhydrides which can be used include 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2,3,3',4'-benzophenonetetracarboxylic dianhydride. 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

另外，四羧酸二酐亦可於起到本實施形態之效果的範圍內使用 現有公知之其他四羧酸二酐。 Further, tetracarboxylic dianhydride can also be used within the range of the effects of the embodiment. Other tetracarboxylic dianhydrides are known in the art.

其他四羧酸二酐例如可列舉2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)甲烷二酐、2,2-雙(4-(4-胺基-苯氧基)苯基)丙烷、1,3-二氫-1,3-二側氧基-5-異苯并呋喃羧酸-1,4-伸苯基酯、4-(2,5-二側氧基四氫呋喃-3-基)-1,2,3,4-四氫化萘-1,2-二羧酸酐、2,3,5,6-吡啶四羧酸二酐、及3,4,9,10-苝四羧酸二酐。該等四羧酸二酐可單獨使用，亦可將2種以上混合使用。 Examples of the other tetracarboxylic dianhydride include 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and 1,1. - bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane Anhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 2,2-bis(4-(4-amino-phenoxy)phenyl)propane, 1,3-dihydro-1,3 - Bis-oxy-5-isobenzofurancarboxylic acid-1,4-phenylene ester, 4-(2,5-di-oxytetrahydrofuran-3-yl)-1,2,3,4- Tetrahydronaphthalene-1,2-dicarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 3,4,9,10-decanetetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

其他可使用之二胺例如可列舉以下者。 Other diamines which can be used include, for example, the following.

3,3'-二甲基-4,4'-二胺基-聯苯、2,2'-二甲基-4,4'-二胺基-聯苯、3,3'-二乙基-4,4'-二胺基-聯苯、2,2'-二乙基-4,4'-二胺基-聯苯、1,4-環己基二胺、對苯二甲胺、間二甲苯二胺、1,5-二胺基-萘、3,3'-二甲氧基聯苯胺、4,4'-(或3,4'-、3,3'-、2,4'-)二胺基-二苯基甲烷、4,4'-(或3,4'-、3,3'-、2,4'-)二胺基-二苯醚、4,4'-二苯甲酮二胺、3,3'-二苯甲酮二胺、4,4'-雙(4-胺基-7苯氧基)聯苯、1,4-雙(4-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、3,3-二甲基-4,4'-二胺基-二苯基甲烷、3,3',5,5'-四甲基-4,4'-二胺基-二苯基甲烷、2,2'-雙(4-胺基-苯基)丙烷、5,5'-亞甲基-雙-(鄰胺基苯甲酸)、3,5-二胺基-苯甲酸、3,3'-二羥基-4,4'-二胺基-聯苯等芳香族二胺 3,3'-Dimethyl-4,4'-diamino-biphenyl, 2,2'-dimethyl-4,4'-diamino-biphenyl, 3,3'-diethyl -4,4'-diamino-biphenyl, 2,2'-diethyl-4,4'-diamino-biphenyl, 1,4-cyclohexyldiamine, p-xylylenediamine, between Xylene diamine, 1,5-diamino-naphthalene, 3,3'-dimethoxybenzidine, 4,4'- (or 3,4'-, 3,3'-, 2,4' -) Diamino-diphenylmethane, 4,4'-(or 3,4'-, 3,3'-, 2,4'-)diamino-diphenyl ether, 4,4'-di Benzophenone diamine, 3,3'-benzophenone diamine, 4,4'-bis(4-amino-7phenoxy)biphenyl, 1,4-bis(4-amino-benzene Oxy)benzene, 1,3-bis(4-amino-phenoxy)benzene, 2,2-bis[4-(4-amino-phenoxy)phenyl]propane, 3,3-di Methyl-4,4'-diamino-diphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diamino-diphenylmethane, 2,2'- Bis(4-Amino-phenyl)propane, 5,5'-methylene-bis-(o-aminobenzoic acid), 3,5-diamino-benzoic acid, 3,3'-dihydroxy- Aromatic diamines such as 4,4'-diamino-biphenyl

2,6-二胺基-吡啶、2,4-二胺基-吡啶、2,4-二胺基-均三嗪、2,7-二胺基-苯并呋喃、2,7-二胺基-咔唑、3,7-二胺基-啡噻嗪、2,5-二胺基-1,3,4-噻二唑、2,4-二胺基-6-苯基-均三嗪等雜環式二胺 2,6-Diamino-pyridine, 2,4-diamino-pyridine, 2,4-diamino-s-triazine, 2,7-diamino-benzofuran, 2,7-diamine Base-carbazole, 3,7-diamino-phenothiazine, 2,5-diamino-1,3,4-thiadiazole, 2,4-diamino-6-phenyl-all Heterocyclic diamine

丙二胺、丁二胺、己二胺、2,2-二甲基丙二胺、1,4-環己二胺、3,3'-二胺基-聯苯-4,4'-二醇、3,3'-二胺基-聯苯-4,4'-二醇、4,3'-二胺基-聯苯-3,4'-二醇、4,4'-二胺基-聯苯-3,3',5,5'-四醇、3,3'-二胺基-聯苯- 4,4',5,5'-四醇、3,3'-二胺基-二苯甲酮、4,4'-二胺基-二苯甲酮、3,3'-二胺基-二苯醚、4,4'-二胺基-二苯醚、1,3-雙(3-胺基-苯氧基)苯、1,4-雙(4-胺基-苯氧基)苯、雙(3-(3-胺基-苯氧基)苯基)醚、雙(4-(4-胺基-苯氧基)苯基)醚、1,3-雙(3-(3-胺基-苯氧基)苯氧基)苯、1,4-雙(4-(4-胺基-苯氧基)苯氧基)苯、雙(3-(3-(3-胺基-苯氧基)苯氧基)苯基)醚、雙(4-(4-(4-胺基-苯氧基)苯氧基)苯基)醚、1,3-雙(3-(3-(3-胺基-苯氧基)苯氧基)苯氧基)苯、1,4-雙(4-(4-(4-胺基-苯氧基)苯氧基)苯氧基)苯、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-(4-胺基-苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基-苯氧基)苯基]丁烷等二胺 Propylenediamine, butanediamine, hexamethylenediamine, 2,2-dimethylpropanediamine, 1,4-cyclohexanediamine, 3,3'-diamino-biphenyl-4,4'-di Alcohol, 3,3'-diamino-biphenyl-4,4'-diol, 4,3'-diamino-biphenyl-3,4'-diol, 4,4'-diamine -biphenyl-3,3',5,5'-tetraol, 3,3'-diamino-biphenyl- 4,4',5,5'-tetraol, 3,3'-diamino-benzophenone, 4,4'-diamino-benzophenone, 3,3'-diamino- Diphenyl ether, 4,4'-diamino-diphenyl ether, 1,3-bis(3-amino-phenoxy)benzene, 1,4-bis(4-amino-phenoxy)benzene , bis(3-(3-amino-phenoxy)phenyl)ether, bis(4-(4-amino-phenoxy)phenyl)ether, 1,3-bis(3-(3- Amino-phenoxy)phenoxy)benzene, 1,4-bis(4-(4-amino-phenoxy)phenoxy)benzene, bis(3-(3-(3-amino)- Phenoxy)phenoxy)phenyl)ether, bis(4-(4-(4-amino-phenoxy)phenoxy)phenyl)ether, 1,3-bis(3-(3- (3-amino-phenoxy)phenoxy)phenoxy)benzene, 1,4-bis(4-(4-(4-amino-phenoxy)phenoxy)phenoxy)benzene , 4,4'-bis(3-Amino-phenoxy)biphenyl, 4,4'-bis(4-amino-phenoxy)biphenyl, 2,2-bis[4-(3- Amino-phenoxy)phenyl]propane, 2,2-bis[4-(4-amino-phenoxy)phenyl]propane, 2,2-bis[4-(3-amino-benzene) Diamines such as oxy)phenyl]butane

α,ω-雙(2-胺基-乙基)聚二甲基矽氧烷、α,ω-雙(3-胺基-丙基)聚二甲基矽氧烷、α,ω-雙(4-胺基-丁基)聚二甲基矽氧烷、α,ω-雙(4-胺基-苯基)聚二甲基矽氧烷、α,ω-雙(3-胺基-丙基)聚二苯基矽氧烷等聚矽氧二胺 α,ω-bis(2-amino-ethyl)polydimethyloxane, α,ω-bis(3-amino-propyl)polydimethyloxane, α,ω-double ( 4-amino-butyl)polydimethyloxane, α,ω-bis(4-amino-phenyl)polydimethyloxane, α,ω-bis(3-amino-propyl Poly(nonoxyl diamine) such as polydiphenyl sulfoxane

該等二胺可單獨使用，亦可將2種以上混合而使用。 These diamines may be used singly or in combination of two or more.

其次，對聚醯亞胺前驅物之製造方法加以敍述。本實施形態之聚醯亞胺前驅物之製造方法包含公知之方法，可製造聚醯亞胺前驅物之方法全部可應用。其中，較佳為於有機溶劑中進行反應。 Next, a method for producing a polyimide precursor is described. The method for producing the polyimine precursor of the present embodiment includes a known method, and all of the methods for producing a polyimide precursor are applicable. Among them, it is preferred to carry out the reaction in an organic solvent.

此種反應中所使用之溶劑例如可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯、1,2-二甲氧基乙烷、四氫呋喃、1,3-二烷、1,4-二烷、二甲基亞碸、苯、甲苯、二甲苯、均三甲苯、苯酚、甲酚、苯甲酸乙酯、及苯甲酸丁酯。該等溶劑可單獨使用，亦可將2種以上混合而使用。 Examples of the solvent used in such a reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone. 1,2-dimethoxyethane, tetrahydrofuran, 1,3-two Alkane, 1,4-two Alkane, dimethyl hydrazine, benzene, toluene, xylene, mesitylene, phenol, cresol, ethyl benzoate, and butyl benzoate. These solvents may be used singly or in combination of two or more.

上述溶劑較佳為N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯，尤佳為N-甲基-2-吡咯啶酮。 The above solvent is preferably N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and more preferably N-A. Base-2-pyrrolidone.

該反應中之反應原料之濃度通常為2質量%~80質量%，較佳為5 質量%~30質量%。 The concentration of the reaction raw material in the reaction is usually 2% by mass to 80% by mass, preferably 5 Mass%~30% by mass.

反應之四羧酸二酐與二胺之莫耳比為0.8~1.2之範圍內。於該範圍內之情形時，可提高分子量，延展性等亦優異。莫耳比較佳為0.9~1.1，更佳為0.92~1.07。 The molar ratio of the tetracarboxylic dianhydride to the diamine in the reaction is in the range of 0.8 to 1.2. In the case of this range, the molecular weight can be improved, and the ductility and the like are also excellent. The molar ratio is preferably 0.9 to 1.1, more preferably 0.92 to 1.07.

聚醯亞胺前驅物之重量平均分子量較佳為1000以上1000000以下。此處，所謂重量平均分子量係指以已知之數量平均分子量的聚苯乙烯為標準，藉由凝膠滲透層析法而測定的分子量。重量平均分子量更佳為10000以上500000以下，最佳為20000以上300000以下。若重量平均分子量為1000以上1000000以下，則使用樹脂組合物而獲得之樹脂層之拉伸度得到改善，機械物性優異。另外，於塗佈等加工時，可藉由所期望之膜厚而無滲出地塗佈。 The weight average molecular weight of the polyimide precursor is preferably from 1,000 to 1,000,000. Here, the weight average molecular weight means a molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The weight average molecular weight is more preferably 10,000 or more and 500,000 or less, and most preferably 20,000 or more and 300,000 or less. When the weight average molecular weight is 1,000 or more and 1,000,000 or less, the degree of stretching of the resin layer obtained by using the resin composition is improved, and the mechanical properties are excellent. Further, at the time of processing such as coating, it can be applied without bleeding by a desired film thickness.

聚醯亞胺前驅物可藉由如下所示之方法而獲得。首先，使反應原料於室溫至80℃下進行聚縮合反應，藉此而製造聚醯胺酸。 The polyimine precursor can be obtained by the method shown below. First, a polycondensation reaction is carried out by subjecting a reaction raw material to a polycondensation reaction at room temperature to 80 ° C.

又，聚醯亞胺前驅物之聚合物主鏈之末端亦可藉由包含單胺衍生物或羧酸衍生物之封端劑而進行封端。藉由對聚醯亞胺之聚合物主鏈之末端進行密封，源自末端官能基之儲存穩定性優異。 Further, the terminal of the polymer main chain of the polyimide precursor may be blocked by a terminal blocking agent containing a monoamine derivative or a carboxylic acid derivative. By sealing the end of the polymer backbone of the polyimide, the storage stability derived from the terminal functional group is excellent.

包含單胺衍生物之封端劑例如可列舉苯胺、鄰甲苯胺、間甲苯胺、對甲苯胺、2,3-二甲苯胺、2,6-二甲苯胺、3,4-二甲苯胺、3,5-二甲苯胺、鄰氯苯胺、間氯苯胺、對氯苯胺、鄰溴苯胺、間溴苯胺、對溴苯胺、鄰硝基苯胺、對硝基苯胺、間硝基苯胺、鄰胺基-苯酚、對胺基-苯酚、間胺基-苯酚、鄰胺基苯甲醚、間胺基苯甲醚、對胺基苯甲醚、鄰乙氧基苯胺、間乙氧基苯胺、對乙氧基苯胺、鄰胺基-苯甲醛、對胺基-苯甲醛、間胺基-苯甲醛、鄰胺基-苯腈、對胺基-苯腈、間胺基-苯腈、2-胺基-聯苯、3-胺基-聯苯、4-胺基-聯苯、2-胺基-苯基苯基醚、3-胺基-苯基苯基醚、4-胺基-苯基苯基醚、2-胺基-二苯甲酮、3-胺基-二苯甲酮、4-胺基-二苯甲酮、2-胺基-苯基苯基硫醚、3- 胺基-苯基苯基硫醚、4-胺基-苯基苯基硫醚、2-胺基-苯基苯基碸、3-胺基-苯基苯基碸、4-胺基-苯基苯基碸、α-萘胺、β-萘胺、1-胺基-2-萘酚、5-胺基-1-萘酚、2-胺基-1-萘酚、4-胺基-1-萘酚、5-胺基-2-萘酚、7-胺基-2-萘酚、8-胺基-1-萘酚、8-胺基-2-萘酚、1-胺基-蒽、2-胺基-蒽、9-胺基-蒽等芳香族單胺。該等中較佳為使用苯胺之衍生物。該等可單獨使用，亦可將2種以上混合而使用。 Examples of the blocking agent containing a monoamine derivative include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-dimethylaniline, 2,6-dimethylaniline, and 3,4-dimethylaniline. 3,5-xylyleneamine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, p-nitroaniline, m-nitroaniline, ortho-amine - phenol, p-amino-phenol, m-amino-phenol, o-aminoanisole, m-aminoanisole, p-aminoanisole, o-ethoxyaniline, m-ethoxyaniline, p-B Oxyaniline, o-amino-benzaldehyde, p-amino-benzaldehyde, m-amino-benzaldehyde, o-amino-benzonitrile, p-amino-benzonitrile, m-amino-benzonitrile, 2-amino group -biphenyl, 3-amino-biphenyl, 4-amino-biphenyl, 2-amino-phenylphenyl ether, 3-amino-phenylphenyl ether, 4-amino-phenylbenzene Ether, 2-amino-benzophenone, 3-amino-benzophenone, 4-amino-benzophenone, 2-amino-phenylphenyl sulfide, 3- Amino-phenylphenyl sulfide, 4-amino-phenylphenyl sulfide, 2-amino-phenylphenylhydrazine, 3-amino-phenylphenylhydrazine, 4-amino-benzene Phenyl hydrazine, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 5-amino-1-naphthol, 2-amino-1-naphthol, 4-amino group- 1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-amino group- Aromatic monoamine such as hydrazine, 2-amino-hydrazine, 9-amino-hydrazine. It is preferred to use a derivative of aniline. These may be used alone or in combination of two or more.

包含羧酸衍生物之封端劑主要可列舉羧酸酐衍生物。 The blocking agent containing a carboxylic acid derivative is mainly a carboxylic anhydride derivative.

羧酸酐衍生物例如可列舉鄰苯二甲酸酐、2,3-二苯甲酮二羧酸酐、3,4-二苯甲酮二羧酸酐、2,3-二羧基苯基苯基醚酐、3,4-二羧基苯基苯基醚酐、2,3-聯苯二羧酸酐、3,4-聯苯二羧酸酐、2,3-二羧基苯基苯基碸酐、3,4-二羧基苯基苯基碸酐、2,3-二羧基苯基苯基硫醚酐、3,4-二羧基苯基苯基硫醚酐、1,2-萘二羧酸酐、2,3-萘二羧酸酐、1,8-萘二羧酸酐、1,2-蒽二羧酸酐、2,3-蒽二羧酸酐、及1,9-蒽二羧酸酐等芳香族二羧酸酐。該等芳香族二羧酸酐中，較佳為使用鄰苯二甲酸酐。該等可單獨使用，亦可將2種以上混合而使用。 Examples of the carboxylic anhydride derivative include phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, and 2,3-dicarboxyphenyl phenyl ether anhydride. 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenyl phthalic anhydride, 3,4- Dicarboxyphenyl phenyl phthalic anhydride, 2,3-dicarboxyphenyl phenyl thioether anhydride, 3,4-dicarboxyphenyl phenyl thioether anhydride, 1,2-naphthalene dicarboxylic anhydride, 2,3- An aromatic dicarboxylic anhydride such as naphthalene dicarboxylic anhydride, 1,8-naphthalene dicarboxylic anhydride, 1,2-anthracene dicarboxylic anhydride, 2,3-indane dicarboxylic anhydride, and 1,9-fluorene dicarboxylic anhydride. Among these aromatic dicarboxylic anhydrides, phthalic anhydride is preferably used. These may be used alone or in combination of two or more.

所得之聚醯亞胺前驅物溶液可並不脫溶劑地直接使用，亦可進而調配必要之溶劑、添加劑等而用作本實施形態之樹脂組合物。 The obtained polyimide intermediate precursor solution can be used as it is without desolvation, and a necessary solvent, additive or the like can be further used as the resin composition of the present embodiment.

(b)聚矽氧系界面活性劑或氟系界面活性劑 (b) Polyoxo-based surfactant or fluorine-based surfactant

本實施形態之聚矽氧系界面活性劑若為具有矽氧烷結構作為非極性部位者，則並無特別限定，較佳為於分子內具有2個以上1000個以下之Si-O鍵作為非極性部位，於分子內具有1個以上100個以下之聚醚基、羥基、羧基、或磺基作為極性部位之聚矽氧系界面活性劑。 The polyfluorene-based surfactant of the present embodiment is not particularly limited as long as it has a siloxane structure as a non-polar site, and it is preferred to have two or more and 1,000 or less Si-O bonds in the molecule. The polar site has a polyether group having one or more 100 or less polyether groups, a hydroxyl group, a carboxyl group, or a sulfo group as a polar portion in the molecule.

為了表現出與聚醯亞胺或聚醯亞胺前驅物之極性之不同，作為非極性部位之1分子內之Si-O鍵之個數較佳為2以上。就與聚醯亞胺或聚醯亞胺前驅物之均一之膜形成性之觀點而言，作為非極性部位之1分子內之Si-O鍵之個數較佳為1000以下，更佳為500以下，進而較佳 為100以下。 In order to exhibit a difference in polarity from a polyimide or a polyimide precursor, the number of Si-O bonds in one molecule of the non-polar portion is preferably 2 or more. The number of Si-O bonds in one molecule of the non-polar portion is preferably 1000 or less, and more preferably 500, from the viewpoint of uniform film formation property of the polyimide or the polyimide precursor. Hereinafter, it is further preferred It is 100 or less.

就與無機基板之親和性之觀點而言，作為極性部位之1分子內之聚醚基、羥基、羧基、或磺基之個數較佳為1以上。就耐熱性之觀點而言，作為極性部位之1分子內之聚醚基、羥基、羧基、或磺基之個數較佳為100以下，更佳為70以下，進而較佳為50以下。 The number of the polyether group, the hydroxyl group, the carboxyl group, or the sulfo group in one molecule of the polar portion is preferably 1 or more from the viewpoint of affinity with the inorganic substrate. From the viewpoint of heat resistance, the number of the polyether group, the hydroxyl group, the carboxyl group, or the sulfo group in one molecule of the polar portion is preferably 100 or less, more preferably 70 or less, still more preferably 50 or less.

所添加之聚矽氧系界面活性劑之分子量之最大值可調整為藉由清漆之溶劑乾燥及固化步驟中之加熱，使聚矽氧系界面活性劑聚集至聚醯亞胺樹脂層與無機基板之界面，獲得聚醯亞胺樹脂層對無機基板之良好之剝離性的大小。因此，聚矽氧系界面活性劑之分子量較佳為20000以下，更佳為5000以下。又，所添加之聚矽氧系界面活性劑之分子量之最小值可調整為藉由清漆之溶劑乾燥及固化步驟中之加熱，使聚矽氧系界面活性劑並不揮發地留於聚醯亞胺樹脂層內，獲得聚醯亞胺樹脂層對無機基板之良好的剝離性的大小。因此，聚矽氧系界面活性劑之分子量較佳為50以上，更佳為100以上。 The maximum molecular weight of the added polyoxo-based surfactant can be adjusted to concentrate the poly-n-oxide surfactant to the polyimide layer and the inorganic substrate by heating in the solvent drying and curing step of the varnish. The interface is obtained to obtain a good peelability of the polyimide film to the inorganic substrate. Therefore, the molecular weight of the polyoxymethylene surfactant is preferably 20,000 or less, more preferably 5,000 or less. Moreover, the minimum value of the molecular weight of the added polyoxo-based surfactant can be adjusted to be maintained in the solvent drying and curing step of the varnish, so that the polyoxon-based surfactant is not volatilized in the poly In the amine resin layer, the size of the polyimide substrate with good peelability to the inorganic substrate was obtained. Therefore, the molecular weight of the polyoxymethylene surfactant is preferably 50 or more, more preferably 100 or more.

又，本實施形態之氟系界面活性劑若為具有C-F鍵結構作為非極性部位者則並無特別限定，為於分子內具有3個以上100個以下C-F鍵作為極性部位，於分子內具有1個以上100個以下之聚醚基、羥基、羧基、或磺基作為極性部位的氟系界面活性劑。 In addition, the fluorine-based surfactant of the present embodiment is not particularly limited as long as it has a CF bond structure as a non-polar site, and has three or more CF bonds in the molecule as polar sites, and has 1 in the molecule. One or more of 100 or less polyether groups, hydroxyl groups, carboxyl groups, or sulfo groups are used as fluorine-based surfactants of polar sites.

為了表現出與聚醯亞胺或聚醯亞胺前驅物之極性之不同，作為非極性部位之1分子內之C-F鍵之個數較佳為3以上。就與聚醯亞胺或聚醯亞胺前驅物之均一之膜形成性之觀點而言，作為非極性部位之1分子內之C-F鍵之個數較佳為100以下，更佳為70以下，進而較佳為50以下。 In order to exhibit a difference in polarity from a polyimide or a polyimide precursor, the number of C-F bonds in one molecule of the non-polar portion is preferably 3 or more. The number of CF bonds in one molecule of the non-polar portion is preferably 100 or less, and more preferably 70 or less, from the viewpoint of uniform film formation property of the polyimine or the polyimide precursor. More preferably, it is 50 or less.

就與無機基板之親和性之觀點而言，作為極性部位之1分子內之聚醚基、羥基、羧基、或磺基之個數較佳為1以上。就耐熱性之觀點而言，作為極性部位之1分子內之聚醚基、羥基、羧基、或磺基之個 數較佳為100以下，更佳為70以下，進而較佳為50以下。 The number of the polyether group, the hydroxyl group, the carboxyl group, or the sulfo group in one molecule of the polar portion is preferably 1 or more from the viewpoint of affinity with the inorganic substrate. From the viewpoint of heat resistance, one of a polyether group, a hydroxyl group, a carboxyl group, or a sulfo group within one molecule of a polar portion The number is preferably 100 or less, more preferably 70 or less, still more preferably 50 or less.

所添加之氟系界面活性劑之分子量之最大值可調整為藉由清漆之溶劑乾燥及固化步驟中之加熱，氟系界面活性劑集於聚醯亞胺樹脂層與無機基板之界面，獲得聚醯亞胺樹脂層對無機基板之良好之剝離性的大小。因此，氟系界面活性劑之分子量較佳為10000以下，更佳為5000以下。又，所添加之氟系界面活性劑之分子量之最小值可調整為藉由清漆之溶劑乾燥及固化步驟中之加熱，使氟系界面活性劑不揮發地留於聚醯亞胺樹脂層內，獲得聚醯亞胺樹脂層對無機基板之良好的剝離性的大小。因此，氟系界面活性劑之分子量較佳為50以上，更佳為100以上。 The maximum molecular weight of the added fluorine-based surfactant can be adjusted to be heated by the solvent drying and curing step of the varnish, and the fluorine-based surfactant is collected at the interface between the polyimide layer and the inorganic substrate to obtain a poly The good peelability of the quinone imine resin layer to the inorganic substrate. Therefore, the molecular weight of the fluorine-based surfactant is preferably 10,000 or less, more preferably 5,000 or less. Further, the minimum value of the molecular weight of the fluorine-based surfactant to be added can be adjusted so that the fluorine-based surfactant is left in the polyimide layer without being volatilized by the solvent drying in the varnish and the heating in the curing step. The size of the polyimide resin layer having good peelability to the inorganic substrate was obtained. Therefore, the molecular weight of the fluorine-based surfactant is preferably 50 or more, and more preferably 100 or more.

聚矽氧系界面活性劑可列舉聚氧乙烯(POE)改質有機聚矽氧烷、聚氧乙烯‧聚氧丙烯(POE‧POP)改質有機聚矽氧烷、POE山梨醇酐改質有機聚矽氧烷、POE甘油基改質有機聚矽氧烷等經親水基改質之有機聚矽氧烷等。 Polyoxymethylene surfactants include polyoxyethylene (POE) modified organic polyoxyalkylene, polyoxyethylene ‧ polyoxypropylene (POE POP) modified organic polyoxyalkylene, POE sorbitol modified organic An organic polyoxane modified with a hydrophilic group such as a polyoxyalkylene or a POE glycerol-modified organic polyoxyalkylene.

具體例可列舉DBE-712、DBE-821(Azmax公司製造)、KF-6015、KF-6016、KF-6017、KF-6028(信越化學工業公司製造)、ABIL-EM97(Goldschmidt公司製造)、Polyflow KL-100、Polyflow KL-401、Polyflow KL-402、Polyflow KL-700(共榮社化學製)等。 Specific examples thereof include DBE-712, DBE-821 (manufactured by Azmax Corporation), KF-6015, KF-6016, KF-6017, KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.), ABIL-EM97 (manufactured by Goldschmidt Co., Ltd.), and Polyflow. KL-100, Polyflow KL-401, Polyflow KL-402, Polyflow KL-700 (manufactured by Kyoeisha Chemical Co., Ltd.).

氟系界面活性劑可列舉全氟烷基羧酸鹽、全氟烷基磷酸酯、全氟烷基磺酸鹽等陰離子性氟系界面活性劑，或全氟烷基環氧乙烷加成物、全氟烷基胺氧化物、全氟烷基聚氧乙烯乙醇、全氟烷基烷氧基化物、氟化烷基酯等非離子性氟系界面活性劑等。 Examples of the fluorine-based surfactant include an anionic fluorine-based surfactant such as a perfluoroalkyl carboxylate, a perfluoroalkyl phosphate, or a perfluoroalkylsulfonate, or a perfluoroalkyl ethylene oxide adduct. A nonionic fluorine-based surfactant such as a perfluoroalkylamine oxide, a perfluoroalkylpolyoxyethyleneethanol, a perfluoroalkyl alkoxylate or a fluorinated alkyl ester.

具體例可列舉LE-604、LE-605、LINC-151-EPA(共榮社化學公司製造)、Megafac(註冊商標)F171、172、173(DIC公司製造)、Fluorad(註冊商標)FC430、FC431(住友3M公司製造)、Asahi Guard AG(註冊商標)710、Surflon(註冊商標)S-382、SC-101、102、103、 104、105(旭硝子公司製造)等。 Specific examples thereof include LE-604, LE-605, LINC-151-EPA (manufactured by Kyoeisha Chemical Co., Ltd.), Megafac (registered trademark) F171, 172, and 173 (manufactured by DIC Corporation), Fluorad (registered trademark) FC430, and FC431. (manufactured by Sumitomo 3M), Asahi Guard AG (registered trademark) 710, Surflon (registered trademark) S-382, SC-101, 102, 103, 104, 105 (made by Asahi Glass Co., Ltd.).

至於本實施形態之樹脂組合物中所添加之(b)成分之添加量，就玻璃基板剝離聚醯亞胺樹脂層之剝離性之觀點而言，相對於聚醯亞胺或聚醯亞胺前驅物100質量份較佳為0.001質量份以上，更佳為0.01質量份以上。另一方面，就聚醯亞胺樹脂層對玻璃基板之密接性、聚醯亞胺之耐熱性之觀點而言，上述添加量較佳為10質量份以下，更佳為5質量份以下。藉由使上述添加量為10質量份以下，可於裝置之製造步驟中防止由於產生逸氣而造成之裝置污染。 The amount of the component (b) to be added to the resin composition of the present embodiment is relative to the polyimide or polyimine precursor from the viewpoint of the peeling property of the glass substrate from the release of the polyimide film. The amount of the substance is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more. On the other hand, the addition amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, from the viewpoint of the adhesion of the polyimide film to the glass substrate and the heat resistance of the polyimide. By making the above-mentioned addition amount 10 parts by mass or less, it is possible to prevent device contamination due to generation of outgas in the manufacturing steps of the apparatus.

本實施形態中之(b)成分之添加量可藉由液體層析質量分析(LC-MS)而測定。 The amount of the component (b) added in the present embodiment can be measured by liquid chromatography mass spectrometry (LC-MS).

(c)烷氧基矽烷化合物 (c) alkoxydecane compound

本實施形態之烷氧基矽烷化合物若為具有選自由胺基、胺基甲酸酯基、羧基、芳基、酸酐基、醯胺基及聚合性環狀醚基所組成之群中之至少1種官能基的烷氧基矽烷化合物，則並無特別限定。藉由具有該等官能基，與聚醯胺酸或聚醯亞胺之相溶性提高，由於芳香族重疊或醯亞胺之分子間相互作用、與聚醯胺酸或聚醯亞胺中之胺基或酸酐基之反應而造成之聚醯亞胺樹脂層於玻璃基板上之密接性提高。 The alkoxydecane compound of the present embodiment is at least 1 selected from the group consisting of an amine group, a urethane group, a carboxyl group, an aryl group, an acid anhydride group, a guanamine group, and a polymerizable cyclic ether group. The functional alkoxydecane compound is not particularly limited. By having such functional groups, the compatibility with polyglycolic acid or polyamidiamine is improved, due to aromatic overlap or intermolecular interaction of quinone imine, and amine in polylysine or polyimine The adhesion of the polyimide resin layer to the glass substrate due to the reaction of the group or the acid anhydride group is improved.

就聚醯亞胺樹脂層之自玻璃基板之剝離性變良好之觀點而言，較佳為本實施形態之烷氧基矽烷化合物具有選自胺基甲酸酯基、羧基、醯胺基及芳基之群組的至少1種之官能基。 The alkoxydecane compound of the present embodiment preferably has a group selected from the group consisting of a urethane group, a carboxyl group, a decyl group and a aryl group, from the viewpoint that the releasability of the polyimide film from the glass substrate is improved. At least one functional group of the group.

本實施形態之烷氧基矽烷化合物具體而言為下述通式(I)所表示之矽烷化合物。 The alkoxydecane compound of the present embodiment is specifically a decane compound represented by the following formula (I).

R1R2 aSi(R3)3-a‧‧‧(I) R 1 R 2 a Si(R 3 ) 3-a ‧‧‧(I)

{式中，R1係於碳原子數為1~20之直鏈狀、支鏈狀、或環狀之有機基中具有選自胺基、胺基甲酸酯基、羧基、芳基、酸酐基、醯胺基及聚合性環狀醚基之群組的至少1種官能基的有機基，R2係包含光 聚合性不飽和雙鍵基或聚合性環狀醚鍵基之碳原子數為2~20之基、碳原子數為6~20之芳基、碳原子數為2~20之烷基芳基、亦可經巰基或胺基取代之碳原子數為1~20之烷基、碳原子數為5~20之環烷基、或包含羧基或二羧酸酐基之碳原子數為4~20之基，R3係選自由甲氧基、乙氧基、丙氧基、異丙氧基所組成之群中之至少1種一價有機基、羥基、或氯(Cl)，而且a為0或1之整數} In the formula, R 1 is selected from the group consisting of an amine group, a carbamate group, a carboxyl group, an aryl group, and an acid anhydride in a linear, branched or cyclic organic group having 1 to 20 carbon atoms. An organic group having at least one functional group of a group of a fluorenyl group and a polymerizable cyclic ether group, and the number of carbon atoms of the R 2 -based photopolymerizable unsaturated double bond group or the polymerizable cyclic ether bond group is a base of 2 to 20, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms which may be substituted by a mercapto group or an amine group, a cycloalkyl group having 5 to 20 carbon atoms or a group having 4 to 20 carbon atoms including a carboxyl group or a dicarboxylic anhydride group, and R 3 is selected from a methoxy group, an ethoxy group, a propoxy group, and an isopropyl group. At least one monovalent organic group, hydroxyl group, or chlorine (Cl) in the group consisting of oxy groups, and a is an integer of 0 or 1}

此處，所謂具有胺基之烷氧基矽烷化合物為R1之碳原子數為1~20之直鏈狀、支鏈狀、或環狀之有機基中具有胺基之烷氧基矽烷化合物。例如可列舉胺基丙基三甲氧基矽烷、胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基二乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷等。 Here, the alkoxydecane compound having an amine group is an alkoxydecane compound having an amine group in a linear, branched or cyclic organic group having 1 to 20 carbon atoms and having R 1 . For example, aminopropyltrimethoxydecane, aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(amine) can be cited. Benzyl)-3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(Amino B 3-aminopropylmethyldiethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropylmethyldimethyl Oxaloxane, 3-aminopropyldiethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, and the like.

所謂具有胺基甲酸酯基之烷氧基矽烷化合物為R1之碳原子數為1~20之直鏈狀、支鏈狀、或環狀之有機基中具有胺基甲酸酯基的烷氧基矽烷化合物。例如可列舉(3-三甲氧基矽烷基丙基)-第三丁基胺基甲酸酯、及(3-三乙氧基矽烷基丙基)-第三丁基胺基甲酸酯。 The alkoxy decane compound having a urethane group is an alkyl group having a urethane group in a linear, branched or cyclic organic group having 1 to 20 carbon atoms of R 1 . Oxydecane compound. For example, (3-trimethoxydecylpropyl)-t-butylaminocarbamate, and (3-triethoxydecylpropyl)-t-butylaminoformate are mentioned.

所謂具有酸酐基之烷氧基矽烷化合物為R1之碳原子數為1~20之直鏈狀、支鏈狀、或環狀之有機基中具有二羧酸酐基的烷氧基矽烷化合物。 The alkoxydecane compound having an acid anhydride group is an alkoxydecane compound having a dicarboxylic anhydride group in a linear, branched or cyclic organic group having 1 to 20 carbon atoms and having R 1 .

作為R1而較佳之有機基例如可列舉琥珀酸酐基(R1-1)、環己二羧酸酐基(R1-2)、4-甲基-環己二羧酸酐基(R1-3)、5-甲基-環己二羧酸酐基(R1-4)、聯環庚烷二羧酸酐基(R1-5)、7-氧雜-聯環庚烷二羧酸酐基(R1-6)、及鄰苯二甲酸酐基(R1-7)。 Preferred examples of the organic group as R 1 include a succinic anhydride group (R 1 -1), a cyclohexanedicarboxylic anhydride group (R 1 -2), and a 4-methyl-cyclohexanedicarboxylic anhydride group (R 1 -3). , 5-methyl-cyclohexanedicarboxylic anhydride group (R 1 -4), bicycloheptane dicarboxylic anhydride group (R 1 -5), 7-oxa-bicycloheptane dicarboxylic anhydride group (R 1 -6), and phthalic anhydride groups (R 1 -7).

所謂具有羧基之烷氧基矽烷化合物為R1之碳原子數為1~20之直鏈狀、支鏈狀、或環狀之有機基中含有羧基的烷氧基矽烷化合物。 The alkoxydecane compound having a carboxyl group is an alkoxydecane compound having a carboxyl group in a linear, branched or cyclic organic group having 1 to 20 carbon atoms in R 1 .

作為R1而較佳之有機基例如可列舉琥珀酸基或其半酯基(R1-8)、環己二羧酸基或其半酯基(R1-9)、4-甲基-環己二羧酸基或其半酯基(R1-10)、5-甲基-環己二羧酸基或其半酯基(R1-11)、聯環庚烷二羧酸基或其半酯基(R1-12)、7-氧雜-聯環庚烷二羧酸基或其半酯基(R1-13)、鄰苯二甲酸基或其半酯基(R1-14)。 Preferred examples of the organic group as R 1 include a succinic acid group or a half ester group thereof (R 1 -8), a cyclohexanedicarboxylic acid group or a half ester group thereof (R 1 -9), and a 4-methyl-ring. Hexadicarboxylic acid group or its half ester group (R 1 -10), 5-methyl-cyclohexanedicarboxylic acid group or its half ester group (R 1 -11), bicycloheptane dicarboxylic acid group or Semi-ester group (R 1 -12), 7-oxa-bicycloheptane dicarboxylic acid group or its half ester group (R 1 -13), phthalic acid group or its half ester group (R 1 -14) ).

所謂具有芳基之烷氧基矽烷化合物為R1之碳原子數為1~20之直鏈狀、支鏈狀、或環狀之有機基中具有1個以上碳原子數為6~20之芳香族環的烷氧基矽烷化合物。例如可列舉苯基三甲氧基矽烷、苯基三乙氧基矽烷、苯基甲基二甲氧基矽烷、苯基甲基二乙氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、及N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷之鹽酸鹽。 The so-called aromatic group having an alkoxy compound of silicon alkoxy carbon atoms of R 1 is from 1 to 20 of the linear, branched, or cyclic organic group having one or more of a number of aromatic carbon atoms of 6 to 20 Acyclic alkoxydecane compound. Examples thereof include phenyltrimethoxydecane, phenyltriethoxydecane, phenylmethyldimethoxydecane, phenylmethyldiethoxydecane, diphenyldimethoxydecane, and diphenyl. Diethoxy decane, and the hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane.

所謂具有醯胺基之烷氧基矽烷化合物為通式(I)中之R1於碳原子數為1~20之直鏈狀、支鏈狀、或環狀之有機基中具有醯胺基的烷氧基矽烷化合物。 The alkoxydecane compound having a mercaptoamine group is a compound of the formula (I) wherein R 1 has a mercapto group in a linear, branched or cyclic organic group having 1 to 20 carbon atoms. Alkoxydecane compound.

上述具有醯胺基之烷氧基矽烷化合物可藉由具有胺基之烷氧基矽烷化合物與羧酸、醯氯、二羧酸酐、或四羧酸酐之反應，或具有羧基、醯氯基、或酸酐基之烷氧基矽烷化合物與胺之反應而獲得。 The alkoxydecane compound having a mercaptoamine group may be reacted with a carboxylic acid, hydrazine chloride, a dicarboxylic anhydride, or a tetracarboxylic anhydride by an alkoxydecane compound having an amine group, or may have a carboxyl group, a fluorenyl chloride group, or Obtained by the reaction of an acid anhydride-based alkoxydecane compound with an amine.

其中，就反應之容易性與所得之反應物之純度之觀點而言，較佳為藉由具有胺基之烷氧基矽烷化合物與二羧酸酐或四羧酸酐之反應而獲得，或藉由具有酸酐基之烷氧基矽烷化合物與胺之反應而獲得之具有醯胺基的烷氧基矽烷化合物。 Among them, from the viewpoint of the easiness of the reaction and the purity of the obtained reactant, it is preferably obtained by a reaction of an alkoxydecane compound having an amine group with a dicarboxylic anhydride or a tetracarboxylic anhydride, or by having An alkoxydecane compound having a mercaptoamine group obtained by reacting an acid anhydride-based alkoxydecane compound with an amine.

於使具有胺基之烷氧基矽烷化合物與酸酐反應之情形時，具有胺基之烷氧基矽烷化合物可列舉前述之化合物。二羧酸酐例如可列舉琥珀酸酐、環己二羧酸酐、4-甲基-環己二羧酸酐、5-甲基-環己二羧 酸酐、聯環庚烷二羧酸酐、7-氧雜聯環庚烷二羧酸酐、四氫鄰苯二甲酸酐、偏苯三酸酐、均苯四甲酸酐、己二酸酐、鄰苯二甲酸酐、(3-三甲氧基矽烷基丙基)琥珀酸酐、(3-三乙氧基矽烷基丙基)琥珀酸酐等多元酸酐。又，四羧酸酐例如可列舉均苯四甲酸二酐、3,3',4,4'-聯苯四羧酸二酐、2,3,3',4'-聯苯四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、對伸苯基雙(偏苯三甲酸單酯酸酐)、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、3,3'-氧雙鄰苯二甲酸二酐、及4,4'-氧雙鄰苯二甲酸二酐。該等可分別單獨使用、或將2種以上組合使用。 In the case where an alkoxydecane compound having an amino group is reacted with an acid anhydride, the alkoxydecane compound having an amine group may, for example, be a compound as described above. Examples of the dicarboxylic acid anhydride include succinic anhydride, cyclohexanedicarboxylic anhydride, 4-methyl-cyclohexanedicarboxylic anhydride, and 5-methyl-cyclohexanedicarboxylate. Anhydride, bicycloheptane dicarboxylic anhydride, 7-oxabicycloheptane dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3) a polybasic acid anhydride such as trimethoxydecylpropyl succinic anhydride or (3-triethoxydecylpropyl) succinic anhydride. Further, examples of the tetracarboxylic anhydride include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyltetracarboxylic dianhydride. , 2,2',3,3'-biphenyltetracarboxylic dianhydride, p-phenylene bis(trimellitic acid monoester anhydride), 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2 3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-oxydiphthalic dianhydride, and 4,4'-oxydiphthalic dianhydride. These may be used alone or in combination of two or more.

於使具有酸酐基之烷氧基矽烷化合物與胺反應之情形時，具有酸酐基之烷氧基矽烷化合物可列舉前述之化合物。胺例如可列舉氨、甲胺、乙胺、丙胺、異丙胺、丁胺、第三丁胺、戊胺、己胺、2-乙基己胺、庚胺、辛胺、壬胺、癸胺、十一烷胺、十二烷胺、十四烷胺、十六烷胺、1-胺基十八烷、苯胺、苯甲胺、環丙基胺、環丁基胺、環戊基胺、環己基胺、環庚基胺、環辛基胺、2-胺基甲苯、3-胺基甲苯、4-胺基甲苯、2,4-二甲基苯胺、2,3-二甲基苯胺、2,5-二甲基苯胺、2,6-二甲基苯胺、3,4-二甲基苯胺、3,5-二甲基苯胺、2,4,5-三甲基苯胺、2,4,6-三甲基苯胺、2,3,4,5-四甲基苯胺、2,3,5,6-四甲基苯胺、2,3,4,6-四甲基苯胺、2-乙基-3-己基苯胺、2-乙基-4-己基苯胺、2-乙基-5-己基苯胺、2-乙基-6-己基苯胺、3-乙基-4-己基苯胺、3-乙基-5-己基苯胺、3-乙基-2-己基苯胺、4-乙基-2-己基苯胺、5-乙基-2-己基苯胺、6-乙基-2-己基苯胺、4-乙基-3-己基苯胺、5-乙基-3-己基苯胺、1,2-苯二胺、1,3-苯二胺、1,4-苯二胺、2-胺基苯甲胺、3-胺基苯甲胺、4-胺基苯甲胺、2-(4-胺基苯基)乙基胺、2-(3-胺基苯基)乙基胺、2-(2-胺基苯基)乙基胺、2,3-二胺基甲苯、2,4-二胺基甲苯、2,5-二胺基甲苯、2,6-二胺基甲苯、3,4-二胺基甲苯、2,3-二甲基-對苯二胺、2,5-二甲基-對苯二胺、2,6-二甲基-對苯二胺、2,4-二甲基-間苯二 胺、2,5-二甲基-間苯二胺、2,6-二甲基-間苯二胺、4,5-二甲基-間苯二胺、3,4-二甲基-鄰苯二胺、3,5-二甲基-鄰苯二胺、3,6-二甲基-鄰苯二胺、1,3-二胺基-2,4,6-三甲基苯、2,3,5,6-四甲基-1,4-苯二胺、2,4,5,6-四甲基-1,3-苯二胺、3,4,5,6-四甲基-1,2-苯二胺、2,4-二胺基-3,5-二乙基甲苯、2,3-二胺基-4,5-二乙基甲苯、2,4-二胺基-4,6-二乙基甲苯、2,3-二胺基-5,6-二乙基甲苯、2,4-二胺基-3,6-二乙基甲苯、2,5-二胺基-3,4-二乙基甲苯、2,5-二胺基-3,6-二乙基甲苯、2,5-二胺基-4,6-二乙基甲苯、2,3-二胺基-4,5-二乙基甲苯、2,3-二胺基-4,6-二乙基甲苯、2,3-二胺基-4,5,6-三乙基甲苯、2,4-二胺基-3,5,6-三乙基甲苯、2,5-二胺基-3,4,6-三乙基甲苯、2-甲氧基苯胺、3-甲氧基苯胺、4-甲氧基苯胺、2-甲氧基-3-甲基苯胺、2-甲氧基-4-甲基苯胺、2-甲氧基-5-甲基苯胺、2-甲氧基-6-甲基苯胺、3-甲氧基-2-甲基苯胺、3-甲氧基-4-甲基苯胺、3-甲氧基-5-甲基苯胺、3-甲氧基-6-甲基苯胺、4-甲氧基-2-甲基苯胺、4-甲氧基-3-甲基苯胺、2-乙氧基苯胺、3-乙氧基苯胺、4-乙氧基苯胺、4-甲氧基-5-甲基苯胺、4-甲氧基-6-甲基苯胺、2-甲氧基-3-乙基苯胺、2-甲氧基-4-乙基苯胺、2-甲氧基-5-乙基苯胺、2-甲氧基-6-乙基苯胺、3-甲氧基-2-乙基苯胺、3-甲氧基-4-乙基苯胺、3-甲氧基-5-乙基苯胺、3-甲氧基-6-乙基苯胺、4-甲氧基-2-乙基苯胺、4-甲氧基-3-乙基苯胺、2-甲氧基-3,4,5-三甲基苯胺、3-甲氧基-2,4,5-三甲基苯胺、及4-甲氧基-2,3,5-三甲基苯胺。該等可分別單獨使用、或將2種以上組合使用。 In the case of reacting an alkoxydecane compound having an acid anhydride group with an amine, the alkoxydecane compound having an acid anhydride group may, for example, be a compound as described above. Examples of the amine include ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, pentylamine, hexylamine, 2-ethylhexylamine, heptylamine, octylamine, decylamine, decylamine, Undecylamine, dodecylamine, tetradecylamine, hexadecylamine, 1-aminooctadecane, aniline, benzylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, ring Hexylamine, cycloheptylamine, cyclooctylamine, 2-aminotoluene, 3-aminotoluene, 4-aminotoluene, 2,4-dimethylaniline, 2,3-dimethylaniline, 2 , 5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,5-trimethylaniline, 2,4, 6-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,5,6-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2-ethyl 3-hexylaniline, 2-ethyl-4-hexylaniline, 2-ethyl-5-hexylaniline, 2-ethyl-6-hexylaniline, 3-ethyl-4-hexylaniline, 3-ethyl 5-5-hexylaniline, 3-ethyl-2-hexylaniline, 4-ethyl-2-hexylaniline, 5-ethyl-2-hexylaniline, 6-ethyl-2-hexylaniline, 4-ethyl -3-hexylaniline, 5-ethyl-3-hexylaniline, 1,2-phenylenediamine, 1,3-phenylenediamine 1,4-phenylenediamine, 2-aminobenzylamine, 3-aminobenzylamine, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, 2-(3 -aminophenyl)ethylamine, 2-(2-aminophenyl)ethylamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene , 2,6-diaminotoluene, 3,4-diaminotoluene, 2,3-dimethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,6-di Methyl-p-phenylenediamine, 2,4-dimethyl-m-phenylene Amine, 2,5-dimethyl-m-phenylenediamine, 2,6-dimethyl-m-phenylenediamine, 4,5-dimethyl-m-phenylenediamine, 3,4-dimethyl-ortho Phenylenediamine, 3,5-dimethyl-o-phenylenediamine, 3,6-dimethyl-o-phenylenediamine, 1,3-diamino-2,4,6-trimethylbenzene, 2 ,3,5,6-tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetramethyl-1,3-phenylenediamine, 3,4,5,6-tetramethyl -1,2-phenylenediamine, 2,4-diamino-3,5-diethyltoluene, 2,3-diamino-4,5-diethyltoluene, 2,4-diamino -4,6-diethyltoluene, 2,3-diamino-5,6-diethyltoluene, 2,4-diamino-3,6-diethyltoluene, 2,5-diamine 3-3,4-diethyltoluene, 2,5-diamino-3,6-diethyltoluene, 2,5-diamino-4,6-diethyltoluene, 2,3-di Amino-4,5-diethyltoluene, 2,3-diamino-4,6-diethyltoluene, 2,3-diamino-4,5,6-triethyltoluene, 2, 4-diamino-3,5,6-triethyltoluene, 2,5-diamino-3,4,6-triethyltoluene, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-methoxy-3-methylaniline, 2-methoxy-4-methylaniline, 2-methoxy-5-methylaniline, 2-methoxy-6 -methylaniline, 3-methoxy-2-methylaniline, 3- Oxy-4-methylaniline, 3-methoxy-5-methylaniline, 3-methoxy-6-methylaniline, 4-methoxy-2-methylaniline, 4-methoxy 3-methylaniline, 2-ethoxyaniline, 3-ethoxyaniline, 4-ethoxyaniline, 4-methoxy-5-methylaniline, 4-methoxy-6-methyl Aniline, 2-methoxy-3-ethylaniline, 2-methoxy-4-ethylaniline, 2-methoxy-5-ethylaniline, 2-methoxy-6-ethylaniline, 3-methoxy-2-ethylaniline, 3-methoxy-4-ethylaniline, 3-methoxy-5-ethylaniline, 3-methoxy-6-ethylaniline, 4- Methoxy-2-ethylaniline, 4-methoxy-3-ethylaniline, 2-methoxy-3,4,5-trimethylaniline, 3-methoxy-2,4,5 -trimethylaniline, and 4-methoxy-2,3,5-trimethylaniline. These may be used alone or in combination of two or more.

所謂具有聚合性環狀醚基之烷氧基矽烷化合物為R1之碳原子數為1~20之直鏈狀、支鏈狀、或環狀之有機基中具有如縮水甘油基或環氧環己基這樣的具有反應性之環狀醚基的烷氧基矽烷化合物。例如可列舉3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙 基甲基二乙氧基矽烷、2-(3,4-環氧環己基)三甲氧基矽烷、2-(3,4-環氧環己基)三乙氧基矽烷、2-(3,4-環氧環己基)甲基二甲氧基矽烷、2-(3,4-環氧環己基)甲基二乙氧基矽烷。 Silane called an alkoxy group having a cyclic ether compound having a polymerizable group of the carbon atoms R 1 is a 1 to 20 of the linear, branched, or cyclic organic group with the glycidyl group or an epoxy ring such as An alkoxydecane compound having a reactive cyclic ether group such as hexyl. Examples thereof include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 3-glycidol. Oxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)trimethoxydecane, 2-(3,4-epoxycyclohexyl)triethoxydecane, 2-( 3,4-epoxycyclohexyl)methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)methyldiethoxydecane.

可與上述合併添加的烷氧基矽烷化合物之具體例可列舉甲基三甲氧基矽烷、甲基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、二乙基二甲氧基矽烷、二乙基二乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、環己基三甲氧基矽烷、環己基三乙氧基矽烷、環己基甲基二甲氧基矽烷、環己基甲基二乙氧基矽烷、二環戊基二甲氧基矽烷、二環戊基二乙氧基矽烷、十八烷基三甲氧基矽烷、十八烷基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基甲基二乙氧基矽烷、甲基三氯矽烷、苯基三氯矽烷、二甲基二氯矽烷、三甲基氯矽烷、三乙基氯矽烷、第三丁基二甲基氯矽烷、三異丙基氯矽烷等。該等可分別單獨使用、或將2種以上組合使用。 Specific examples of the alkoxydecane compound which may be added in combination with the above may include methyltrimethoxydecane, methyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, and B. Trimethoxy decane, ethyl triethoxy decane, diethyl dimethoxy decane, diethyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, cyclohexyl trimethyl Oxoxane, cyclohexyltriethoxydecane, cyclohexylmethyldimethoxydecane, cyclohexylmethyldiethoxydecane, dicyclopentyldimethoxydecane, dicyclopentyldiethoxy Decane, octadecyltrimethoxydecane, octadecyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropylmethyldi Methoxydecane, 3-mercaptopropylmethyldiethoxydecane, methyltrichlorodecane, phenyltrichlorodecane, dimethyldichlorodecane, trimethylchlorodecane, triethylchlorodecane, Tributyldimethylchlorodecane, triisopropylchlorodecane, and the like. These may be used alone or in combination of two or more.

至於本實施形態之樹脂組合物中所添加之(c)成分之添加量，就玻璃基板對聚醯亞胺樹脂層之密接性之觀點而言，相對於聚醯亞胺或聚醯亞胺前驅物100質量份較佳為0.001質量份以上，更佳為0.01質量份以上。另一方面，就玻璃基板剝離聚醯亞胺樹脂層之剝離性、聚醯亞胺之耐熱性之觀點而言，上述添加量較佳為9質量份以下，更佳為5質量份以下。 The amount of the component (c) to be added to the resin composition of the present embodiment is relative to the polyimide or polyimine precursor from the viewpoint of the adhesion of the glass substrate to the polyimide film. The amount of the substance is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more. On the other hand, the amount of addition is preferably 9 parts by mass or less, and more preferably 5 parts by mass or less, from the viewpoint of the peeling property of the polyimide substrate layer and the heat resistance of the polyimide.

本實施形態中之(c)成分之添加量可藉由液體層析質量分析(LC-MS)而測定。 The amount of the component (c) in the present embodiment can be measured by liquid chromatography mass spectrometry (LC-MS).

(d)溶劑 (d) solvent

本實施形態之樹脂組合物亦可溶解於溶劑中，採用作為清漆狀樹脂組合物之形態。此處所使用的溶劑可列舉N-甲基-2-吡咯啶酮 (NMP)、γ-丁內酯、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、二乙二醇二甲醚、二乙二醇二***、二乙二醇二丁醚、丙二醇單甲醚、二丙二醇單甲醚、丙二醇單甲醚乙酸酯、乳酸甲酯、乳酸乙酯、乳酸丁酯、甲基-1,3-丁二醇乙酸酯、1,3-丁二醇-3-單甲醚、丙酮酸甲酯、丙酮酸乙酯、甲基-3-甲氧基丙酸酯等，可單獨使用亦可混合使用。 The resin composition of the present embodiment may be dissolved in a solvent and used as a varnish-like resin composition. The solvent used herein may, for example, be N-methyl-2-pyrrolidone. (NMP), γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butyl Glycol acetate, 1,3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, etc., may be used alone or in combination. .

其中，更佳為非質子性極性溶劑，具體而言可列舉N-甲基-2-吡咯啶酮(NMP)、γ-丁內酯等。尤佳為N-甲基-2-吡咯啶酮(NMP)。 Among them, an aprotic polar solvent is more preferable, and specific examples thereof include N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone. More preferably N-methyl-2-pyrrolidone (NMP).

此種溶劑之使用量因所得之膜厚而異，相對於聚醯亞胺或聚醯亞胺前驅物100質量份，於10質量份~10000質量份之範圍內使用。 The amount of such a solvent to be used varies depending on the film thickness obtained, and is used in the range of 10 parts by mass to 10,000 parts by mass based on 100 parts by mass of the polyimide or polyimide precursor.

於本實施形態之樹脂組合物及聚醯亞胺樹脂層中，亦可包含上述成分以外之成分，其他添加成分設為並不對聚醯亞胺樹脂與無機基板之180°剝離強度造成影響之程度的添加量，以可同時實現良好之密接性與剝離性之方式進行調整。 In the resin composition and the polyimide resin layer of the present embodiment, components other than the above components may be contained, and other additive components are not affected by the 180° peel strength of the polyimide film and the inorganic substrate. The amount of addition is adjusted in such a manner that good adhesion and peelability can be achieved at the same time.

其次，對本實施形態之積層體加以說明。本實施形態之積層體可藉由如下之方法而獲得：將上述清漆狀之藉由醯亞胺化處理而成為5%熱分解溫度為350℃以上之聚醯亞胺的聚醯亞胺前驅物組合物塗佈於無機基板上，實施熱處理對聚醯亞胺前驅物進行聚醯亞胺化而形成聚醯亞胺樹脂層的方法；或者將5%熱分解溫度為350℃以上之聚醯亞胺組合物塗佈於無機基板上，實施熱處理而將溶劑除去的方法。 Next, the laminated body of this embodiment will be described. The laminate of the present embodiment can be obtained by the following method: a phthalocyanine precursor of a polyimine having a 5% thermal decomposition temperature of 350 ° C or more by imidization of the varnish. Coating the composition on an inorganic substrate, performing a heat treatment on the polyamidene precursor to polyiminate to form a polyimine resin layer; or 5% thermal decomposition temperature of 350 ° C or more A method in which an amine composition is applied onto an inorganic substrate and subjected to heat treatment to remove the solvent.

此處，作為無機基板，自於裝置形成步驟中進行位置對準之方面考慮，較佳為透明，尤佳為玻璃基板。玻璃基板可使用無鹼玻璃基板、鈉鈣玻璃基板、石英玻璃基板等，於多數半導體製造步驟中使用無鹼玻璃基板，無機基板較佳為無鹼玻璃基板。 Here, the inorganic substrate is preferably transparent, and is preferably a glass substrate from the viewpoint of performing alignment in the device forming step. As the glass substrate, an alkali-free glass substrate, a soda lime glass substrate, a quartz glass substrate or the like can be used, and an alkali-free glass substrate is used in many semiconductor manufacturing steps, and the inorganic substrate is preferably an alkali-free glass substrate.

又，無機基板包含為了控制與聚醯亞胺組合物膜之密接性及剝離性而預先用偶合劑對無機基板之表面進行了處理者。 Further, the inorganic substrate includes a surface in which the surface of the inorganic substrate is previously treated with a coupling agent in order to control the adhesion to the polyimide film composition and the releasability.

又，至於製造本實施形態之積層體之方法，可藉由公知之方法而於無機基板上展開本實施形態之樹脂組合物，進行熱處理而進行製造。 Moreover, as for the method of producing the laminated body of the present embodiment, the resin composition of the present embodiment can be developed on an inorganic substrate by a known method, and heat-treated to produce the resin composition.

展開方法例如可列舉旋塗、狹縫塗佈及刮刀塗佈之公知之塗佈方法。又，熱處理係於無機基板上展開樹脂組合物後，主要以脫溶劑為目的而在300℃以下之溫度下進行1分鐘~300分鐘之熱處理，進一步在氮等惰性環境下、300℃~550℃之溫度下進行1分鐘~300分鐘之熱處理而對聚醯亞胺前驅物進行聚醯亞胺化。 The development method is, for example, a known coating method of spin coating, slit coating, and doctor blade coating. In addition, after the resin composition is developed on the inorganic substrate, the heat treatment is performed at a temperature of 300 ° C or lower for the purpose of desolvation, and further, in an inert atmosphere such as nitrogen, at 300 ° C to 550 ° C for 1 minute to 300 minutes. The polyimine imide is polyimidized by heat treatment at a temperature of from 1 minute to 300 minutes.

本實施形態之積層體藉由對本實施形態之樹脂組合物進行熱處理而顯示出優異之耐熱性、尺寸穩定性、於無機基板上之耐熱密接性，可應用為可撓性裝置之裝置形成時的基板。特別係於形成低溫多晶矽薄型半導體或氧化物半導體時之熱老化步驟或準分子雷射步驟等於惰性環境下超過300℃之步驟、更具體而言為300℃~500℃下，亦可並不自積層體剝離聚醯亞胺樹脂層地良好地形成裝置。另外，於形成裝置後，藉由於聚醯亞胺樹脂層與玻璃界面切入切口而剝去之方法或藉由雷射而將積層體之樹脂接著層除去之方法、於空氣下等進行熱處理之方法等，可自積層體容易地剝離形成有裝置之聚醯亞胺樹脂層。另外，所謂「樹脂接著層」係於樹脂接著用無機基板表面所設的無機層或有機層，於本實施形態中，可具有樹脂接著層亦可無樹脂接著層。 The laminated body of the present embodiment exhibits excellent heat resistance, dimensional stability, and heat-resistant adhesion to an inorganic substrate by heat-treating the resin composition of the present embodiment, and can be applied to a device for forming a flexible device. Substrate. In particular, the heat aging step or the excimer laser step in forming a low temperature polycrystalline thin semiconductor or oxide semiconductor is equal to a step of exceeding 300 ° C in an inert environment, more specifically, 300 ° C to 500 ° C, or not The laminate peels the polyimide layer to form a device well. Further, after the device is formed, a method in which the polyimide film is cut by a slit at the interface between the polyimide film and the glass, or a method in which the resin is subsequently removed by laser, or a method of heat-treating under air or the like Alternatively, the polyimine resin layer on which the device is formed can be easily peeled off from the laminate. In addition, the "resin adhesive layer" is an inorganic layer or an organic layer provided on the surface of the inorganic substrate, and may have a resin adhesive layer or a resin-free adhesive layer in the present embodiment.

藉由本實施形態，可將聚醯亞胺樹脂層自無機基板乾淨地剝去，可於聚醯亞胺樹脂層之剝離面並無缺陷等之狀態下形成。 According to the present embodiment, the polyimide film can be cleanly peeled off from the inorganic substrate, and can be formed in a state where the peeling surface of the polyimide film is not defective.

其次，對在低溫多晶矽、氧化物半導體TFT驅動型之有機EL可撓性顯示器之製造中使用本實施形態之樹脂組合物之情形加以說明。 Next, a case where the resin composition of the present embodiment is used in the production of a low-temperature polysilicon or an oxide semiconductor TFT-driven organic EL flexible display will be described.

圖1~圖7係表示使用本實施形態之樹脂組合物的可撓性顯示器之製造步驟的剖面模式圖。 1 to 7 are cross-sectional schematic views showing a manufacturing procedure of a flexible display using the resin composition of the present embodiment.

首先，如圖1A所示般，例如準備包含無鹼玻璃基板之第1基板11。其次，如圖1B所示般，藉由如下方法而形成第1聚醯亞胺樹脂層12：於第1基板11之表面塗佈上述藉由本實施形態之醯亞胺化處理而成為5%熱分解溫度為350℃以上之聚醯亞胺的聚醯亞胺前驅物樹脂組合物，其次藉由熱處理而進行聚醯亞胺化的方法；或塗佈5%熱分解溫度為350℃以上之聚醯亞胺樹脂組合物，其次藉由熱處理將溶劑除去的方法。 First, as shown in FIG. 1A, for example, a first substrate 11 including an alkali-free glass substrate is prepared. Next, as shown in FIG. 1B, the first polyimide layer 12 is formed by coating the surface of the first substrate 11 with the 5% imidization treatment of the present embodiment. a polyimine imide precursor resin composition having a decomposition temperature of 350 ° C or more, followed by a polyimidization by heat treatment; or a coating of 5% thermal decomposition temperature of 350 ° C or higher The quinone imine resin composition is a method of removing the solvent by heat treatment.

其次，如圖2所示般，於第1基板11之第1聚醯亞胺樹脂層12之上部形成第1障壁層101。 Next, as shown in FIG. 2, the first barrier layer 101 is formed on the upper portion of the first polyimide layer 12 of the first substrate 11.

另外，如圖2所示般，於第1障壁層101上依序形成半導體層102、閘極絕緣膜103、閘極電極104、層間絕緣膜105、接觸孔106、源極-汲極電極107a、107b，形成薄膜電晶體(TFT)108。 Further, as shown in FIG. 2, the semiconductor layer 102, the gate insulating film 103, the gate electrode 104, the interlayer insulating film 105, the contact hole 106, and the source-drain electrode 107a are sequentially formed on the first barrier layer 101. 107b, forming a thin film transistor (TFT) 108.

此處，半導體層102係由多晶矽而形成。半導體層102可藉由如下方式而形成：首先形成非晶矽，使其結晶化而變化為多晶矽。此種結晶化方法例如可列舉RTA(Rapid Thermal Annealing，快速熱退火)、SPC(Solid Phase Crystallzation，固相結晶)、ELA(Excimer Laser Annealing，準分子雷射退火)、MIC(Metal Induced Crystallization，金屬誘發結晶)、MILC(Metal Induced Lateral Crystallization，金屬誘導橫向結晶)及SLS(Sequential Lateral Solidification，連續橫向固化)。 Here, the semiconductor layer 102 is formed of polysilicon. The semiconductor layer 102 can be formed by first forming an amorphous germanium, crystallizing it, and changing to polycrystalline germanium. Examples of such a crystallization method include RTA (Rapid Thermal Annealing), SPC (Solid Phase Crystallization), ELA (Excimer Laser Annealing), and MIC (Metal Induced Crystallization). Induced crystallization), MILC (Metal Induced Lateral Crystallization) and SLS (Sequential Lateral Solidification).

其次，於TFT 108之上部形成顯示器元件。如圖3所示般，首先於源極-汲極電極107a、107b之上部形成平坦化層109。其次，為了於TFT 108之上部形成有機發光元件(OLED)，首先於源極-汲極電極107a、107b之一電極107b上形成接觸孔110而與第1電極111電性連結。第1電極111作為其後有機發光元件中所具備的電極中的一電極而發揮功能。 Next, a display element is formed on the upper portion of the TFT 108. As shown in FIG. 3, a planarization layer 109 is first formed on the upper portions of the source-drain electrodes 107a and 107b. Next, in order to form an organic light-emitting element (OLED) on the upper portion of the TFT 108, first, a contact hole 110 is formed on one of the source-drain electrodes 107a and 107b, and is electrically connected to the first electrode 111. The first electrode 111 functions as one of the electrodes included in the subsequent organic light-emitting element.

其次，如圖4所示般，於第1電極111上以其至少一部分露出之方 式藉由絕緣性物質形成圖案化之像素定義膜112。其次，於第1電極111之露出之部分形成包含發光層之中間層113。以該中間層113為中心，形成與第1電極111對向之第2電極114。藉此而獲得有機發光元件(OLED)(圖6中之210)。 Next, as shown in FIG. 4, at least a part of the first electrode 111 is exposed. The patterned pixel defining film 112 is formed by an insulating material. Next, an intermediate layer 113 including a light-emitting layer is formed on the exposed portion of the first electrode 111. The second electrode 114 facing the first electrode 111 is formed around the intermediate layer 113. Thereby, an organic light emitting element (OLED) (210 in Fig. 6) is obtained.

其次，對上述有機發光元件進行密封。另行製造圖5中所示之密封構件201，將密封構件201與有機發光元件之上部結合後，分離密封構件201之第2基板202。 Next, the above organic light emitting element is sealed. The sealing member 201 shown in FIG. 5 is separately manufactured, and after the sealing member 201 is bonded to the upper portion of the organic light emitting element, the second substrate 202 of the sealing member 201 is separated.

密封構件201可如圖5所示般，於例如包含無鹼玻璃基板之第2基板202之一主表面上形成第2聚醯亞胺樹脂層203，進而於第2聚醯亞胺樹脂層203之表面形成第2障壁層204而獲得。此處，第2聚醯亞胺樹脂層203可使用本實施形態之樹脂組合物而形成。其次，如圖6所示般，於有機發光元件210之上部配置密封構件201後，將該等貼合。 As shown in FIG. 5, the sealing member 201 can form a second polyimide layer 203 on the main surface of one of the second substrates 202 including the alkali-free glass substrate, and further on the second polyimide layer 203. The surface of the second barrier layer 204 is obtained. Here, the second polyimine resin layer 203 can be formed using the resin composition of the present embodiment. Next, as shown in FIG. 6, after the sealing member 201 is placed on the upper portion of the organic light-emitting element 210, the layers are bonded together.

最後，於氧之存在下、圖6所示之狀態下，例如於空氣環境下、300℃~350℃下實施熱處理。藉此可剝離與第1聚醯亞胺樹脂層12相接之第1基板11，且可剝離與第2聚醯亞胺樹脂層203相接之第2基板202。其結果獲得如圖7所示之可撓性顯示器100。 Finally, heat treatment is performed in the presence of oxygen in the state shown in Fig. 6, for example, in an air atmosphere at 300 ° C to 350 ° C. Thereby, the first substrate 11 that is in contact with the first polyimide film layer 12 can be peeled off, and the second substrate 202 that is in contact with the second polyimide film layer 203 can be peeled off. As a result, the flexible display 100 as shown in FIG. 7 is obtained.

於以上所說明之可撓性顯示器100之製造方法中，藉由使用本實施形態之樹脂組合物而起到如下上述之效果。 In the method for producing the flexible display 100 described above, the above-described effects are obtained by using the resin composition of the present embodiment.

首先，對聚醯亞胺前驅物進行聚醯亞胺化而形成之第1聚醯亞胺樹脂層12由於5%熱分解溫度為350℃以上，因此具有可耐受可撓性顯示器100之製造所需之例如超過350℃之熱處理步驟的耐熱性。具體而言，可耐受上述半導體層102之多晶矽化等之步驟。 First, the first polyimine resin layer 12 formed by polyimidization of a polyimide precursor has a 5% thermal decomposition temperature of 350 ° C or higher, thereby having the capability of withstanding the manufacture of the flexible display 100 The heat resistance of the heat treatment step of, for example, more than 350 ° C is required. Specifically, the step of polysiliconization or the like of the above semiconductor layer 102 can be endured.

具有選自由胺基、胺基甲酸酯基、羧基、芳基、酸酐基、醯胺基及聚合性環狀醚基所組成之群中之至少1種官能基的烷氧基矽烷化合物與並不具有該等基之烷氧基矽烷化合物相比較而言，與聚醯亞胺相互作用，於對樹脂組合物進行加熱時難以揮發，於400℃以上之醯 亞胺化‧配向時有效地摻入至聚醯亞胺樹脂層，因此對於無機基板，以所期望之厚度保持聚醯亞胺樹脂層，於長時間之熱處理時表現出良好之耐熱密接性(長期密接性)。其結果為，於形成半導體層102時，首先形成非晶矽層，為了使其結晶化而採用上述RTA、SPC、MIC、MIL或SLS等時，包含第1基板11及第1聚醯亞胺樹脂層12之積層體的溫度達到350℃~500℃，且直至多晶矽化完結而放置6分鐘~5小時。然而，藉由使用本實施形態之樹脂組合物，第1聚醯亞胺樹脂層12之長期密接性優異，因此可抑制於多晶矽化之最中產生第1聚醯亞胺樹脂層12自第1基板11剝離等異常。 An alkoxydecane compound having at least one functional group selected from the group consisting of an amine group, a urethane group, a carboxyl group, an aryl group, an acid anhydride group, a guanamine group, and a polymerizable cyclic ether group, and The alkoxydecane compound which does not have such a base is relatively difficult to volatilize when it is heated by the resin composition, and it is difficult to volatilize at 400 ° C or more. The imidization ‧ is effectively incorporated into the polyimide layer in the alignment, so that the polyimide substrate is maintained at a desired thickness for the inorganic substrate, and exhibits good heat-resistant adhesion during long-time heat treatment ( Long-term closeness). As a result, when the semiconductor layer 102 is formed, an amorphous germanium layer is first formed, and when the RTA, SPC, MIC, MIL, or SLS is used for crystallization, the first substrate 11 and the first polyimide are included. The temperature of the laminate of the resin layer 12 reaches 350 ° C to 500 ° C, and is allowed to stand for 6 minutes to 5 hours until the polycrystalline germanium is completed. However, by using the resin composition of the present embodiment, the first polyimine resin layer 12 is excellent in long-term adhesion, and thus it is possible to suppress the occurrence of the first polyimine resin layer 12 from the first in the polysiliconization. The substrate 11 is peeled off or the like.

又，藉由形成聚醯亞胺時之熱處理而將烷氧基矽烷化合物導入至聚醯亞胺中，因此表現出例如在惰性環境下超過400℃之耐熱密接性(初始密接性)。藉此而於上述可撓性顯示器100之製造中具有抑制產生外觀異常之效果。 Further, since the alkoxydecane compound is introduced into the polyimide by heat treatment in the formation of the polyimide, it exhibits heat-resistant adhesion (initial adhesion) of, for example, 400 ° C in an inert atmosphere. Thereby, in the manufacture of the above-mentioned flexible display 100, the effect of suppressing the appearance abnormality is suppressed.

又，本實施形態之樹脂組合物及聚醯亞胺樹脂層係包含聚矽氧界面活性劑或氟系界面活性劑者。藉此可使對於無機基板之剝離性提高。 Further, the resin composition and the polyimide layer of the present embodiment include a polyoxyn surfactant or a fluorine-based surfactant. Thereby, the peeling property with respect to an inorganic substrate can be improved.

如上所述，於本實施形態中，藉由於聚醯亞胺或聚醯亞胺前驅物中添加聚矽氧界面活性劑或氟系界面活性劑，且添加具有規定官能基之烷氧基矽烷化合物，可形成在製成聚醯亞胺樹脂層時對於無機基板具有良好之密接性及剝離性的樹脂組合物及使用其之積層體。 As described above, in the present embodiment, a polyoxynium surfactant or a fluorine-based surfactant is added to a polyimide or a polyimide precursor, and an alkoxydecane compound having a predetermined functional group is added. A resin composition having good adhesion and releasability to an inorganic substrate when formed into a polyimide film can be formed, and a laminate using the laminate.

於以上之說明中，列舉多晶矽半導體驅動型可撓性顯示器為例而加以說明，但本實施形態之可撓性裝置之製造方法例如亦可應用於如IGZO這樣的金屬氧化物半導體驅動型可撓性裝置中。 In the above description, a polycrystalline germanium semiconductor-driven flexible display is described as an example. However, the method of manufacturing the flexible device of the present embodiment can be applied to, for example, a metal oxide semiconductor-driven type such as IGZO. In the sex device.

又，用本實施形態之方法而剝離了聚醯亞胺樹脂層之玻璃基板由於聚醯亞胺之容易剝離性，可自玻璃基板上將聚醯亞胺樹脂層全部剝離。因此，對於玻璃基板表面，通過利用氧電漿或酸、鹼溶液之容 易的玻璃基板清洗步驟，藉此可回收所使用之玻璃基板。 Further, the glass substrate from which the polyimide resin layer was peeled off by the method of the present embodiment can be completely peeled off from the glass substrate by the polyetherimide resin. Therefore, for the surface of the glass substrate, by using oxygen plasma or acid, alkali solution An easy glass substrate cleaning step whereby the glass substrate used can be recovered.

其次，本發明者等人反覆進行了努力研究，結果發現藉由製成含有聚醯亞胺與特定化合物而成的可撓性裝置用基板，可使膜厚不均變小，進而於使用上述可撓性裝置用基板而製成裝置時顯示出良好之動作響應性，基於該發現而完成本發明。 Then, the inventors of the present invention have conducted intensive studies, and as a result, it has been found that by using a substrate for a flexible device comprising a polyimine and a specific compound, film thickness unevenness can be reduced, and The present invention has been completed based on the findings when the device for a flexible device is used as a device to exhibit good operational responsiveness.

本發明之可撓性裝置用基板係具有可撓性之成為例如薄的膜狀者，於可撓性記憶體、感測器、RF-ID等可撓性裝置中使用。代表性地用於可撓性顯示器中。 The substrate for a flexible device of the present invention is flexible, for example, a thin film, and is used in a flexible device such as a flexible memory, a sensor, or an RF-ID. Typically used in flexible displays.

為了如上所述地使用薄的膜狀的可撓性裝置用基板而獲得穩定之裝置動作，重要的是成為裝置之各功能層之形成面的可撓性裝置用基板之表面的平坦性高，因此必須使可撓性裝置用基板之膜厚不均變小。又，當然可撓性裝置用基板必須具有良好之可撓性，為了獲得良好之可撓性，構成可撓性裝置用基板之組成及厚度亦成為重要之要素。 In order to obtain a stable device operation by using a thin film-shaped substrate for a flexible device as described above, it is important that the surface of the flexible device substrate which is the formation surface of each functional layer of the device has high flatness. Therefore, it is necessary to reduce the film thickness unevenness of the substrate for a flexible device. Further, of course, the substrate for a flexible device must have good flexibility, and in order to obtain good flexibility, the composition and thickness of the substrate for a flexible device are also important elements.

具有可撓性之可撓性裝置用基板例如可運至連續捲繞(roll-to-roll)步驟，供至裝置形成製程。因此，一般情況下，可撓性裝置用基板可於包含裝置之各功能層的可撓性裝置之狀態下於市場上銷售，亦可以可撓性裝置用基板而單獨於市場上銷售。 The flexible substrate for flexible device can be transported, for example, to a roll-to-roll step for the device forming process. Therefore, in general, the substrate for a flexible device can be marketed in a state in which the flexible device of each functional layer of the device is included, or can be sold separately on the market for the flexible device substrate.

以下，對本發明之一實施形態(以下略記為「實施形態」)加以詳細說明。再者，本發明並不限定於以下之實施形態，可以於其主旨之範圍內進行各種變形而實施。 Hereinafter, an embodiment (hereinafter, abbreviated as "the embodiment") of the present invention will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

<可撓性裝置用基板> <Substrate for flexible device>

本實施形態之可撓性裝置用基板含有：(α)5%熱分解溫度為350℃以上之聚醯亞胺、(β)具有下述通式(1)所表示之化學結構及/或下述通式(2)所表示之化學結構之化合物、(γ)具有由下述通式(3)所表示之化學結構、羥基、羧基及磺基所組成之群中之1種以上之化合 物、(δ)具有下述通式(4)所表示之化學結構之化合物。 The substrate for a flexible device of the present embodiment contains (α) 5% polyimine having a thermal decomposition temperature of 350 ° C or higher, and (β) having a chemical structure represented by the following general formula (1) and/or The compound of the chemical structure represented by the formula (2), (γ) has a chemical structure represented by the following formula (3), a combination of one or more of a group consisting of a hydroxyl group, a carboxyl group and a sulfo group. And (δ) a compound having a chemical structure represented by the following formula (4).

此處，於下述[化9]中表示通式(1)所表示之聚矽氧系界面活性劑之非極性部位。 Here, the non-polar portion of the polyfluorene-based surfactant represented by the general formula (1) is represented by the following [Chemical Formula 9].

又，於下述[化10]中表示通式(2)所表示之氟系界面活性劑之非極性部位。 Moreover, the nonpolar portion of the fluorine-based surfactant represented by the general formula (2) is shown in the following [Chemical Formula 10].

又，於下述[化11]中表示通式(3)所表示之聚矽氧系、氟系界面活性劑之極性部位之一態樣。 In addition, in the following [Chemical Formula 11], one of the polar portions of the polyfluorene-based or fluorine-based surfactant represented by the general formula (3) is shown.

[化11] 通式(3)-(CH2)nO- General formula (3)-(CH 2 ) n O-

(n表示1以上5以下之整數) (n represents an integer of 1 or more and 5 or less)

又，於下述[化12]中表示通式(4)所表示之3官能烷氧基矽烷在水解縮合物基。 Further, in the following [Chemical Formula 12], the trifunctional alkoxydecane represented by the formula (4) is represented by a hydrolysis condensate group.

[化12]通式(4)-Si(OH)3 [12]-(Si)-Si(OH) 3

以下，對構成本實施形態之可撓性裝置用基板的各材料加以說明。 Hereinafter, each material constituting the substrate for a flexible device of the present embodiment will be described.

<聚醯亞胺> <polyimine]

本實施形態中所使用之聚醯亞胺係5%熱分解溫度為350℃以上者。此種聚醯亞胺典型的是藉由如下方式而獲得：對藉由使四羧酸二酐與二胺反應而獲得之聚醯亞胺前驅物進行加熱處理等而進行醯亞胺化。 The polyamidene used in the present embodiment has a 5% thermal decomposition temperature of 350 ° C or higher. Such a polyimine is typically obtained by subjecting a polyimine precursor obtained by reacting a tetracarboxylic dianhydride with a diamine to heat treatment or the like to carry out oxime imidization.

至於此處所使用之聚醯亞胺前驅物，自耐熱性、機械強度之方面而言，較佳為使選自由均苯四甲酸二酐、3,3',4,4'-聯苯四羧酸二酐、2,3,3',4'-聯苯四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、對伸苯基雙(偏苯三甲酸單酯酸酐)、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、3,3'-氧雙鄰苯二甲酸二酐、及4,4'-氧雙鄰苯二甲酸二酐所組成之群中之至少1種為全部四羧酸二酐之80mol%以上，且使選自由對苯二胺、間苯二胺、聯苯胺、4,4'-(或3,4'-、3,3'-、2,4'-)二胺基-二苯 醚、5-胺基-2-(對胺基-苯基)苯并唑、6-胺基-2-(對胺基-苯基)苯并唑、5-胺基-2-(間胺基-苯基)苯并唑、及6-胺基-2-(間胺基-苯基)苯并唑所組成之群中之至少1種為全部二胺之80mol%以上，進行反應而獲得之聚醯亞胺或聚醯胺酸。 As for the polyimine precursor used herein, it is preferably selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylate in terms of heat resistance and mechanical strength. Acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, p-phenylene bis(trimellitic acid) Monoester anhydride), 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-oxydiphthalic dianhydride, and At least one of the group consisting of 4,4'-oxydiphthalic dianhydride is 80 mol% or more of all tetracarboxylic dianhydrides, and is selected from p-phenylenediamine, m-phenylenediamine, and benzidine. , 4,4'-(or 3,4'-,3,3'-,2,4'-)diamino-diphenyl ether, 5-amino-2-(p-amino-phenyl)benzene and Azole, 6-amino-2-(p-amino-phenyl)benzo Azole, 5-amino-2-(m-amino-phenyl)benzo Azole, and 6-amino-2-(m-amino-phenyl)benzo At least one of the group consisting of azoles is a polyimine or a polyamine obtained by reacting at least 80 mol% of all diamines.

就透明性、耐熱性之觀點而言，聚醯亞胺或聚醯亞胺前驅物較佳為使作為四羧酸二酐之選自由含氟基之芳香族酸二酐、脂環式酸二酐、含硫之酸二酐所組成之群中之至少1種、或作為二胺之選自由含氟基之芳香族二胺、脂環式二胺、含硫二胺所組成之群中之至少1種反應而獲得之聚醯亞胺或聚醯胺酸。 From the viewpoint of transparency and heat resistance, the polyimide or polyimine precursor is preferably a tetracarboxylic dianhydride selected from a fluorine-containing aromatic acid dianhydride and an alicyclic acid At least one of a group consisting of an anhydride and a sulfuric acid dianhydride, or a group of a diamine selected from the group consisting of a fluorine-containing aromatic diamine, an alicyclic diamine, and a sulfur-containing diamine Polyimine or polylysine obtained by at least one reaction.

含氟基之芳香族酸二酐可列舉2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、2,2-雙(4-(3,4-二羧基苯氧基)苯基)六氟丙烷二酐、2,2-雙(4-(3,4-二羧基苯甲醯氧基)苯基)六氟丙烷二酐、及2,2'-雙(三氟甲基)-4,4'-雙(3,4-二羧基苯氧基)聯苯二酐等。 Examples of the fluorine-containing aromatic acid dianhydride include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and 2,2-bis(4-(3,4-dicarboxyphenoxy) group. Phenyl) hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane dianhydride, and 2,2'-bis(trifluoro Methyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride.

脂環式酸二酐可列舉雙環[2,2,2]辛-7-烯-2,3,5,6-四羧酸二酐、2,3,5,6-環己烷四羧酸二酐、3,3',4,4'-聯環己烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、環丁烷四羧酸二酐等。 Examples of the alicyclic acid dianhydride include bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and 2,3,5,6-cyclohexanetetracarboxylic acid. Diacetic anhydride, 3,3',4,4'-bicyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and the like.

含硫之酸二酐可列舉雙(3,4-二羧基苯基)碸二酐等。 Examples of the sulfur-containing acid dianhydride include bis(3,4-dicarboxyphenyl)ruthenium anhydride.

含氟基之芳香族二胺可列舉1,1,1,3,3,3-六氟-2,2-雙(4-胺基-苯基)丙烷、2,2'-雙(三氟甲基)聯苯胺、2,2-雙(3-胺基-4-羥基苯基)六氟丙烷、2,2'-雙(3-胺基-2,4-二羥基苯基)六氟丙烷、2,2'-雙(4-胺基-3,5-二羥基苯基)六氟丙烷、2,2-雙[4-(3-胺基-苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、2,2-雙[4-(4-胺基-苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷等。 Examples of the fluorine-containing aromatic diamine include 1,1,1,3,3,3-hexafluoro-2,2-bis(4-amino-phenyl)propane and 2,2'-bis(trifluoro). Methyl)benzidine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-2,4-dihydroxyphenyl)hexafluoro Propane, 2,2'-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 2,2-bis[4-(3-amino-phenoxy)phenyl]-1 1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-amino-phenoxy)phenyl]-1,1,1,3,3,3-hexa Fluoropropane, etc.

脂環式二胺可列舉1,4-二胺基環己烷、1,3-二胺基環己烷、4,4'-二胺基二環己基甲烷、4,4'-二胺基二環己基丙烷、2,3-二胺基雙環[2.2.1]庚烷、2,5-二胺基雙環[2.2.1]庚烷、2,6-二胺基雙環[2.2.1]庚烷、2,7-二胺基雙環[2.2.1]庚烷、2,5-雙(胺基甲基)-雙環[2.2.1]庚烷、 2,6-雙(胺基甲基)-雙環[2.2.1]庚烷、2,3-雙(胺基甲基)-雙環[2.2.1]庚烷等。 Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, and 4,4'-diamino group. Dicyclohexylpropane, 2,3-diaminobicyclo[2.2.1]heptane, 2,5-diaminobicyclo[2.2.1]heptane, 2,6-diaminobicyclo[2.2.1] Heptane, 2,7-diaminobicyclo[2.2.1]heptane, 2,5-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,3-bis(aminomethyl)-bicyclo[2.2.1]heptane, and the like.

含硫二胺可列舉4,4'-(或3,4'-、3,3'-、2,4'-)二胺基-二苯基碸、4,4'-(或3,4'-、3,3'-、2,4'-)二胺基-二苯基硫醚、4,4'-二(4-胺基-苯氧基)苯基碸、4,4'-二(3-胺基-苯氧基)苯基碸、3,3'-二胺基-二苯基碸、3,3'-二甲基-4,4'-二胺基-聯苯-6,6'-二碸、雙(3-胺基-苯基)硫醚、雙(4-胺基-苯基)硫醚、雙(3-胺基-苯基)亞碸、雙(4-胺基-苯基)亞碸、雙(3-胺基-苯基)碸、雙(4-胺基-苯基)碸等。 Examples of the sulfur-containing diamine include 4,4'-(or 3,4'-, 3,3'-, 2,4'-)diamino-diphenylanthracene, 4,4'- (or 3,4). '-, 3,3'-, 2,4'-)diamino-diphenyl sulfide, 4,4'-bis(4-amino-phenoxy)phenylhydrazine, 4,4'- Bis(3-Amino-phenoxy)phenylindole, 3,3'-diamino-diphenylanthracene, 3,3'-dimethyl-4,4'-diamino-biphenyl- 6,6'-diindole, bis(3-amino-phenyl) sulfide, bis(4-amino-phenyl) sulfide, bis(3-amino-phenyl) anthracene, double (4 -Amino-phenyl) anthracene, bis(3-amino-phenyl)anthracene, bis(4-amino-phenyl)anthracene, and the like.

其他可使用之四羧酸二酐可列舉3,3',4,4'-二苯甲酮四羧酸二酐、2,3,3',4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐等。該等四羧酸二酐可單獨或將2種以上混合使用。 Other tetracarboxylic dianhydrides which can be used include 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2,3,3',4'-benzophenonetetracarboxylic dianhydride. 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

另外，四羧酸二酐亦可於起到本實施形態之效果的範圍內使用現有公知之其他四羧酸二酐。 Further, tetracarboxylic dianhydride may be used in the range of the effect of the present embodiment, and other conventionally known tetracarboxylic dianhydrides may be used.

其他四羧酸二酐例如可列舉2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)甲烷二酐、2,2-雙(4-(4-胺基-苯氧基)苯基)丙烷、1,3-二氫-1,3-二側氧基-5-異苯并呋喃羧酸-1,4-伸苯基酯、4-(2,5-二側氧基四氫呋喃-3-基)-1,2,3,4-四氫化萘-1,2-二羧酸酐、2,3,5,6-吡啶四羧酸二酐、及、3,4,9,10-苝四羧酸二酐。該等四羧酸二酐可單獨使用，亦可將2種以上混合使用。 Examples of the other tetracarboxylic dianhydride include 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and 1,1. - bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane Anhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 2,2-bis(4-(4-amino-phenoxy)phenyl)propane, 1,3-dihydro-1,3 - Bis-oxy-5-isobenzofurancarboxylic acid-1,4-phenylene ester, 4-(2,5-di-oxytetrahydrofuran-3-yl)-1,2,3,4- Tetrahydronaphthalene-1,2-dicarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 3,4,9,10-decanetetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

其他可使用之二胺例如可列舉以下者。 Other diamines which can be used include, for example, the following.

3,3'-二甲基-4,4'-二胺基-聯苯、2,2'-二甲基-4,4'-二胺基-聯苯、3,3'-二乙基-4,4'-二胺基-聯苯、2,2'-二乙基-4,4'-二胺基-聯苯、1,4-環己基二胺、對苯二甲胺、間二甲苯二胺、1,5-二胺基-萘、3,3'-二甲氧基聯苯胺、4,4'-(或3,4'-、3,3'-、2,4'-)二胺基-二苯基甲烷、4,4'-(或 3,4'-、3,3'-、2,4'-)二胺基-二苯醚、4,4'-二苯甲酮二胺、3,3'-二苯甲酮二胺、4,4'-雙(4-胺基-7苯氧基)聯苯、1,4-雙(4-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、3,3-二甲基-4,4'-二胺基-二苯基甲烷、3,3',5,5'-四甲基-4,4'-二胺基-二苯基甲烷、2,2'-雙(4-胺基-苯基)丙烷、5,5'-亞甲基-雙-(鄰胺基苯甲酸)、3,5-二胺基-苯甲酸、3,3'-二羥基-4,4'-二胺基-聯苯等芳香族二胺、2,6-二胺基-吡啶、2,4-二胺基-吡啶、2,4-二胺基-均三嗪、2,7-二胺基-苯并呋喃、2,7-二胺基-咔唑、3,7-二胺基-啡噻嗪、2,5-二胺基-1,3,4-噻二唑、2,4-二胺基-6-苯基-均三嗪等雜環式二胺、丙二胺、丁二胺、己二胺、2,2-二甲基丙二胺、1,4-環己二胺3,3'-二胺基-聯苯-4,4'-二醇、3,3'-二胺基-聯苯-4,4'-二醇、4,3'-二胺基-聯苯-3,4'-二醇、4,4'-二胺基-聯苯-3,3',5,5'-四醇、3,3'-二胺基-聯苯-4,4',5,5'-四醇、3,3'-二胺基-二苯甲酮、4,4'-二胺基-二苯甲酮、3,3'-二胺基-二苯醚、4,4'-二胺基-二苯醚、1,3-雙(3-胺基-苯氧基)苯、1,4-雙(4-胺基-苯氧基)苯、雙(3-(3-胺基-苯氧基)苯基)醚、雙(4-(4-胺基-苯氧基)苯基)醚、1,3-雙(3-(3-胺基-苯氧基)苯氧基)苯、1,4-雙(4-(4-胺基-苯氧基)苯氧基)苯、雙(3-(3-(3-胺基-苯氧基)苯氧基)苯基)醚、雙(4-(4-(4-胺基-苯氧基)苯氧基)苯基)醚、1,3-雙(3-(3-(3-胺基-苯氧基)苯氧基)苯氧基)苯、1,4-雙(4-(4-(4-胺基-苯氧基)苯氧基)苯氧基)苯、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-(4-胺基-苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基-苯氧基)苯基]丁烷等二胺、α,ω-雙(2-胺基-乙基)聚二甲基矽氧烷、α,ω-雙(3-胺基-丙基)聚二甲基矽氧烷、α,ω-雙(4-胺基-丁基)聚二甲基矽氧烷、α,ω-雙(4-胺基-苯基)聚二甲基矽氧烷、α,ω-雙(3-胺基-丙基)聚二苯基矽氧烷等聚矽氧二胺。 3,3'-Dimethyl-4,4'-diamino-biphenyl, 2,2'-dimethyl-4,4'-diamino-biphenyl, 3,3'-diethyl -4,4'-diamino-biphenyl, 2,2'-diethyl-4,4'-diamino-biphenyl, 1,4-cyclohexyldiamine, p-xylylenediamine, between Xylene diamine, 1,5-diamino-naphthalene, 3,3'-dimethoxybenzidine, 4,4'- (or 3,4'-, 3,3'-, 2,4' -) diamino-diphenylmethane, 4,4'- (or 3,4'-,3,3'-,2,4'-)diamino-diphenyl ether, 4,4'-benzophenone diamine, 3,3'-benzophenone diamine, 4,4'-bis(4-amino-7-phenoxy)biphenyl, 1,4-bis(4-amino-phenoxy)benzene, 1,3-bis(4-amino-phenoxy) Benzo, 2,2-bis[4-(4-amino-phenoxy)phenyl]propane, 3,3-dimethyl-4,4'-diamino-diphenylmethane, 3 , 3',5,5'-tetramethyl-4,4'-diamino-diphenylmethane, 2,2'-bis(4-amino-phenyl)propane, 5,5'-Asia Aromatic diamines such as methyl-bis-(o-aminobenzoic acid), 3,5-diamino-benzoic acid, 3,3'-dihydroxy-4,4'-diamino-biphenyl, 2 ,6-Diamino-pyridine, 2,4-diamino-pyridine, 2,4-diamino-s-triazine, 2,7-diamino-benzofuran, 2,7-diamino -carbazole, 3,7-diamino-phenothiazine, 2,5-diamino-1,3,4-thiadiazole, 2,4-diamino-6-phenyl-s-triazine Heterocyclic diamine, propylenediamine, butanediamine, hexamethylenediamine, 2,2-dimethylpropanediamine, 1,4-cyclohexanediamine 3,3'-diamino-biphenyl- 4,4'-diol, 3,3'-diamino-biphenyl-4,4'-diol, 4,3'-diamino-biphenyl-3,4'-diol, 4, 4'-Diamino-biphenyl-3,3',5,5'-tetraol, 3,3'-diamino-biphenyl-4,4',5,5'- Alcohol, 3,3'-diamino-benzophenone, 4,4'-diamino-benzophenone, 3,3'-diamino-diphenyl ether, 4,4'-diamine -diphenyl ether, 1,3-bis(3-amino-phenoxy)benzene, 1,4-bis(4-amino-phenoxy)benzene, bis(3-(3-amino)- Phenoxy)phenyl)ether, bis(4-(4-amino-phenoxy)phenyl)ether, 1,3-bis(3-(3-amino-phenoxy)phenoxy) Benzene, 1,4-bis(4-(4-amino-phenoxy)phenoxy)benzene, bis(3-(3-(3-amino-phenoxy)phenoxy)phenyl) Ether, bis(4-(4-(4-amino-phenoxy)phenoxy)phenyl)ether, 1,3-bis(3-(3-(3-amino-phenoxy)benzene) Oxy)phenoxy)benzene, 1,4-bis(4-(4-(4-amino-phenoxy)phenoxy)phenoxy)benzene, 4,4'-bis(3-amine Bis-phenoxy)biphenyl, 4,4'-bis(4-amino-phenoxy)biphenyl, 2,2-bis[4-(3-amino-phenoxy)phenyl]propane , diamines such as 2,2-bis[4-(4-amino-phenoxy)phenyl]propane, 2,2-bis[4-(3-amino-phenoxy)phenyl]butane , α,ω-bis(2-amino-ethyl)polydimethyloxane, α,ω-bis(3-amino-propyl)polydimethyloxane, α,ω-double (4-Amino-butyl)polydimethyloxane, α,ω-bis(4-amino-phenyl)polydimethyloxane, A polyoxydiamine such as α,ω-bis(3-amino-propyl)polydiphenyloxane.

該等二胺可單獨使用，亦可將2種以上混合而使用。上述聚醯亞胺前驅物之製造方法包含公知之方法，可製造聚醯亞胺前驅物之方法全部可應用。其中，較佳為於有機溶劑中進行反應。 These diamines may be used singly or in combination of two or more. The method for producing the above polyimine precursor includes a known method, and all of the methods for producing a polyimide precursor are applicable. Among them, it is preferred to carry out the reaction in an organic solvent.

此種反應中所使用之溶劑例如可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯、1,2-二甲氧基乙烷、四氫呋喃、1,3-二烷、1,4-二烷、二甲基亞碸、苯、甲苯、二甲苯、均三甲苯、苯酚、甲酚、苯甲酸乙酯、及苯甲酸丁酯。該等可單獨使用，亦可將2種以上混合而使用。 Examples of the solvent used in such a reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone. 1,2-dimethoxyethane, tetrahydrofuran, 1,3-two Alkane, 1,4-two Alkane, dimethyl hydrazine, benzene, toluene, xylene, mesitylene, phenol, cresol, ethyl benzoate, and butyl benzoate. These may be used alone or in combination of two or more.

上述溶劑較佳為N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯，尤佳為N-甲基-2-吡咯啶酮。 The above solvent is preferably N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and more preferably N-A. Base-2-pyrrolidone.

該反應中之反應原料之濃度通常為2質量%~80質量%，較佳為5質量%~30質量%。 The concentration of the reaction raw material in the reaction is usually 2% by mass to 80% by mass, preferably 5% by mass to 30% by mass.

反應之四羧酸二酐與二胺之莫耳比為0.8~1.2之範圍內。於該範圍內之情形時，可提高分子量，延展性等亦優異。莫耳比較佳為0.9~1.1，更佳為0.92~1.07。 The molar ratio of the tetracarboxylic dianhydride to the diamine in the reaction is in the range of 0.8 to 1.2. In the case of this range, the molecular weight can be improved, and the ductility and the like are also excellent. The molar ratio is preferably 0.9 to 1.1, more preferably 0.92 to 1.07.

聚醯亞胺前驅物之重量平均分子量較佳為1000以上1000000以下。此處，所謂重量平均分子量係指以已知之數量平均分子量的聚苯乙烯為標準，藉由凝膠滲透層析法而測定的分子量。重量平均分子量更佳為10000以上500000以下，最佳為20000以上300000以下。若重量平均分子量為1000以上1000000以下，則使用樹脂組合物而獲得之樹脂層之拉伸度得到改善，機械物性優異。另外，於塗佈等加工時，可藉由所期望之膜厚而無滲出地塗佈。 The weight average molecular weight of the polyimide precursor is preferably from 1,000 to 1,000,000. Here, the weight average molecular weight means a molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The weight average molecular weight is more preferably 10,000 or more and 500,000 or less, and most preferably 20,000 or more and 300,000 or less. When the weight average molecular weight is 1,000 or more and 1,000,000 or less, the degree of stretching of the resin layer obtained by using the resin composition is improved, and the mechanical properties are excellent. Further, at the time of processing such as coating, it can be applied without bleeding by a desired film thickness.

聚醯亞胺前驅物可藉由如下所示之方法而獲得。首先，使反應原料於室溫至80℃下進行聚縮合反應，藉此而製造聚醯胺酸。 The polyimine precursor can be obtained by the method shown below. First, a polycondensation reaction is carried out by subjecting a reaction raw material to a polycondensation reaction at room temperature to 80 ° C.

又，聚醯亞胺前驅物之聚合物主鏈之末端亦可藉由包含單胺衍生物或羧酸衍生物之封端劑而進行封端。藉由對聚醯亞胺之聚合物主 鏈之末端進行密封，源自末端官能基之儲存穩定性優異。 Further, the terminal of the polymer main chain of the polyimide precursor may be blocked by a terminal blocking agent containing a monoamine derivative or a carboxylic acid derivative. By polymerizing the polyimine The end of the chain is sealed, and the storage stability derived from the terminal functional group is excellent.

包含單胺衍生物之封端劑例如可列舉苯胺、鄰甲苯胺、間甲苯胺、對甲苯胺、2,3-二甲苯胺、2,6-二甲苯胺、3,4-二甲苯胺、3,5-二甲苯胺、鄰氯苯胺、間氯苯胺、對氯苯胺、鄰溴苯胺、間溴苯胺、對溴苯胺、鄰硝基苯胺、對硝基苯胺、間硝基苯胺、鄰胺基-苯酚、對胺基-苯酚、間胺基-苯酚、鄰胺基苯甲醚、間胺基苯甲醚、對胺基苯甲醚、鄰乙氧基苯胺、間乙氧基苯胺、對乙氧基苯胺、鄰胺基-苯甲醛、對胺基-苯甲醛、間胺基-苯甲醛、鄰胺基-苯腈、對胺基-苯腈、間胺基-苯腈、2-胺基-聯苯、3-胺基-聯苯、4-胺基-聯苯、2-胺基-苯基苯基醚、3-胺基-苯基苯基醚，4-胺基-苯基苯基醚、2-胺基-二苯甲酮、3-胺基-二苯甲酮、4-胺基-二苯甲酮、2-胺基-苯基苯基硫醚、3-胺基-苯基苯基硫醚、4-胺基-苯基苯基硫醚、2-胺基-苯基苯基碸、3-胺基-苯基苯基碸、4-胺基-苯基苯基碸、α-萘胺、β-萘胺、1-胺基-2-萘酚、5-胺基-1-萘酚、2-胺基-1-萘酚、4-胺基-1-萘酚、5-胺基-2-萘酚、7-胺基-2-萘酚、8-胺基-1-萘酚、8-胺基-2-萘酚、1-胺基-蒽、2-胺基-蒽、9-胺基-蒽等芳香族單胺。該等中較佳為使用苯胺之衍生物。該等可單獨使用，亦可將2種以上混合而使用。 Examples of the blocking agent containing a monoamine derivative include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-dimethylaniline, 2,6-dimethylaniline, and 3,4-dimethylaniline. 3,5-xylyleneamine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, p-nitroaniline, m-nitroaniline, ortho-amine - phenol, p-amino-phenol, m-amino-phenol, o-aminoanisole, m-aminoanisole, p-aminoanisole, o-ethoxyaniline, m-ethoxyaniline, p-B Oxyaniline, o-amino-benzaldehyde, p-amino-benzaldehyde, m-amino-benzaldehyde, o-amino-benzonitrile, p-amino-benzonitrile, m-amino-benzonitrile, 2-amino group -biphenyl, 3-amino-biphenyl, 4-amino-biphenyl, 2-amino-phenylphenyl ether, 3-amino-phenylphenyl ether, 4-amino-phenylbenzene Ether, 2-amino-benzophenone, 3-amino-benzophenone, 4-amino-benzophenone, 2-amino-phenylphenyl sulfide, 3-amino group- Phenylphenyl sulfide, 4-amino-phenylphenyl sulfide, 2-amino-phenylphenylhydrazine, 3-amino-phenylphenylhydrazine, 4-amino-phenylphenyl碸, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 5-amino-1-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthalene Phenol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-amino-purine, 2 An aromatic monoamine such as an amine-fluorene or a 9-amino-hydrazine. It is preferred to use a derivative of aniline. These may be used alone or in combination of two or more.

包含羧酸衍生物之封端劑主要可列舉羧酸酐衍生物。 The blocking agent containing a carboxylic acid derivative is mainly a carboxylic anhydride derivative.

羧酸酐衍生物例如可列舉鄰苯二甲酸酐、2,3-二苯甲酮二羧酸酐、3,4-二苯甲酮二羧酸酐、2,3-二羧基苯基苯基醚酸酐、3,4-二羧基苯基苯基醚酸酐、2,3-聯苯二羧酸酐、3,4-聯苯二羧酸酐、2,3-二羧基苯基苯基碸酐、3,4-二羧基苯基苯基碸酐、2,3-二羧基苯基苯基硫醚酐、3,4-二羧基苯基苯基硫醚酐、1,2-萘二羧酸酐、2,3-萘二羧酸酐、1,8-萘二羧酸酐、1,2-蒽二羧酸酐、2,3-蒽二羧酸酐、及1,9-蒽二羧酸酐等芳香族二羧酸酐。該等芳香族二羧酸酐中，較佳為使用鄰苯二甲酸酐。該等可單獨使用，亦可將2種以上混合而使用。 Examples of the carboxylic anhydride derivative include phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, and 2,3-dicarboxyphenyl phenyl ether anhydride. 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenyl phthalic anhydride, 3,4- Dicarboxyphenyl phenyl phthalic anhydride, 2,3-dicarboxyphenyl phenyl thioether anhydride, 3,4-dicarboxyphenyl phenyl thioether anhydride, 1,2-naphthalene dicarboxylic anhydride, 2,3- An aromatic dicarboxylic anhydride such as naphthalene dicarboxylic anhydride, 1,8-naphthalene dicarboxylic anhydride, 1,2-anthracene dicarboxylic anhydride, 2,3-indane dicarboxylic anhydride, and 1,9-fluorene dicarboxylic anhydride. Among these aromatic dicarboxylic anhydrides, phthalic anhydride is preferably used. These may be used alone or in combination of two or more.

所得之聚醯亞胺前驅物溶液可並不脫溶劑地直接使用，亦可進而調配必要之溶劑、添加劑等而用作本實施形態之樹脂組合物。而且，可如下所述般將該樹脂組合物塗佈於無機基板之表面，實施規定之熱處理等而形成聚醯亞胺樹脂層，將其自無機基板剝離，藉此而獲得包含聚醯亞胺樹脂層之可撓性裝置用基板。於可撓性裝置用基板中包含對上述聚醯亞胺或聚醯亞胺前驅物實施了規定之熱處理之狀態下的5%熱分解溫度為350℃以上之聚醯亞胺。 The obtained polyimide intermediate precursor solution can be used as it is without desolvation, and a necessary solvent, additive or the like can be further used as the resin composition of the present embodiment. Further, the resin composition can be applied to the surface of the inorganic substrate, and a predetermined heat treatment or the like can be applied to form a polyimide film, and the polyimide resin layer can be peeled off from the inorganic substrate to obtain a polyimine. A substrate for a flexible device of a resin layer. The substrate for a flexible device contains a polyimide having a 5% thermal decomposition temperature of 350 ° C or higher in a state in which the polyimine or the polyimide precursor is subjected to a predetermined heat treatment.

<具有通式(1)所表示之化學結構之化合物> <Compound having a chemical structure represented by the general formula (1)>

具有通式(1)所表示之化學結構之化合物係源自2官能聚矽氧化合物之化合物。該化合物之例子可列舉以二甲基矽氧烷為代表之聚矽氧油或其改質物、或於二甲基矽氧烷上鍵結有親水性基之聚矽氧系界面活性劑。該化合物若於其分子中具有通式(1)之結構即可，亦可於側鏈或末端鍵結上述親水性基。 The compound having the chemical structure represented by the general formula (1) is derived from a compound of a bifunctional polyoxo compound. Examples of the compound include a polyoxyxylene oil represented by dimethyloxane or a modified product thereof, or a polyoxynoxy surfactant in which a hydrophilic group is bonded to dimethyloxane. The compound may have a structure of the formula (1) in its molecule, and may also bond the above hydrophilic group at a side chain or a terminal.

為了使該化合物含有於可撓性裝置用基板中，簡便的是將上述聚醯亞胺前驅物與該化合物溶解於溶劑中，藉由加熱而將溶劑除去。 In order to allow the compound to be contained in a substrate for a flexible device, it is convenient to dissolve the polyimine precursor and the compound in a solvent, and to remove the solvent by heating.

若具有通式(1)之化學結構，則於可撓性裝置用基板中，該化合物可藉由熱而反應、分解。於包含該化合物之情形時，可控制表面張力，可使可撓性裝置用基板之表面粗糙度變小。 When the chemical structure of the formula (1) is present, the compound can be reacted and decomposed by heat in the substrate for a flexible device. When the compound is contained, the surface tension can be controlled to make the surface roughness of the substrate for a flexible device small.

<具有通式(2)所表示之化學結構之化合物> <Compound having a chemical structure represented by the general formula (2)>

具有通式(2)所表示之化學結構之化合物係源自氟化烴之化合物。作為該化合物，代表性的是氟系界面活性劑，具體而言可列舉全氟烷基羧酸鹽、全氟烷基磷酸酯、全氟烷基磺酸鹽等陰離子性氟系界面活性劑，或全氟烷基環氧乙烷加成物、全氟烷基胺氧化物、全氟烷基聚氧乙烯乙醇、全氟烷基烷氧基化物、氟化烷基酯等非離子性氟系界面活性劑等。作為通式(2)所表示之化合物，若具有源自氟化烴之結構即可，因此可使用上述氟系界面活性劑本身，亦可使用除去氟系 界面活性劑之親水性基而成者。 The compound having the chemical structure represented by the general formula (2) is derived from a compound of a fluorinated hydrocarbon. Typical examples of the compound include a fluorine-based surfactant, and specific examples thereof include an anionic fluorine-based surfactant such as a perfluoroalkyl carboxylate, a perfluoroalkyl phosphate, or a perfluoroalkylsulfonate. Or a perfluoroalkyl ethylene oxide adduct, a perfluoroalkylamine oxide, a perfluoroalkyl polyoxyethylene ethanol, a perfluoroalkyl alkoxylate, a fluorinated alkyl ester, etc. Surfactant and the like. The compound represented by the formula (2) may have a structure derived from a fluorinated hydrocarbon. Therefore, the fluorine-based surfactant itself may be used, or a fluorine-based catalyst may be used. The hydrophilic base of the surfactant is the one.

為了使該化合物含有於可撓性裝置用基板中，簡便的是將上述聚醯亞胺前驅物與該化合物溶解於溶劑中，藉由加熱而將溶劑除去。 In order to allow the compound to be contained in a substrate for a flexible device, it is convenient to dissolve the polyimine precursor and the compound in a solvent, and to remove the solvent by heating.

若具有通式(2)之化學結構，則於可撓性裝置用基板中，該化合物可藉由熱而反應、分解。於包含該化合物之情形時，可控制表面張力，可使可撓性裝置用基板之表面粗糙度變小。 When the chemical structure of the formula (2) is present, the compound can be reacted and decomposed by heat in the substrate for a flexible device. When the compound is contained, the surface tension can be controlled to make the surface roughness of the substrate for a flexible device small.

<具有由通式(3)所表示之化學結構、羥基、羧基及磺基所組成之群中之1種以上之化合物> <Compound having one or more of the chemical structure represented by the general formula (3), a hydroxyl group, a carboxyl group, and a sulfo group>

具有由通式(3)所表示之化學結構、羥基、羧基及磺基所組成之群中之1種以上之化合物係源自界面活性劑之化合物。作為該化合物之代表性化合物為聚矽氧系、氟系界面活性劑，該化合物之例子可列舉：於二甲基矽氧烷上鍵結有親水性基之聚矽氧系界面活性劑，全氟烷基羧酸鹽、全氟烷基磷酸酯、全氟烷基磺酸鹽等陰離子性氟系界面活性劑，或全氟烷基環氧乙烷加成物、全氟烷基胺氧化物、全氟烷基聚氧乙烯乙醇、全氟烷基烷氧基化物、氟化烷基酯等非離子性氟系界面活性劑等。通式(3)所表示之化合物若具有界面活性劑之親水性基即可，因此可使用上述聚矽氧系、氟系界面活性劑本身，亦可使用自該等界面活性劑除去疏水性基而成者。 One or more compounds having a chemical structure represented by the formula (3), a hydroxyl group, a carboxyl group, and a sulfo group are derived from a surfactant-based compound. A representative compound of the compound is a polyfluorene-based or fluorine-based surfactant. Examples of the compound include a polyoxyn-based surfactant in which a hydrophilic group is bonded to dimethyloxane. An anionic fluorine-based surfactant such as a fluoroalkyl carboxylate, a perfluoroalkyl phosphate or a perfluoroalkyl sulfonate, or a perfluoroalkyl ethylene oxide adduct or a perfluoroalkylamine oxide A nonionic fluorine-based surfactant such as a perfluoroalkyl polyoxyethylene ethanol, a perfluoroalkyl alkoxylate or a fluorinated alkyl ester. When the compound represented by the formula (3) has a hydrophilic group of a surfactant, the polyfluorene-based or fluorine-based surfactant itself may be used, and the hydrophobic group may be removed from the surfactant. Founder.

為了使該化合物含有於可撓性裝置用基板中，簡便的是將上述聚醯亞胺前驅物與該化合物溶解於溶劑中，藉由加熱而將溶劑除去。 In order to allow the compound to be contained in a substrate for a flexible device, it is convenient to dissolve the polyimine precursor and the compound in a solvent, and to remove the solvent by heating.

若具有通式(3)之化學結構，則於可撓性裝置用基板中，該化合物可藉由熱而反應、分解。於包含該化合物之情形時，可控制表面張力，可使可撓性裝置用基板之表面粗糙度變小。 When the chemical structure of the formula (3) is present, the compound can be reacted and decomposed by heat in the substrate for a flexible device. When the compound is contained, the surface tension can be controlled to make the surface roughness of the substrate for a flexible device small.

<具有通式(4)所表示之化學結構之化合物> <Compound having a chemical structure represented by the general formula (4)>

具有通式(4)所表示之化學結構之化合物係源自3官能聚矽氧化合物之化合物。該化合物之例子可列舉3官能烷氧基矽烷之水解縮合 物。為了獲得該化合物而使用的3官能烷氧基矽烷可列舉胺基丙基三甲氧基矽烷、胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷等。為了使該化合物含有於可撓性裝置用基板中，簡便的是與前述通式(1)所表示之化合物同樣地將上述聚醯亞胺前驅物與該化合物溶解於溶劑中，藉由加熱而將溶劑除去。 The compound having the chemical structure represented by the general formula (4) is derived from a compound of a trifunctional polyoxo compound. Examples of the compound include hydrolytic condensation of a trifunctional alkoxydecane Things. The trifunctional alkoxydecane used for obtaining the compound may, for example, be aminopropyltrimethoxydecane, aminopropyltriethoxydecane or N-2-(aminoethyl)-3-aminopropyl Trimethoxy decane, N-2-(aminoethyl)-3-aminopropyltriethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxylate Decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, and the like. In order to allow the compound to be contained in the substrate for a flexible device, it is convenient to dissolve the polyimine precursor and the compound in a solvent in the same manner as the compound represented by the above formula (1) by heating. The solvent is removed.

若具有通式(4)之化學結構，則於可撓性裝置用基板中，該化合物可藉由熱而反應、分解。於包含該化合物之情形時，可縮小可撓性裝置用基板之膜厚不均。其理由並不確定，推測由於源自3官能聚矽氧化合物之化合物由於加熱而偏析於表面，表面張力減少，從而表現出上述效果。 When the chemical structure of the formula (4) is present, the compound can be reacted and decomposed by heat in the substrate for a flexible device. When the compound is contained, the film thickness unevenness of the substrate for a flexible device can be reduced. The reason for this is not certain. It is presumed that the compound derived from the trifunctional polyoxo compound segregates on the surface due to heating, and the surface tension is reduced, thereby exhibiting the above effects.

至於本實施形態之可撓性裝置用基板中所含之(β)成分之添加量，就膜厚均一性及可撓性之觀點而言，相對於(α)之聚醯亞胺100質量份，較佳為0.0001質量份~9質量份，更佳為0.001質量份~5質量份。 The amount of the (β) component contained in the substrate for a flexible device of the present embodiment is 100 parts by mass relative to the (α) polyimine from the viewpoint of film thickness uniformity and flexibility. It is preferably 0.0001 part by mass to 9 parts by mass, more preferably 0.001 part by mass to 5 parts by mass.

又，至於本實施形態之可撓性裝置用基板中所含之(γ)成分之添加量，就膜厚均一性及可撓性之觀點而言，相對於(α)之聚醯亞胺100質量份，較佳為0.0001質量份~10質量份，更佳為0.0001質量份~5質量份。 In addition, as for the addition amount of the (γ) component contained in the substrate for a flexible device of the present embodiment, the poly(imine) 100 with respect to (α) is obtained from the viewpoint of film thickness uniformity and flexibility. The mass part is preferably 0.0001 part by mass to 10 parts by mass, more preferably 0.0001 part by mass to 5 parts by mass.

<可撓性裝置> <Flexible device>

本實施形態之可撓性裝置之種類並無特別限定，代表性的是有機EL可撓性顯示器。以下，對在低溫多晶矽、氧化物半導體TFT驅動型之有機EL可撓性顯示器之製造中使用之情形加以說明。 The type of the flexible device of the present embodiment is not particularly limited, and is typically an organic EL flexible display. Hereinafter, a case of use in the production of a low-temperature polysilicon or an oxide semiconductor TFT-driven organic EL flexible display will be described.

圖1~圖7係表示使用本實施形態之樹脂組合物的可撓性顯示器 之製造步驟的剖面模式圖。 1 to 7 show a flexible display using the resin composition of the present embodiment. A schematic cross-sectional view of the manufacturing steps.

首先，如圖1A所示般，例如準備包含無鹼玻璃基板之第1基板11。其次，如圖1B所示般，藉由如下之方法而形成第1聚醯亞胺樹脂層12：於第1基板11之表面上，塗佈上述之藉由本實施形態之醯亞胺化處理而成為5%熱分解溫度為350℃以上之聚醯亞胺的聚醯亞胺前驅物樹脂組合物，其次藉由熱處理進行聚醯亞胺化的方法；或塗佈5%熱分解溫度為350℃以上之聚醯亞胺樹脂組合物，其次藉由熱處理將溶劑除去的方法。 First, as shown in FIG. 1A, for example, a first substrate 11 including an alkali-free glass substrate is prepared. Next, as shown in FIG. 1B, the first polyimine resin layer 12 is formed by coating the surface of the first substrate 11 with the above-described iridization treatment of the present embodiment. a polyiminoimine precursor resin composition having a 5% thermal decomposition temperature of 350 ° C or more, followed by a polyimidization by heat treatment; or a coating 5% thermal decomposition temperature of 350 ° C The above polyimine resin composition is a method of removing a solvent by heat treatment.

其次，如圖2所示般，於第1基板11之第1聚醯亞胺樹脂層12之上部形成第1障壁層101。 Next, as shown in FIG. 2, the first barrier layer 101 is formed on the upper portion of the first polyimide layer 12 of the first substrate 11.

另外，如圖2所示般，於第1障壁層101上依序形成半導體層102、閘極絕緣膜103、閘極電極104、層間絕緣膜105、接觸孔106、源極-汲極電極107a、107b，形成薄膜電晶體(TFT)108。 Further, as shown in FIG. 2, the semiconductor layer 102, the gate insulating film 103, the gate electrode 104, the interlayer insulating film 105, the contact hole 106, and the source-drain electrode 107a are sequentially formed on the first barrier layer 101. 107b, forming a thin film transistor (TFT) 108.

此處，半導體層102係由多晶矽而形成。半導體層102可藉由如下方式而形成：首先形成非晶矽，使其結晶化而變化為多晶矽。此種結晶化方法例如可列舉RTA(Rapid Thermal Annealing，快速熱退火)、SPC(Solid Phase Crystallzation，固相結晶)、ELA(Excimer Laser Annealing，準分子雷射退火)、MIC(Metal Induced Crystallization，金屬誘發結晶)、MILC(Metal Induced Lateral Crystallization，金屬誘導橫向結晶)及SLS(Sequential Lateral Solidification，連續橫向固化)。 Here, the semiconductor layer 102 is formed of polysilicon. The semiconductor layer 102 can be formed by first forming an amorphous germanium, crystallizing it, and changing to polycrystalline germanium. Examples of such a crystallization method include RTA (Rapid Thermal Annealing), SPC (Solid Phase Crystallization), ELA (Excimer Laser Annealing), and MIC (Metal Induced Crystallization). Induced crystallization), MILC (Metal Induced Lateral Crystallization) and SLS (Sequential Lateral Solidification).

其次，於TFT 108之上部形成顯示器元件。如圖3所示般，首先於源極-汲極電極107a、107b之上部形成平坦化層109。其次，為了於TFT 108之上部形成有機發光元件(OLED)，首先於源極-汲極電極107a、107b之一電極107b上形成接觸孔110而與第1電極111電性連結。第1電極111作為其後有機發光元件中所具備的電極中的一電極而發揮功能。 Next, a display element is formed on the upper portion of the TFT 108. As shown in FIG. 3, a planarization layer 109 is first formed on the upper portions of the source-drain electrodes 107a and 107b. Next, in order to form an organic light-emitting element (OLED) on the upper portion of the TFT 108, first, a contact hole 110 is formed on one of the source-drain electrodes 107a and 107b, and is electrically connected to the first electrode 111. The first electrode 111 functions as one of the electrodes included in the subsequent organic light-emitting element.

其次，如圖4所示般，於第1電極111上以其至少一部分露出之方式藉由絕緣性物質形成圖案化之像素定義膜112。其次，於第1電極111之露出之部分形成包含發光層之中間層113。以該中間層113為中心，形成與第1電極111對向之第2電極114。藉此而獲得有機發光元件(OLED)(圖6中之210)。 Next, as shown in FIG. 4, the patterned pixel defining film 112 is formed of an insulating material on the first electrode 111 so that at least a part thereof is exposed. Next, an intermediate layer 113 including a light-emitting layer is formed on the exposed portion of the first electrode 111. The second electrode 114 facing the first electrode 111 is formed around the intermediate layer 113. Thereby, an organic light emitting element (OLED) (210 in Fig. 6) is obtained.

其次，對上述有機發光元件進行密封。另行製造圖5中所示之密封構件201，將密封構件201與有機發光元件之上部結合後，分離密封構件201之第2基板202。 Next, the above organic light emitting element is sealed. The sealing member 201 shown in FIG. 5 is separately manufactured, and after the sealing member 201 is bonded to the upper portion of the organic light emitting element, the second substrate 202 of the sealing member 201 is separated.

密封構件201可如圖5所示般，於例如包含無鹼玻璃基板之第2基板202之一主表面上形成第2聚醯亞胺樹脂層203，進而於第2聚醯亞胺樹脂層203之表面形成第2障壁層204而獲得。此處，第2聚醯亞胺樹脂層203可使用本實施形態之樹脂組合物而形成。其次，如圖6所示般，於有機發光元件210之上部配置密封構件201後，將該等貼合。 As shown in FIG. 5, the sealing member 201 can form a second polyimide layer 203 on the main surface of one of the second substrates 202 including the alkali-free glass substrate, and further on the second polyimide layer 203. The surface of the second barrier layer 204 is obtained. Here, the second polyimine resin layer 203 can be formed using the resin composition of the present embodiment. Next, as shown in FIG. 6, after the sealing member 201 is placed on the upper portion of the organic light-emitting element 210, the layers are bonded together.

最後，於氧之存在下、圖6所示之狀態下，例如於空氣環境下、300℃~350℃下實施熱處理。藉此可自第1聚醯亞胺樹脂層12剝離第1基板11，且自第2聚醯亞胺樹脂層203剝離第2基板202。其結果獲得如圖7所示之可撓性顯示器100。 Finally, heat treatment is performed in the presence of oxygen in the state shown in Fig. 6, for example, in an air atmosphere at 300 ° C to 350 ° C. Thereby, the first substrate 11 can be peeled off from the first polyimide phase resin layer 12, and the second substrate 202 can be peeled off from the second polyimide film layer 203. As a result, the flexible display 100 as shown in FIG. 7 is obtained.

第1聚醯亞胺樹脂層12及第2聚醯亞胺樹脂層203分別相當於可撓性裝置用基板。可撓性裝置用基板係具有可撓性之薄的膜狀的絕緣基板。 Each of the first polyimine resin layer 12 and the second polyimide resin layer 203 corresponds to a substrate for a flexible device. The substrate for a flexible device has a flexible film-shaped insulating substrate.

所謂基板，一般係指於其表面可形成功能層的基材或支撐構件，包含貼合於裝置之表面而具有包覆功能或保護功能的可撓性之板狀物。 The substrate generally refers to a substrate or a support member on which a functional layer can be formed, and a flexible plate member having a coating function or a protective function attached to the surface of the device.

又，本實施形態之可撓性裝置可設為包含聚醯亞胺樹脂層之構成，上述聚醯亞胺樹脂層含有(α)5%熱分解溫度為350℃以上之聚醯亞胺、(β)具有上述[化9]之通式(1)所表示之化學結構及/或上述[化10]之 通式(2)所表示之化學結構之化合物、(γ)具有由上述[化11]之通式(3)所表示之化學結構、羥基、羧基、磺基所組成之群中之1種以上之化合物、(δ)具有上述[化12]之通式(4)所表示之化學結構之化合物，聚醯亞胺樹脂層亦可並不構成基板。 Further, the flexible device of the present embodiment may be configured to include a polyimine resin layer containing (α) 5% polyimine having a thermal decomposition temperature of 350 ° C or higher, ( β) has the chemical structure represented by the above formula (1) and/or the above-mentioned [Chemical Formula 10] The compound of the chemical structure represented by the formula (2) and (γ) have one or more of the group consisting of a chemical structure represented by the above formula (3), a hydroxyl group, a carboxyl group, and a sulfo group. The compound (δ) has a chemical structure represented by the above formula (4), and the polyimide layer may not constitute a substrate.

於上述構成中，聚醯亞胺樹脂層不僅為可撓性裝置之表面所顯現之層之情形，亦可為在可撓性裝置中所存在之層。 In the above configuration, the polyimide layer is not only a layer which appears on the surface of the flexible device but also a layer which is present in the flexible device.

以上所說明之本實施形態之可撓性裝置用基板起到如下上述之效果。亦即，於本實施形態中，可使可撓性裝置用基板之膜厚不均變小。膜厚例如可藉由光學式膜厚計而測定。 The substrate for a flexible device of the present embodiment described above has the following effects. In other words, in the present embodiment, the film thickness unevenness of the substrate for a flexible device can be made small. The film thickness can be measured, for example, by an optical film thickness meter.

本實施形態之可撓性裝置用基板之厚度較佳為5μm~200μm。 尤佳為10μm~30μm。若為5μm以上，則機械強度優異；若為200μm以下，則彎曲性、輕量性優異。 The thickness of the substrate for a flexible device of the present embodiment is preferably 5 μm to 200 μm. It is preferably 10 μm to 30 μm. When it is 5 μm or more, the mechanical strength is excellent, and when it is 200 μm or less, the flexibility and the lightweight property are excellent.

於本實施形態中，對上述較高之厚度尺寸而言，可將基板之膜厚不均抑制為50nm以下(相對於寬度10cm之膜厚不均)。 In the present embodiment, the film thickness unevenness of the substrate can be suppressed to 50 nm or less (uneven film thickness with respect to the width of 10 cm) for the above-mentioned high thickness dimension.

又，於使用本實施形態之可撓性裝置用基板而製造的可撓性裝置、或包含可撓性聚醯亞胺樹脂層之可撓性裝置中，於電氣特性等之特性評價中，可顯示良好之面內均一性。其原因在於：可撓性裝置用基板之膜厚不均較小、且基板表面之平面化度高，因此可於面內均一地形成在基板表面所形成的構成裝置之各層。 Further, in the flexible device manufactured using the substrate for a flexible device of the present embodiment or the flexible device including the flexible polyimide film layer, in the evaluation of characteristics such as electrical characteristics, Show good in-plane uniformity. This is because the substrate for a flexible device has a small thickness unevenness and a high degree of planarization of the substrate surface, so that each layer of the constituent device formed on the surface of the substrate can be uniformly formed in the plane.

又，理由尚不確定，但可使可撓性裝置用基板之可撓性提高，可製造即使較大程度地彎曲可撓性裝置亦難以損傷、耐久性優異之可撓性裝置。 In addition, the reason is not certain, but the flexibility of the substrate for a flexible device can be improved, and a flexible device which is hard to be damaged even if the flexible device is bent to a large extent and is excellent in durability can be manufactured.

[實施例] [Examples]

以下，依照實施例對本實施形態加以詳細說明。但本實施形態並不受以下實施例任何限定。 Hereinafter, this embodiment will be described in detail in accordance with the embodiments. However, the present embodiment is not limited to the following examples.

[合成例1] [Synthesis Example 1] (聚醯胺酸清漆P-1之合成) (Synthesis of polyamic acid varnish P-1)

於500ml三口可分離式燒瓶上安裝氮氣導入管。於氮氣下、油浴30℃下，放入N-甲基-2-吡咯啶酮(NMP)270.0g、3,3',4,4'-聯苯四羧酸二酐(BPDA)21.94g，進行攪拌直至均一地分散。另外，每次少量地添加對苯二胺(PPD)8.06g後，於油浴80℃下進行4小時之加熱，獲得聚醯胺酸清漆P-1。重量平均分子量為27萬。 A nitrogen introduction tube was attached to a 500 ml three-neck separable flask. Under nitrogen, oil bath 30 ° C, put N-methyl-2-pyrrolidone (NMP) 270.0g, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) 21.94g Stirring was carried out until uniformly dispersed. Further, after adding 8.06 g of p-phenylenediamine (PPD) in a small amount, it was heated in an oil bath at 80 ° C for 4 hours to obtain a polyamic acid varnish P-1. The weight average molecular weight is 270,000.

[合成例2] [Synthesis Example 2] (聚醯胺酸清漆P-2之合成) (Synthesis of polyglycolic acid varnish P-2)

於500ml三口可分離式燒瓶上安裝氮氣導入管。於氮氣下、油浴30℃下，放入N-甲基-2-吡咯啶酮(NMP)270.0g、4,4'-氧雙鄰苯二甲酸二酐(ODPA)22.14g，進行攪拌直至均一地分散。另外，每次少量地添加2,2'-雙(三氟甲基)聯苯胺(TFMB)22.86g後，於油浴80℃下進行4小時之加熱，獲得聚醯胺酸清漆P-2。重量平均分子量為20萬。 A nitrogen introduction tube was attached to a 500 ml three-neck separable flask. Under nitrogen and at an oil bath of 30 ° C, 270.0 g of N-methyl-2-pyrrolidone (NMP) and 22.14 g of 4,4'-oxydiphthalic dianhydride (ODPA) were placed and stirred until Uniformly dispersed. Further, 22.86 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB) was added in small portions, and the mixture was heated in an oil bath at 80 ° C for 4 hours to obtain a polyamic acid varnish P-2. The weight average molecular weight is 200,000.

[合成例3] [Synthesis Example 3] (聚醯亞胺清漆P-3之合成) (Synthesis of polyamid varnish P-3)

於500ml三口可分離式燒瓶上安裝氮氣導入管、迪恩-斯達克裝置。於氮氣下、油浴30℃下，放入N-甲基-2-吡咯啶酮(NMP)185.0g、甲苯100.0g、4,4'-氧雙鄰苯二甲酸二酐(ODPA)7.38g，進行攪拌直至均一地分散。另外，每次少量地添加2,2'-雙(三氟甲基)聯苯胺(TFMB)7.62g後，於油浴120℃下進行4小時之加熱。其後，放入N-甲基-2-吡咯啶酮(NMP)100.0g，於油浴120℃下進行加熱，藉此將甲苯除去，獲得聚醯亞胺清漆P-3。重量平均分子量為15萬。 A nitrogen inlet tube and a Dean-Stark unit were installed in a 500 ml three-neck separable flask. Under nitrogen, oil bath 30 ° C, placed N-methyl-2-pyrrolidone (NMP) 185.0g, toluene 100.0g, 4,4'-oxydiphthalic dianhydride (ODPA) 7.38g Stirring was carried out until uniformly dispersed. Further, 7.62 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB) was added in small portions, and then heated in an oil bath at 120 ° C for 4 hours. Thereafter, 100.0 g of N-methyl-2-pyrrolidone (NMP) was placed and heated in an oil bath at 120 ° C to remove toluene to obtain a polyimine varnish P-3. The weight average molecular weight is 150,000.

[合成例4] [Synthesis Example 4] (聚醯胺酸清漆P-4之合成) (Synthesis of polyamic acid varnish P-4)

於500ml三口可分離式燒瓶上安裝氮氣導入管。於氮氣下、油浴30℃下，放入N-甲基-2-吡咯啶酮(NMP)255.0g、4,4'-氧雙鄰苯二甲 酸二酐(ODPA)16.84g，進行攪拌直至均一地分散。另外，每次少量地添加2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷(HF-BAPP)28.16g後，於油浴80℃下進行4小時之加熱，獲得聚醯胺酸清漆P-4。重量平均分子量為18萬。 A nitrogen introduction tube was attached to a 500 ml three-neck separable flask. Under nitrogen, oil bath 30 ° C, put N-methyl-2-pyrrolidone (NMP) 255.0g, 4,4'-oxybisphthalic acid 16.84 g of acid dianhydride (ODPA) was stirred until uniformly dispersed. Further, after adding 28.16 g of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HF-BAPP) in a small amount, heating was carried out in an oil bath at 80 ° C for 4 hours. , obtaining polyamic acid varnish P-4. The weight average molecular weight is 180,000.

[合成例5] [Synthesis Example 5] (聚醯胺酸清漆P-5之合成) (Synthesis of polyamic acid varnish P-5)

於500ml三口可分離式燒瓶上安裝氮氣導入管。於氮氣下、油浴30℃下，放入N-甲基-2-吡咯啶酮(NMP)255.0g、2,2-雙(3,4-無水二羧基苯基)-六氟丙烷(6FDA)26.15g，進行攪拌直至均一地分散。另外，每次少量地添加2,2'-雙(三氟甲基)聯苯胺(TFMB)18.85g後，於油浴80℃下進行4小時之加熱，獲得聚醯胺酸清漆P-5。重量平均分子量為17萬。 A nitrogen introduction tube was attached to a 500 ml three-neck separable flask. Under nitrogen, oil bath 30 ° C, put N-methyl-2-pyrrolidone (NMP) 255.0g, 2,2-bis(3,4-anhydrodicarboxyphenyl)-hexafluoropropane (6FDA 26.15 g, stirring was carried out until uniformly dispersed. Further, 18.85 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB) was added in small portions, and the mixture was heated in an oil bath at 80 ° C for 4 hours to obtain a polyamic acid varnish P-5. The weight average molecular weight is 170,000.

[合成例6] [Synthesis Example 6] (聚醯胺酸清漆P-6之合成) (Synthesis of polyglycolic acid varnish P-6)

於500ml三口可分離式燒瓶上安裝氮氣導入管。於氮氣下、油浴30℃下，放入N-甲基-2-吡咯啶酮(NMP)255.0g、環己烷四羧酸二酐(PMDA-HH)18.53g，進行攪拌直至均一地分散。另外，每次少量地添加2,2'-雙(三氟甲基)聯苯胺(TFMB)31.42g後，於油浴80℃下進行4小時之加熱，獲得聚醯胺酸清漆P-6。重量平均分子量為19萬。 A nitrogen introduction tube was attached to a 500 ml three-neck separable flask. Under nitrogen, an oil bath at 30 ° C, 255.0 g of N-methyl-2-pyrrolidone (NMP) and 18.53 g of cyclohexane tetracarboxylic dianhydride (PMDA-HH) were placed and stirred until uniformly dispersed. . Further, 31.42 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB) was added in small portions, and the mixture was heated in an oil bath at 80 ° C for 4 hours to obtain a polyamic acid varnish P-6. The weight average molecular weight is 190,000.

[實施例1~26及比較例1~4] [Examples 1 to 26 and Comparative Examples 1 to 4] (聚醯胺酸及聚醯亞胺組合物之製備) (Preparation of poly-proline and polyimine composition)

如表1及表2所示般製備各種成分，加以混合。藉由孔徑為2.5微米之PTFE製過濾器對其進行加壓過濾，獲得實施例1~26及比較例1~4之清漆狀組合物。 Various components were prepared and mixed as shown in Tables 1 and 2. The varnish composition of Examples 1 to 26 and Comparative Examples 1 to 4 was obtained by pressure filtration through a PTFE filter having a pore size of 2.5 μm.

此處，所使用之(B)聚矽氧化合物或氟化合物及(C)烷氧基矽烷化合物如下所示。另外，比較例4中所含之烷氧基矽烷化合物為甲基三甲氧基矽烷，並不相當於具有選自由醯胺基、胺基、胺基甲酸酯基、羧基、芳基、酸酐基及聚合性環狀醚基所組成之群中之至少1種官能基的烷氧基矽烷化合物。 Here, the (B) polyoxyl compound or fluorine compound and (C) alkoxydecane compound used are as follows. Further, the alkoxydecane compound contained in Comparative Example 4 is methyltrimethoxydecane, and does not correspond to having a selected from the group consisting of a mercaptoamine group, an amine group, an aminoester group, a carboxyl group, an aryl group, and an acid anhydride group. And an alkoxydecane compound having at least one functional group in the group consisting of a polymerizable cyclic ether group.

(B)聚矽氧化合物或氟化合物 (B) polyoxyl compounds or fluorine compounds

A-1 DBE-712(Azmax公司製造) A-1 DBE-712 (manufactured by Azmax Corporation)

A-2 DBE-821(Azmax公司製造) A-2 DBE-821 (manufactured by Azmax)

A-3 Polyflow KL-100(共榮社化學公司製造) A-3 Polyflow KL-100 (manufactured by Kyoeisha Chemical Co., Ltd.)

A-4 Polyflow KL-401(共榮社化學公司製造) A-4 Polyflow KL-401 (manufactured by Kyoeisha Chemical Co., Ltd.)

A-5 Polyflow KL-402(共榮社化學公司製造) A-5 Polyflow KL-402 (manufactured by Kyoeisha Chemical Co., Ltd.)

A-6 Polyflow KL700(共榮社化學公司製造) A-6 Polyflow KL700 (manufactured by Kyoeisha Chemical Co., Ltd.)

A-7 LE-604(共榮社化學公司製造) A-7 LE-604 (manufactured by Kyoeisha Chemical Co., Ltd.)

A-8 LE-605(共榮社化學公司製造) A-8 LE-605 (manufactured by Kyoeisha Chemical Co., Ltd.)

A-9 LINC-151-EPA(共榮社化學公司製造) A-9 LINC-151-EPA (manufactured by Kyoeisha Chemical Co., Ltd.)

(C)烷氧基矽烷化合物 (C) alkoxydecane compound

S-1 3-(三乙氧基矽烷基丙基)琥珀酸酐(GELEST公司製造) S-1 3-(triethoxydecylpropyl) succinic anhydride (manufactured by GELEST)

S-2 3-縮水甘油氧基丙基三甲氧基矽烷(GELEST公司製造) S-2 3-glycidoxypropyltrimethoxydecane (GELEST)

S-3 3-胺基丙基三乙氧基矽烷(GELEST公司製造) S-3 3-aminopropyltriethoxydecane (GELEST)

S-4 3-胺基丙基三乙氧基矽烷與鄰苯二甲酸酐之1：1反應物 1:1 reaction of S-4 3-aminopropyltriethoxydecane with phthalic anhydride

S-5 3-胺基丙基三甲氧基矽烷與鄰苯二甲酸酐之1：1反應物 1:1 reaction of S-5 3-aminopropyltrimethoxydecane with phthalic anhydride

S-6 (3-三乙氧基矽烷基丙基)-第三丁基胺基甲酸酯(GELEST公司製造) S-6 (3-triethoxydecylpropyl)-t-butylaminocarbamate (GELEST)

S-7 3-胺基丙基三乙氧基矽烷與異氰酸苯酯之1：1反應物 1:1 reaction of S-7 3-aminopropyltriethoxydecane with phenyl isocyanate

S-8 3,3',4,4'-二苯甲酮四羧酸二酐與3-胺基丙基三乙氧基矽烷之1：2反應物 S-8 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 3-aminopropyltriethoxydecane 1:2 reactant

S-9 甲基三甲氧基矽烷(GELEST公司製造) S-9 methyltrimethoxydecane (manufactured by GELEST)

[聚醯亞胺組合物之膜形成] [Film formation of polyimine composition]

使用棒式塗佈機，將實施例1~26及比較例1~4中所得之清漆狀組合物以固化後之膜厚成為20μm之方式塗佈於藉由鹼清洗法及電漿清洗法對表面進行了清洗的10cm見方的無鹼玻璃基板上。藉由以下之固化條件之任意者對該等塗膜進行固化，於無鹼玻璃基板上形成20μm厚之聚醯亞胺樹脂層。將關於實施例1~26及比較例1~4所應用之固化條件表示於表3、表4中。 The varnish composition obtained in Examples 1 to 26 and Comparative Examples 1 to 4 was applied to the film thickness after curing to 20 μm by a bar coater by an alkali cleaning method and a plasma cleaning method. The surface was cleaned on a 10 cm square non-alkali glass substrate. The coating film was cured by any of the following curing conditions to form a 20 μm-thick polyimide resin layer on the alkali-free glass substrate. The curing conditions applied in Examples 1 to 26 and Comparative Examples 1 to 4 are shown in Tables 3 and 4.

清漆狀組合物之固化條件(均於氮氣環境下實施) Curing conditions of the varnish-like composition (all carried out under a nitrogen atmosphere)

A：140℃×1hr+250℃×1hr+350℃×1hr A: 140 ° C × 1 hr + 250 ° C × 1 hr + 350 ° C × 1 hr

B：140℃×1hr+450℃×1hr B: 140 ° C × 1 hr + 450 ° C × 1 hr

C：140℃×1hr+500℃×1hr C: 140 ° C × 1 hr + 500 ° C × 1 hr

該等實施例1~26、比較例1~4中所得之聚醯亞胺樹脂層之TG/DTA測定之結果為5%熱分解溫度高於400℃。 The results of TG/DTA measurement of the polyimine resin layers obtained in the above Examples 1 to 26 and Comparative Examples 1 to 4 were 5% thermal decomposition temperature higher than 400 °C.

[組合物之評價] [Evaluation of composition]

關於藉由實施例1~26及比較例1~4中所得之清漆狀組合物而製作的聚醯亞胺樹脂層，對以下項目進行評價，將結果表示於表3、表4中。 The polyimine resin layers produced by the varnish compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 4 were evaluated for the following items, and the results are shown in Tables 3 and 4.

1.固化後之聚醯亞胺樹脂層之密接性(於表3、表4中，記為固化後密接性) 1. Adhesion of the polyimide layer after curing (in Tables 3 and 4, it is referred to as adhesion after curing)

於實施例1~26及比較例1~4中所得的清漆狀組合物之於無鹼玻璃基板上所形成的固化後為20μm厚之聚醯亞胺樹脂層中，關於無鹼玻璃基板與聚醯亞胺樹脂層之密接性，藉由目視以如下基準確認塗膜之狀態。 The varnish-like composition obtained in Examples 1 to 26 and Comparative Examples 1 to 4 was formed on an alkali-free glass substrate and cured in a polyimide layer of 20 μm thick, and the non-alkali glass substrate and the poly The adhesion of the quinone imine resin layer was confirmed by visual observation on the basis of the following criteria.

◎：固化後，可於玻璃基板上形成均一之膜。 ◎: After curing, a uniform film can be formed on the glass substrate.

×：固化後，於玻璃基板上聚醯亞胺樹脂層部分性浮起、或剝落 之位置為1處以上。 ×: After curing, the polyimide film layer partially floats or peels off on the glass substrate The position is one or more.

2.無機膜形成後之聚醯亞胺樹脂層之長期密接性(於表3、表4中，記為長期密接性) 2. Long-term adhesion of the polyimide film layer after the formation of the inorganic film (in Tables 3 and 4, it is referred to as long-term adhesion)

於實施例1~26及比較例1~4中所得之清漆狀組合物之於無鹼玻璃基板上所形成的固化後為20μm厚之聚醯亞胺樹脂層上，藉由真空蒸鍍裝置以厚度成為50nm之方式蒸鍍二氧化矽膜。關於將該樣品於350℃×4hr、氮氣環境下進行加熱後之無鹼玻璃基板與聚醯亞胺樹脂層之密接性，藉由目視以如下之基準確認塗膜之狀態。 The varnish-like compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 4 were formed on an alkali-free glass substrate and cured on a 20 μm-thick polyimide resin layer by a vacuum evaporation apparatus. The ruthenium dioxide film was vapor-deposited so that the thickness became 50 nm. The adhesion between the alkali-free glass substrate and the polyimide resin layer after heating the sample at 350 ° C for 4 hr in a nitrogen atmosphere was confirmed by visual observation on the basis of the following criteria.

◎：固化後，於玻璃基板上形成均一之聚醯亞胺樹脂層。 ◎: After curing, a uniform polyimide resin layer was formed on the glass substrate.

×：固化後，於玻璃基板上聚醯亞胺樹脂層部分性浮起、或剝落之位置為1處以上。 X: After curing, the position at which the polyimide resin layer partially floats or peels off on the glass substrate is one or more.

3.透光性評價(於表3、表4中，記為透明性) 3. Transmittance evaluation (in Tables 3 and 4, it is recorded as transparency)

對於實施例1~26及比較例1~4中所得之清漆狀組合物之於玻璃基板上塗膜之固化後為20μm厚之聚醯亞胺樹脂層，使用分光光度計UV-1600PC(島津公司製造)而測定800nm~300nm之透光率，確認550nm之透光率。此時，於參考部放置並無塗膜之無鹼玻璃基板。 The varnish-like composition obtained in Examples 1 to 26 and Comparative Examples 1 to 4 was a 20 μm thick polyimine resin layer after curing on a glass substrate, and a spectrophotometer UV-1600PC (Shimadzu Corporation) was used. The light transmittance of 800 nm to 300 nm was measured, and the light transmittance at 550 nm was confirmed. At this time, an alkali-free glass substrate having no coating film was placed on the reference portion.

4.180°剝離強度評價(於表3、表4中，記為180°剝離強度) 4.180° peel strength evaluation (in Tables 3 and 4, denoted as 180° peel strength)

將實施例1~26及比較例1~4中所得之清漆狀組合物之於玻璃基板上塗膜之固化後為20μm厚之聚醯亞胺樹脂層切出為長10mm、寬10mm，藉由膠帶遮蔽寬10mm之中央部之寬1.0mm。其後，於溫度為23±2℃、濕度為50±5%RH之環境下進行24小時以上之濕度控制，於相同環境下，將藉由膠帶而遮蔽之寬1.0mm之聚醯亞胺樹脂層自玻璃基板以剝離角度為180°、剝離速度為50mm/分進行剝離而測定其應力。 The varnish-like composition obtained in Examples 1 to 26 and Comparative Examples 1 to 4 was cured on a glass substrate and cured to a thickness of 10 mm and a width of 10 mm by a polyimide layer having a thickness of 20 μm. The width of the central portion of the tape covering width of 10 mm is 1.0 mm. Thereafter, the humidity is controlled for 24 hours or more in an environment of a temperature of 23±2° C. and a humidity of 50±5% RH, and a 1.0 mm wide polyimine resin which is shielded by a tape under the same environment is used. The layer was peeled off from the glass substrate at a peeling angle of 180° and a peeling speed of 50 mm/min, and the stress was measured.

5.自玻璃基板剝離聚醯亞胺樹脂層之剝離性評價(於表3、表4中，記為剝離性) 5. Evaluation of peelability of the polyimide film layer peeled off from the glass substrate (in Tables 3 and 4, it is referred to as peelability)

將實施例1~26及比較例1~4中所得之清漆狀組合物之於20cm見方之玻璃基板上所形成的固化後(固化條件：A、B、C)為20μm厚的聚醯亞胺樹脂層中，藉由截切刀於自聚醯亞胺樹脂層之4個邊之邊緣起2cm之部分而切入切口，製作具有1邊為16cm之四邊形之切口的聚醯亞胺樹脂層之樣品。於該樣品之端部貼聚醯亞胺膠帶，提拉聚醯亞胺膠帶，藉此自玻璃基板剝離樣品。此時，藉由以下之基準判斷剝離之容易性。 The varnish-like composition obtained in Examples 1 to 26 and Comparative Examples 1 to 4 was cured on a 20 cm square glass substrate (curing conditions: A, B, C) to be 20 μm thick polyimine. In the resin layer, a slit was cut into a slit by a cutting blade at a distance of 2 cm from the edge of the four sides of the polyimide film to prepare a sample of a polyimide film having a hexagonal cut of 16 cm on one side. . The yttrium imide tape was attached to the end of the sample, and the polyimide tape was pulled to peel the sample from the glass substrate. At this time, the easiness of peeling was judged by the following criteria.

◎：可將密接於玻璃基板上之聚醯亞胺樹脂層容易地剝離。 ◎: The polyimide film layer adhered to the glass substrate can be easily peeled off.

○：密接於玻璃基板上之聚醯亞胺樹脂層密接，於剝離時雖然存在牽連，但聚醯亞胺樹脂層可並不破裂地剝離。 ○: The polyimide film of the polyimide film adhered to the glass substrate was in close contact with each other, and the polyimide layer was peeled off at the time of peeling, but the polyimide film layer was peeled off without breaking.

×：聚醯亞胺樹脂層並未密接於玻璃基板上，或聚醯亞胺樹脂層密接而並不剝落，但膜破裂。 X: The polyimide resin layer was not adhered to the glass substrate, or the polyimide resin layer was adhered without peeling off, but the film was broken.

根據表3、表4可知：包含(a)聚醯亞胺或聚醯亞胺前驅物、(b)聚矽氧系界面活性劑或氟系界面活性劑、(c)具有選自由胺基、胺基甲酸酯基、羧基、芳基、酸酐基、醯胺基及聚合性環狀醚基所組成之群中之至少1種官能基的烷氧基矽烷化合物之樹脂組合物與如比較例1~4之組合物相比而言，可保持固化後之樹脂組合物對無機基板之膜密接性及長期密接性，且於無機基板上所形成之聚醯亞胺樹脂層之剝離性變良好(實施例1~實施例26)。 According to Tables 3 and 4, it is known that (a) a polyimine or a polyimide precursor, (b) a polyoxyn surfactant or a fluorine-based surfactant, (c) has an amine group selected from the group consisting of Resin composition of alkoxydecane compound having at least one functional group of a group consisting of a urethane group, a carboxyl group, an aryl group, an acid anhydride group, a guanamine group, and a polymerizable cyclic ether group, and a comparative example In comparison with the composition of 1 to 4, the film adhesiveness and long-term adhesion of the resin composition after curing to the inorganic substrate can be maintained, and the peeling property of the polyimide film formed on the inorganic substrate becomes good. (Examples 1 to 26).

又，藉由選擇(c)成分之具有選自由胺基甲酸酯基、羧基、醯胺基及芳基所組成之群中之至少1種官能基的烷氧基矽烷化合物，自無機基板剝離聚醯亞胺樹脂層之剝離性變得更良好。 Further, the alkoxydecane compound having at least one functional group selected from the group consisting of a urethane group, a carboxyl group, a guanamine group, and an aryl group of the component (c) is selected and stripped from the inorganic substrate. The peeling property of the polyimide resin layer becomes more favorable.

根據該等之結果可知：實施例1~26之樹脂組合物可製成可撓性裝置之基板，而且積層體可適宜地用作可撓性裝置製造用基板。 As a result of the above, it is understood that the resin compositions of Examples 1 to 26 can be used as a substrate for a flexible device, and the laminate can be suitably used as a substrate for manufacturing a flexible device.

[實施例27] [Example 27]

將作為(A)聚醯胺酸之於合成例1中所示之P-1、作為(B)聚矽氧化合物之DBE-712(Azmax公司製造)、作為(C)烷氧基矽烷化合物之3-胺基丙基三乙氧基矽烷與鄰苯二甲酸酐之1：1反應物、作為(D)溶劑之N-甲基-2-吡咯啶酮(NMP)以10.0：0.05：0.05：89.90之質量比進行調合、混合。藉由孔徑為2.5微米之PTFE製過濾器對其進行加壓過濾而獲得清漆狀組合物。 (A) Poly (proamino acid) is represented by P-1 shown in Synthesis Example 1, DBE-712 (manufactured by Azmax Corporation) as (B) polyfluorene oxide compound, and (C) alkoxydecane compound. a 1:1 reaction of 3-aminopropyltriethoxysilane with phthalic anhydride, N-methyl-2-pyrrolidone (NMP) as a solvent (D) at 10.0:0.05:0.05: The mass ratio of 89.90 is blended and mixed. This was subjected to pressure filtration through a PTFE filter having a pore size of 2.5 μm to obtain a varnish-like composition.

使用棒式塗佈機，將清漆狀組合物以固化後之膜厚成為20μm之方式塗佈於藉由鹼清洗法及電漿清洗法對表面進行了清洗的無鹼玻璃基板上。而且，將所得之塗膜於140℃×1hr+250℃×1hr+350℃×1hr之條件進行固化。 The varnish-like composition was applied to an alkali-free glass substrate which was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. Further, the obtained coating film was cured under the conditions of 140 ° C × 1 hr + 250 ° C × 1 hr + 350 ° C × 1 hr.

[實施例28] [Example 28]

將作為(A)聚醯胺酸之於合成例1中所示之P-1、作為(B)氟化合物之LE-605(共榮社化學公司製造)、作為(C)烷氧基矽烷化合物之3-胺基 丙基三乙氧基矽烷與鄰苯二甲酸酐之1：1反應物、作為(D)溶劑之N-甲基-2-吡咯啶酮(NMP)以10.0：0.09：0.01：89.90之質量比進行調合、混合。藉由孔徑為2.5微米之PTFE製過濾器對其進行加壓過濾而獲得清漆狀組合物。 (A) Poly (proamino acid) is represented by P-1 shown in Synthesis Example 1, LE-605 (manufactured by Kyoeisha Chemical Co., Ltd.) as (B) fluorine compound, and (C) alkoxydecane compound. 3-amino group 1:1 reaction of propyltriethoxysilane with phthalic anhydride, N-methyl-2-pyrrolidone (NMP) as solvent (D) at a mass ratio of 10.0:0.09:0.01:89.90 Make blending and mixing. This was subjected to pressure filtration through a PTFE filter having a pore size of 2.5 μm to obtain a varnish-like composition.

使用棒式塗佈機，將清漆狀組合物以固化後之膜厚成為20μm之方式塗佈於藉由鹼清洗法及電漿清洗法對表面進行了清洗的無鹼玻璃基板上。而且，將所得之塗膜於140℃×1hr+250℃×1hr+350℃×1hr之條件進行固化。 The varnish-like composition was applied to an alkali-free glass substrate which was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. Further, the obtained coating film was cured under the conditions of 140 ° C × 1 hr + 250 ° C × 1 hr + 350 ° C × 1 hr.

[比較例5] [Comparative Example 5]

將作為(A)聚醯胺酸之於合成例1中所示之P-1、作為(B)聚矽氧化合物之DBE-712(Azmax公司製造)、作為(D)溶劑之N-甲基-2-吡咯啶酮(NMP)以10.0：0.05：89.95之質量比加以調合、混合。藉由孔徑為2.5微米之PTFE製過濾器對其進行加壓過濾而獲得清漆狀組合物。 P-1 as (A) polylysine in Synthesis Example 1, DBE-712 (manufactured by Azmax Corporation) as (B) polyfluorene oxide, and N-methyl as (D) solvent The 2-pyrrolidone (NMP) was blended and mixed at a mass ratio of 10.0:0.05:89.95. This was subjected to pressure filtration through a PTFE filter having a pore size of 2.5 μm to obtain a varnish-like composition.

使用棒式塗佈機，將清漆狀組合物以固化後之膜厚成為20μm之方式塗佈於藉由鹼清洗法及電漿清洗法對表面進行了清洗的無鹼玻璃基板上。而且，將所得之塗膜於140℃×1hr+250℃×1hr+350℃×1hr之條件進行固化。 The varnish-like composition was applied to an alkali-free glass substrate which was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. Further, the obtained coating film was cured under the conditions of 140 ° C × 1 hr + 250 ° C × 1 hr + 350 ° C × 1 hr.

[比較例6] [Comparative Example 6]

將作為(A)聚醯胺酸之於合成例1中所示之P-1、作為(B)氟化合物之LE-605(共榮社化學公司製造)、作為(D)溶劑之N-甲基-2-吡咯啶酮(NMP)以10.0：0.09：89.91之比加以調合、混合。藉由孔徑為2.5微米之PTFE製過濾器對其進行加壓過濾而獲得清漆狀組合物。 As the (A) polylysine, P-1 shown in Synthesis Example 1, LE-605 (manufactured by Kyoeisha Chemical Co., Ltd.) as (B) fluorine compound, and N-A as (D) solvent The base-2-pyrrolidone (NMP) was blended and mixed at a ratio of 10.0:0.09:89.91. This was subjected to pressure filtration through a PTFE filter having a pore size of 2.5 μm to obtain a varnish-like composition.

使用棒式塗佈機，將清漆狀組合物以固化後之膜厚成為20μm之方式塗佈於藉由鹼清洗法及電漿清洗法對表面進行了清洗的無鹼玻璃基板上。而且，將所得之塗膜於140℃×1hr+250℃×1hr+350℃×1hr之條件進行固化。 The varnish-like composition was applied to an alkali-free glass substrate which was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. Further, the obtained coating film was cured under the conditions of 140 ° C × 1 hr + 250 ° C × 1 hr + 350 ° C × 1 hr.

[比較例7] [Comparative Example 7]

將作為(A)聚醯胺酸之於合成例1中所示之P-1、作為(C)烷氧基矽烷化合物之3-胺基丙基三乙氧基矽烷與鄰苯二甲酸酐之1：1反應物、作為(D)溶劑之N-甲基-2-吡咯啶酮(NMP)以10.0：0.05：89.95之質量比加以調合、混合。藉由孔徑為2.5微米之PTFE製過濾器對其進行加壓過濾而獲得清漆狀組合物。 As the (A) polylysine, P-1 shown in Synthesis Example 1, 3-aminopropyltriethoxydecane as (C) alkoxydecane compound, and phthalic anhydride The 1:1 reactant and N-methyl-2-pyrrolidone (NMP) as a solvent (D) were blended and mixed at a mass ratio of 10.0:0.05:89.95. This was subjected to pressure filtration through a PTFE filter having a pore size of 2.5 μm to obtain a varnish-like composition.

使用棒式塗佈機，將清漆狀組合物以固化後之膜厚成為20μm之方式塗佈於藉由鹼清洗法及電漿清洗法對表面進行了清洗的無鹼玻璃基板上。而且，將所得之塗膜於140℃×1hr+250℃×1hr+350℃×1hr之條件進行固化。 The varnish-like composition was applied to an alkali-free glass substrate which was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. Further, the obtained coating film was cured under the conditions of 140 ° C × 1 hr + 250 ° C × 1 hr + 350 ° C × 1 hr.

[組合物(可撓性裝置用基板)之結構分析] [Structural analysis of composition (substrate for flexible device)]

於實施例27、28及比較例5~6中，使用TOF-SIMS而實施塗佈於無鹼玻璃基板上且固化而成之包含組合物之可撓性裝置用基板之結構分析。TOF-SIMS之測定條件如下所示。 In Examples 27 and 28 and Comparative Examples 5 to 6, the structural analysis of the substrate for a flexible device containing the composition, which was applied to an alkali-free glass substrate and cured, was carried out using TOF-SIMS. The measurement conditions of TOF-SIMS are as follows.

[分析方法(TOF-SIMS)] [Analytical Method (TOF-SIMS)]

將各試樣切為5mm之四方狀，以測定面向上之方式而安放，供至TOF-SIMS測定。首先，為了除去表面之污染，藉由下述條件進行濺鍍清潔。濺鍍時間設為Si強度變固定為止。 Each sample was cut into a square shape of 5 mm, and placed in a measurement side-up manner, and was subjected to TOF-SIMS measurement. First, in order to remove surface contamination, sputter cleaning was performed under the following conditions. The sputtering time is set such that the Si intensity becomes fixed.

<濺鍍清潔條件> <sputter cleaning conditions>

(測定條件) (measurement conditions)

使用機器：nanoTOF(ULVAC-PHI公司製造) Machine used: nanoTOF (manufactured by ULVAC-PHI)

一次離子：Bi3 ++ Primary ion: Bi 3 ++

加速電壓：30kV Acceleration voltage: 30kV

離子電流：約0.47nA(DC) Ion current: about 0.47nA (DC)

分析面積：200μm×200μm Analysis area: 200μm × 200μm

分析時間：6sec Analysis time: 6sec

檢測離子：正離子 Detection ion: positive ion

中和：使用電子槍(視需要使用+Ar單體) Neutralization: use an electron gun (+Ar monomer if needed)

(濺鍍條件) (sputter condition)

濺鍍離子：Ar2500 + Sputtering Ion: Ar 2500 +

加速電壓：20kV Acceleration voltage: 20kV

離子電流：約5nA Ion current: about 5nA

濺鍍面積：600μm×600μm Sputtering area: 600μm × 600μm

濺鍍時間：30sec Sputtering time: 30sec

中和：使用電子槍 Neutral: Using an electron gun

將表面污染除去後，藉由下述測定條件實施測定。 After the surface contamination was removed, the measurement was carried out under the following measurement conditions.

<分析條件> <Analysis conditions>

(測定條件) (measurement conditions)

使用機器：nanoTOF(ULVAC-PHI公司製造) Machine used: nanoTOF (manufactured by ULVAC-PHI)

一次離子：Bi3 ++ Primary ion: Bi 3 ++

加速電壓：30kV Acceleration voltage: 30kV

離子電流：約0.47nA(DC) Ion current: about 0.47nA (DC)

分析面積：200μm×200μm Analysis area: 200μm × 200μm

分析時間：15min Analysis time: 15min

檢測離子：正離子 Detection ion: positive ion

中和：使用電子槍(視需要使用+Ar單體) Neutralization: use an electron gun (+Ar monomer if needed)

於圖9中表示實施例27、比較例5、比較例7之TOF-SIMS之m/z=78.7~79.3之結果。縱軸表示Total Counts(0.0005amu)。於實施例27及比較例7中，於m/z=78.98~79.00之間檢測出烷氧基矽烷化合物之特徵性峰值(SiO3H3)。 The results of m/z = 78.7 to 79.3 of TOF-SIMS of Example 27, Comparative Example 5, and Comparative Example 7 are shown in Fig. 9 . The vertical axis represents Total Counts (0.0005 amu). In Example 27 and Comparative Example 7, the characteristic peak (SiO 3 H 3 ) of the alkoxydecane compound was detected between m/z = 78.98 and 79.00.

藉由以下基準判斷所得的分析結果。將結果表示於表5中。 The analysis results obtained are judged by the following criteria. The results are shown in Table 5.

○：具有(C)烷氧基矽烷化合物之特徵性峰值。 ○: having a characteristic peak of the (C) alkoxydecane compound.

×：並不具有(C)烷氧基矽烷化合物之特徵性峰值。 ×: Does not have a characteristic peak of the (C) alkoxydecane compound.

於圖10中表示實施例27、比較例5、比較例7之TOF-SIMS之m/z=58.4~59.5之結果。縱軸表示Total Counts(0.0009amu)。又，於圖11中表示實施例27、比較例5、比較例7之TOF-SIMS之m/z=44.5~45.5之結果。縱軸表示Total Counts(0.0008amu)。於實施例27及比較例5中，檢測出界面活性劑之聚矽氧部位之特徵性峰值(SiOCH3)(圖10中所示之m/z=58.99附近)、及親水性基之特徵性峰值(C2H5O)(圖11中所示之m/z=45.03附近)。 The results of m/z = 58.4 to 59.5 of TOF-SIMS of Example 27, Comparative Example 5, and Comparative Example 7 are shown in FIG. The vertical axis represents Total Counts (0.0009 amu). Further, Fig. 11 shows the results of m/z = 44.5 to 45.5 of TOF-SIMS of Example 27, Comparative Example 5, and Comparative Example 7. The vertical axis represents Total Counts (0.0008 amu). In Example 27 and Comparative Example 5, the characteristic peak (SiOCH 3 ) of the polyoxo-oxygen moiety of the surfactant (m/z=58.99 shown in FIG. 10) and the characteristic of the hydrophilic group were detected. Peak (C 2 H 5 O) (m/z = 45.03 shown in Figure 11).

藉由以下基準判斷所得的分析結果。將結果表示於表5中。 The analysis results obtained are judged by the following criteria. The results are shown in Table 5.

○：具有(B)界面活性劑之特徵性峰值。 ○: Has a characteristic peak of (B) surfactant.

×：並不具有(B)界面活性劑之特徵性峰值。 ×: Does not have the characteristic peak of (B) surfactant.

[作為可撓性裝置用基板之評價] [Evaluation as a substrate for a flexible device]

藉由光學式膜厚計測定實施例27、28及比較例5~6中所得之可撓性裝置用基板(具有可撓性之膜狀)之膜厚，藉由以下基準進行判斷。將結果表示於表5中。 The film thicknesses of the substrates for flexible devices (having a flexible film shape) obtained in Examples 27 and 28 and Comparative Examples 5 to 6 were measured by an optical film thickness meter, and were judged based on the following criteria. The results are shown in Table 5.

○：於寬度為10cm之範圍內，膜厚不均為50nm以下 ○: The film thickness is not more than 50 nm in the range of 10 cm in width.

×：於寬度為10cm之範圍內，膜厚不均大於50nm ×: film thickness unevenness is more than 50 nm in a range of 10 cm in width

-：無法測定 -: Unable to measure

[實施例29] [Example 29]

將實施例27中所得之積層體作為可撓性裝置製造用基板，於積 層體上形成第1障壁層。進而於第1障壁層上依序形成半導體層、閘極絕緣膜、閘極電極、層間絕緣膜、接觸孔、源極-汲極電極，形成薄膜電晶體(TFT)。其後，自無鹼玻璃基板剝離TFT裝置而獲得可撓性TFT裝置。評價所得之可撓性TFT裝置之電流-電壓特性，確認顯示良好之面內均一性。 The laminate obtained in Example 27 was used as a substrate for manufacturing a flexible device. A first barrier layer is formed on the layer body. Further, a semiconductor layer, a gate insulating film, a gate electrode, an interlayer insulating film, a contact hole, and a source-drain electrode are sequentially formed on the first barrier layer to form a thin film transistor (TFT). Thereafter, the TFT device was peeled off from the alkali-free glass substrate to obtain a flexible TFT device. The current-voltage characteristics of the obtained flexible TFT device were evaluated, and it was confirmed that the in-plane uniformity was good.

[實施例30] [Example 30]

將實施例28中所得之積層體作為可撓性裝置製造用基板，於積層體上形成第1障壁層。進而於第1障壁層上依序形成半導體層、閘極絕緣膜、閘極電極、層間絕緣膜、接觸孔、源極-汲極電極，形成薄膜電晶體(TFT)。其後，自無鹼玻璃基板剝離TFT裝置而獲得可撓性TFT裝置。評價所得之可撓性TFT裝置之電流-電壓特性，確認顯出良好之面內均一性。 The laminate obtained in Example 28 was used as a substrate for manufacturing a flexible device, and a first barrier layer was formed on the laminate. Further, a semiconductor layer, a gate insulating film, a gate electrode, an interlayer insulating film, a contact hole, and a source-drain electrode are sequentially formed on the first barrier layer to form a thin film transistor (TFT). Thereafter, the TFT device was peeled off from the alkali-free glass substrate to obtain a flexible TFT device. The current-voltage characteristics of the obtained flexible TFT device were evaluated, and it was confirmed that good in-plane uniformity was exhibited.

再者，本發明並不限定於上述實施形態，可進行各種變更而實施。於上述實施形態中，關於隨附圖式中所圖示之大小或形狀等，並不限定於此，可於發揮本發明之效果之範圍內進行適宜變更。 Furthermore, the present invention is not limited to the above embodiment, and various modifications can be made. In the above-described embodiments, the size, shape, and the like as illustrated in the drawings are not limited thereto, and may be appropriately changed within the scope of the effects of the present invention.

於上述實施形態中，列舉將本實施形態之樹脂組合物用於可撓性顯示器之基板中的例子加以說明，但並不限定於此。本發明例如亦可應用於太陽電池之基板、可撓性配線板、可撓性記憶體等、其他可撓性裝置中。 In the above embodiment, an example in which the resin composition of the present embodiment is used for a substrate of a flexible display is described, but the invention is not limited thereto. The present invention can also be applied to, for example, a substrate for a solar cell, a flexible wiring board, a flexible memory, or the like, and other flexible devices.

[產業上之可利用性] [Industrial availability]

本發明例如於可撓性裝置之製造中，特別可用作基板，例如於可撓性顯示器及太陽電池之製造中可適宜地利用。 The present invention is particularly useful as a substrate in the manufacture of a flexible device, for example, in the manufacture of a flexible display and a solar cell.

本申請基於2012年11月8日提出申請之日本專利申請特願2012-246473。其內容全部包含於本文中。 The present application is based on Japanese Patent Application No. 2012-246473 filed on Nov. 8, 2012. Its contents are all included in this article.

11‧‧‧第1基板 11‧‧‧1st substrate

12‧‧‧第1聚醯亞胺樹脂層 12‧‧‧1st polyimide resin layer

Claims (5)

一種可撓性裝置用基板，其特徵在於含有：(α)5%熱分解溫度為350℃以上之聚醯亞胺、(β)具有下述通式(1)所表示之化學結構及/或下述通式(2)所表示之化學結構之化合物、(γ)具有由下述通式(3)所表示之化學結構、羥基、羧基及磺基所組成之群中之1種以上之化合物、及(δ)具有下述通式(4)所表示之化學結構之化合物； [化3]通式(3) -(CH2)nO-(n表示1以上5以下之整數)[化4]通式(4)-Si(OH)3。 A substrate for a flexible device, comprising: (α) 5% of a polyamidene having a thermal decomposition temperature of 350 ° C or higher, (β) having a chemical structure represented by the following formula (1) and/or a compound having a chemical structure represented by the following formula (2), and (γ) having one or more compounds selected from the group consisting of a chemical structure represented by the following formula (3), a hydroxyl group, a carboxyl group, and a sulfo group; And (δ) a compound having a chemical structure represented by the following formula (4); (3) - (CH 2 ) n O- (n represents an integer of 1 or more and 5 or less) [Chemical Formula 4] Formula (4)-Si(OH) 3 . 一種可撓性裝置，其特徵在於：於如請求項1之可撓性裝置用基板上形成有半導體裝置。 A flexible device characterized in that a semiconductor device is formed on a substrate for a flexible device according to claim 1. 如請求項2之可撓性裝置，其中上述半導體裝置為薄膜電晶體。 The flexible device of claim 2, wherein the semiconductor device is a thin film transistor. 如請求項2或3之可撓性裝置，其中上述可撓性裝置為多晶矽半導體或金屬氧化物半導體驅動型可撓性顯示器。 The flexible device of claim 2 or 3, wherein the flexible device is a polycrystalline germanium semiconductor or a metal oxide semiconductor driven flexible display. 一種可撓性裝置，其特徵在於包含聚醯亞胺樹脂層，該聚醯亞胺樹脂層含有：(α)5%熱分解溫度為350℃以上之聚醯亞胺、(β)具有下述通式(1)所表示之化學結構及/或下述通式(2)所表示之化學結構之化合物、(γ)具有由下述通式(3)所表示之化學結構、羥基、羧基及磺基所組成之群中之1種以上之化合物、及(δ)具有下述通式(4)所表示之化學結構之化合物；[化5]通式(1) [化7]通式(3)-(CH2)nO-(n表示1以上5以下之整數)[化8]通式(4)-Si(OH)3。 A flexible device comprising a polyimine resin layer comprising: (α) 5% of a polyamidene having a thermal decomposition temperature of 350 ° C or higher, (β) having the following The chemical structure represented by the formula (1) and/or the chemical structure represented by the following formula (2), (γ) has a chemical structure represented by the following formula (3), a hydroxyl group, a carboxyl group, and One or more compounds of the group consisting of a sulfo group, and (δ) a compound having a chemical structure represented by the following formula (4); [Chemical Formula 5] Formula (1) General formula (3)-(CH 2 ) n O- (n represents an integer of 1 or more and 5 or less) [Chemical Formula 8] General formula (4)-Si(OH) 3 .
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