TWI773715B - Manufacturing method of resin substrate with protective layer and manufacturing method of flexible electronic device - Google Patents

Manufacturing method of resin substrate with protective layer and manufacturing method of flexible electronic device Download PDF

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TWI773715B
TWI773715B TW106145941A TW106145941A TWI773715B TW I773715 B TWI773715 B TW I773715B TW 106145941 A TW106145941 A TW 106145941A TW 106145941 A TW106145941 A TW 106145941A TW I773715 B TWI773715 B TW I773715B
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substrate
protective layer
resin substrate
resin
forming
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TW201833224A (en
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江原和也
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日商日產化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate

Abstract

本發明提供一種基板保護層形成用組成物，其係在基體上形成樹脂基板後，剝離上述樹脂基板而製作樹脂基板時，介於上述基體與樹脂基板之間存在，具有從上述基體的易剝離性，同時具有作為剝離後的樹脂基板之保護層的機能之基板保護層形成用組成物，該組成物包含聚醯胺酸與有機溶劑。 The present invention provides a composition for forming a substrate protective layer, which exists between the substrate and the resin substrate after forming a resin substrate on a substrate, and then peels off the resin substrate to prepare the resin substrate, and has easy peeling from the substrate. A composition for forming a substrate protective layer, which has a function as a protective layer of a resin substrate after peeling, and contains a polyamic acid and an organic solvent.

Description

附保護層的樹脂基板之製造方法與可撓性電子裝置之製造方法 Manufacturing method of resin substrate with protective layer and manufacturing method of flexible electronic device

本發明關於基板保護層形成用組成物。 The present invention relates to a composition for forming a substrate protective layer.

近年來，於電子裝置不僅要求薄型化及輕量化之特性，而且要求賦予能彎曲之機能。因此，代替以往之重的、脆弱、無法彎曲的玻璃基板，要求使用輕量的可撓性塑膠基板。 In recent years, electronic devices have been required not only to be thin and light in weight, but also to have a bendable function. Therefore, a lightweight flexible plastic substrate is required to replace the heavy, fragile, and inflexible glass substrate in the past.

特別是，於新世代顯示器中，要求使用輕量的可撓性塑膠基板(以下，記載為樹脂基板)之主動矩陣型全彩TFT顯示器面板之開發。關於此新世代顯示器的技術，期待對於可撓性顯示器或可撓性智慧型手機、鏡面顯示器等之各式各樣的領域之轉用。 In particular, in a new generation display, development of an active matrix type full-color TFT display panel using a lightweight flexible plastic substrate (hereinafter, referred to as a resin substrate) is required. The technology of this next-generation display is expected to be transferred to various fields such as flexible displays, flexible smartphones, and mirror displays.

因此，以樹脂薄膜作為基板的電子裝置之製造方法係開始各種檢討，於新世代顯示器中，進行既有的TFT顯示器面板製造用之設備能轉用的程序之檢討。 Therefore, various reviews have been initiated on the manufacturing method of electronic devices using resin films as substrates, and a review of the procedures that can be transferred from existing TFT display panel manufacturing equipment in new-generation displays.

例如，專利文獻1、2及3中揭示在玻璃基板上形成非晶矽薄膜層，於該薄膜層上形成塑膠基板後，從玻璃基板側照射雷射而使非晶矽結晶化，藉由伴隨其結晶化 所發生的氫氣，而將塑膠基板從玻璃基板剝離之方法。 For example, Patent Documents 1, 2 and 3 disclose that an amorphous silicon thin film layer is formed on a glass substrate, and a plastic substrate is formed on the thin film layer, and then the amorphous silicon is crystallized by irradiating a laser from the glass substrate side. its crystallization The method of peeling off the plastic substrate from the glass substrate by generating hydrogen gas.

又，專利文獻4中揭示使用專利文獻1~3所揭示的技術，將被剝離層(專利文獻4中記載為「被轉印層」)貼附於塑膠薄膜，而完成液晶顯示裝置之方法。 In addition, Patent Document 4 discloses a method for completing a liquid crystal display device by attaching a peelable layer (described in Patent Document 4 as a "transferable layer") to a plastic film using the techniques disclosed in Patent Documents 1 to 3.

然而，於專利文獻1~4所揭示的方法，尤其專利文獻4所揭示的方法中，有以下之問題：為了使雷射光穿透，必須使用透光性高的基板，為了通過基板，更且使非晶矽中所含有的氫放出，必需充分之比較大的能量之雷射光的照射，有因雷射光之照射而對於被剝離層造成損傷之情況等。 However, the methods disclosed in Patent Documents 1 to 4, especially the method disclosed in Patent Document 4, have the following problems: in order to transmit the laser light, a substrate with high light transmittance must be used, and in order to pass through the substrate, the In order to release the hydrogen contained in the amorphous silicon, it is necessary to irradiate the laser light with a sufficient relatively large energy, and the peeled layer may be damaged by the irradiation of the laser light.

而且，當被剝離層為大面積時，由於在雷射處理需要長時間，而難以提高裝置製作的生產性。 Furthermore, when the layer to be peeled has a large area, it takes a long time for the laser processing, and it is difficult to improve the productivity of the device fabrication.

作為解決如此的問題之手段，於專利文獻5中採用以下的製程：使用現行的玻璃基板作為基體(以下，稱為玻璃基體)，於此玻璃基體上使用如環狀烯烴共聚物的聚合物來形成剝離層，於該剝離層上形成聚醯亞胺薄膜等的耐熱樹脂薄膜(樹脂基板)後，在該薄膜上以真空程序形成ITO透明電極或TFT等並予以密封後，最後剝離‧去除玻璃基體。 As a means to solve such a problem, the following process is adopted in Patent Document 5. A current glass substrate is used as a substrate (hereinafter, referred to as a glass substrate), and a polymer such as a cyclic olefin copolymer is used on the glass substrate. Forming a peeling layer, forming a heat-resistant resin film (resin substrate) such as a polyimide film on the peeling layer, then forming an ITO transparent electrode or TFT on the film by a vacuum process and sealing, and finally peeling and removing the glass matrix.

可是，目前作為TFT，使用移動率比非晶矽TFT快2倍的低溫多晶矽TFT。此低溫多晶矽TFT係在非晶矽蒸鍍後，必須以400℃以上進行脫氫退火，照射脈衝雷射，使矽結晶化(以下，將此等稱為TFT步驟)，但是上述脫氫退火步驟之溫度為既有的聚合物之玻璃轉移溫度(以下Tg)以上。 However, as a TFT at present, a low temperature polysilicon TFT having a mobility twice as fast as that of an amorphous silicon TFT is used. This low-temperature polysilicon TFT requires dehydrogenation annealing at a temperature of 400°C or higher after the vapor deposition of amorphous silicon, and irradiating a pulsed laser to crystallize the silicon (hereinafter, these are referred to as TFT steps). However, the above dehydrogenation annealing step The temperature is equal to or higher than the glass transition temperature (hereinafter Tg) of the existing polymer.

然而，已知既有的聚合物係在被加熱至Tg以上的溫度時，密著性升高(例如，參照專利文獻6)，於加熱處理後剝離層與基體及樹脂基板之密著性升高，將樹脂基板從基體剝離會變困難。 　　[0009] 又，可適用於如此的步驟之耐熱性聚合物係限於聚醯亞胺等之一部分的高耐熱性高分子化合物，但無法溶解於一般的溶劑中。因此，將上述聚醯亞胺用於剝離層時，於剝離樹脂基板後，難以去除玻璃基體上所殘留的剝離層而再利用玻璃基體。 [先前技術文獻] [專利文獻] 　　[0010] 　　[專利文獻1]日本特開平10-125929號公報 　　[專利文獻2]日本特開平10-125931號公報 　　[專利文獻3]國際公開第2005/050754號 　　[專利文獻4]日本特開平10-125930號公報 　　[專利文獻5]日本特開2010-111853號公報 　　[專利文獻6]日本特開2008-188792號公報However, it is known that the adhesiveness of the conventional polymer system increases when heated to a temperature higher than Tg (for example, refer to Patent Document 6), and the adhesiveness of the peeling layer to the base and the resin substrate increases after the heat treatment. high, it becomes difficult to peel the resin substrate from the base. [0009] In addition, the heat-resistant polymer that can be applied to such a step is limited to a part of the high heat-resistant polymer compound such as polyimide, but cannot be dissolved in a general solvent. Therefore, when the said polyimide is used for a peeling layer, after peeling a resin substrate, it is difficult to remove the peeling layer remaining on the glass substrate and reuse the glass substrate. [Prior Art Document] [Patent Document] [0010] [Patent Document 1] Japanese Patent Laid-Open No. 10-125929 [Patent Document 2] Japanese Patent Laid-Open No. 10-125931 [Patent Document 3] International Publication No. 2005/050754 [Patent Document 4] Japanese Patent Laid-Open No. 10-125930 [Patent Document 5] Japanese Patent Laid-Open No. 2010-111853 [Patent Document 6] Japanese Patent Laid-Open No. 2008-188792

[發明所欲解決的課題] 　　[0011] 本發明係鑒於上述情事而完成者，目的在於提供一種基板保護層形成用組成物，其係可容易地進行基體的再利用，可連同可撓性電子裝置的樹脂基板從基體剝離，不對樹脂基板造成損傷或使特性大幅變化。 [解決課題的手段] 　　[0012] 本發明者為了解決上述課題而重複專心致力的檢討，結果發現藉由使用包含聚醯胺酸與有機溶劑之組成物作為基板保護層形成用組成物，可形成具有與基體之適度的密著性和適度的剝離性以及與可撓性電子裝置所用的樹脂基板之優異的密著性之基板保護層，該基板保護層形成用組成物係在基體上形成樹脂基板後，剝離上述樹脂基板而製作樹脂基板時，介於上述基體與樹脂基板之間存在，具有從上述基體的易剝離性，同時具有作為剝離後的樹脂基板之保護層的機能之基板保護層形成用組成物，而完成本發明。 　　[0013] 即，本發明提供： 　　1.一種基板保護層形成用組成物，其係在基體上形成樹脂基板後，連同上述樹脂基板從上述基體剝離上述樹脂基板時，介於上述基體與上述樹脂基板之間存在，具有從上述基體的易剝離性，同時具有作為剝離後的上述樹脂基板之保護層的機能之基板保護層形成用組成物，其特徵為包含聚醯胺酸與有機溶劑。 　　2.如1之基板保護層形成用組成物，其係包含以下述式(1)所示的聚醯胺酸與有機溶劑；

Figure 02_image001
(式中，X表示以下述式(2)所示的芳香族基，Y表示具有氟原子的2價之芳香族基，n表示自然數)
Figure 02_image003
。 　　3.如2之基板保護層形成用組成物，其中上述Y係以下述式(3)所示的芳香族基；
Figure 02_image005
。 　　4.如2或3之基板保護層形成用組成物，其中上述Y係以下述式(4)所示的芳香族基；
Figure 02_image007
。 　　5.如1～4中任一項之基板保護層形成用組成物，其中上述有機溶劑係由具有以下述式(S1)～(S7)所示的構造者選出的至少1種；
Figure 02_image009
(式中，R1 ～R8 互相獨立地表示氫原子或碳數1～10的烷基，R9 及R10 互相獨立地表示氫原子、碳數1～10的烷基或碳數1～10的醯基，b及n表示自然數)。 　　6.如1之基板保護層形成用組成物，其係在上述樹脂基板上，進一步製作電子裝置，將電子裝置連同上述樹脂基板從上述基體剝離時，具有從上述基體的易剝離性，同時具有作為剝離後的樹脂基板之保護層的機能。 　　7.一種基板保護層，其係由如1～6中任一項之基板保護層形成用組成物所得者。 　　8.一種可撓性電子裝置之製造方法，其特徵為包含： 　　在基體上塗佈如6之基板保護層形成用組成物，以最高溫度500℃以上燒成而形成具有從上述基體的易剝離性之基板保護層之步驟， 　　於該基板保護層之上塗佈樹脂基板形成用組成物，以最高溫度500℃以上燒成而形成樹脂基板之步驟， 　　於此樹脂基板上製作電子裝置之步驟，與 　　將上述電子裝置連同上述基板保護層及上述樹脂基板從上述基體剝離之步驟。 　　9.如8之可撓性電子裝置之製造方法，其中上述樹脂基板為聚醯亞胺樹脂基板。 　　10.一種附保護層的樹脂基板之製造方法，其特徵為：在基體上塗佈如1～5中任一項之基板保護層形成用組成物，以最高溫度500℃以上燒成而形成基板保護層後，於該基板保護層之上塗佈樹脂基板形成用組成物，以最高溫度500℃以上燒成，形成樹脂基板後，將上述樹脂基板連同上述基板保護層從基體剝離。 　　11.如10之製造方法，其中上述樹脂基板為聚醯亞胺樹脂基板。 [發明效果] 　　[0014] 藉由使用本發明之基板保護層形成用組成物，可再現性良好地得到具有與基體之適度的密著性和適度的剝離性及與樹脂基板優異的密著性之基板保護層。因此，藉由使用本發明之基板保護層形成用組成物，於可撓性電子裝置之製程中，可不對於基體上所形成的樹脂基板或更在其上設置的電路等造成損傷，將該樹脂基板及基板保護層連同該電路等從該基體分離。因此，本發明之基板保護層形成用組成物係可促進基體之再利用，同時有助於具備樹脂基板的可撓性電子裝置之製程的簡便化或其良率提高等。[Problems to be Solved by the Invention] [0011] The present invention has been accomplished in view of the above-mentioned circumstances, and an object of the present invention is to provide a composition for forming a protective layer of a substrate, which can be easily reused as a substrate, and can be combined with flexible electronic The resin substrate of the device is peeled off from the base body, and the resin substrate is not damaged or the characteristics are not greatly changed. [MEANS TO SOLVE THE PROBLEM] [0012] The inventors of the present invention have repeated intensive examinations in order to solve the above-mentioned problems. As a result, they have found that by using a composition containing a polyamic acid and an organic solvent as a composition for forming a substrate protective layer, it is possible to form a A substrate protective layer having moderate adhesion to a substrate, moderate peelability, and excellent adhesion to a resin substrate used in a flexible electronic device, and the substrate protective layer-forming composition is formed by forming a resin on a substrate After the substrate, when the resin substrate is produced by peeling off the resin substrate, a substrate protective layer exists between the base and the resin substrate, and has easy peelability from the base and functions as a protective layer of the resin substrate after peeling. The composition for formation has been completed, and the present invention has been completed. That is, the present invention provides: 1. a substrate protective layer forming composition, after it forms a resin substrate on a substrate, when peeling off the above-mentioned resin substrate from the above-mentioned substrate together with the above-mentioned resin substrate, between the above-mentioned substrate and the above-mentioned resin The composition for forming a substrate protective layer which exists between the substrates, has easy peelability from the above-mentioned substrate, and has a function as a protective layer of the above-mentioned resin substrate after peeling, is characterized by comprising a polyamic acid and an organic solvent. 2. The composition for forming a substrate protective layer according to 1, which comprises a polyamic acid represented by the following formula (1) and an organic solvent;
Figure 02_image001
(In the formula, X represents an aromatic group represented by the following formula (2), Y represents a divalent aromatic group having a fluorine atom, and n represents a natural number)
Figure 02_image003
. 3. The composition for forming a substrate protective layer according to 2, wherein the above Y is an aromatic group represented by the following formula (3);
Figure 02_image005
. 4. The composition for forming a substrate protective layer according to 2 or 3, wherein the above Y is an aromatic group represented by the following formula (4);
Figure 02_image007
. 5. The composition for forming a substrate protective layer according to any one of 1 to 4, wherein the organic solvent is at least one selected from the group having a structure represented by the following formulae (S1) to (S7);
Figure 02_image009
(wherein, R 1 to R 8 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 9 and R 10 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. 10 is an acyl group, and b and n represent natural numbers). 6. The composition for forming a substrate protective layer according to 1, which is attached to the above-mentioned resin substrate to further manufacture an electronic device, and when the electronic device is peeled off from the above-mentioned substrate together with the above-mentioned resin substrate, it has easy peelability from the above-mentioned substrate, and at the same time has the Function as a protective layer of the resin substrate after peeling. 7. A substrate protective layer obtained from the composition for forming a substrate protective layer according to any one of 1 to 6. 8. A method for manufacturing a flexible electronic device, comprising: coating the substrate protective layer forming composition according to 6 on a substrate, and firing at a maximum temperature of 500° C. or higher to form a substrate having an easily peelable structure from the substrate. The step of forming a substrate protective layer is the step of coating a resin substrate forming composition on the substrate protective layer, and firing at a maximum temperature of 500°C or higher to form a resin substrate. The step of fabricating an electronic device on the resin substrate, and the step of peeling the electronic device together with the substrate protective layer and the resin substrate from the base. 9. The manufacturing method of the flexible electronic device according to 8, wherein the resin substrate is a polyimide resin substrate. 10. A method for producing a resin substrate with a protective layer, characterized in that: coating the substrate protective layer forming composition according to any one of 1 to 5 on a substrate, and firing at a maximum temperature of 500°C or higher to form a substrate After the protective layer is formed, the resin substrate forming composition is applied on the substrate protective layer and fired at a maximum temperature of 500°C or higher to form a resin substrate, and then the resin substrate and the substrate protective layer are peeled off from the base. 11. The manufacturing method according to 10, wherein the resin substrate is a polyimide resin substrate. [Effect of the Invention] [0014] By using the composition for forming a substrate protective layer of the present invention, moderate adhesion to the substrate, moderate peelability, and excellent adhesion to a resin substrate can be obtained with good reproducibility substrate protective layer. Therefore, by using the composition for forming a substrate protective layer of the present invention, the resin substrate formed on the substrate or the circuit provided thereon can be prevented from being damaged during the manufacturing process of the flexible electronic device. The substrate and the substrate protective layer are separated from the substrate together with the circuit and the like. Therefore, the composition for forming a substrate protective layer of the present invention can promote the reuse of the substrate, and at the same time contribute to the simplification of the manufacturing process or the improvement of the yield of the flexible electronic device provided with the resin substrate.

[實施發明的形態] 　　[0015] 以下，更詳細地說明本發明。 　　本發明之基板保護層形成用組成物包含聚醯胺酸與有機溶劑。此處，本發明中所謂的基板保護層，就是以指定之目的設置於玻璃基體正上方之層，作為其典型例，可舉出於可撓性電子裝置之製程中，於基體與由聚醯亞胺等樹脂所構成的可撓性電子裝置之樹脂基板之間，為了在指定的程序中固定該樹脂基板而設置之層。再者，此基板保護層係在上述樹脂基板上形成電子電路等後，連同該樹脂基板從該基體剝離之點，與以往的剝離層不同。 　　[0016] 作為製造聚醯胺酸時所用的二胺成分及酸二酐成分，只要是在上述之製程後，能給予具有連同樹脂基板從基體剝離之性質，即具有與基體的易剝離性，且具有與樹脂基板的密著性之聚醯亞胺膜者，則沒有特別的限定，但從充分地發揮自上述基體的易剝離性及對於樹脂基板的密著性等性質之觀點來看，較佳為使包含芳香族二胺的二胺成分與包含芳香族四羧酸二酐的酸二酐成分反應而得之聚醯胺酸，特佳為如以下述式(1)所示之使用聯苯基四羧酸二酐與具有氟原子的芳香族二胺所得之聚醯胺酸。 　　[0017]

Figure 02_image011
[0018] 式(1)中，X表示以下述式(2)所示的來自聯苯基四羧酸之芳香族基，Y表示來自具有氟原子的芳香族二胺之2價的含有氟原子之芳香族基。 　　n表示自然數，但較佳為2以上之整數。 　　[0019]
Figure 02_image013
[0020] 作為給予以上述式(2)所示的來自聯苯基四羧酸之2價基的聯苯基四羧酸二酐，可舉出以下述式(C1)～(C3)所示者，但於本發明中，特別適合為以式(C1)所示的3,3’,4,4’-聯苯基四羧酸二酐。再者，(C1)～(C3)係可各自單獨使用，也可2種以上組合使用。 　　[0021]
Figure 02_image015
[0022] 又，於本發明中，除了上述聯苯基四羧酸二酐之外，還可使用其他的四羧酸二酐。 　　作為其具體例，可舉出苯均四酸二酐、苯-1,2,3,4-四羧酸二酐、萘-1,2,3,4-四羧酸二酐、萘-1,2,5,6-四羧酸二酐、萘-1,2,6,7-四羧酸二酐、萘-1,2,7,8-四羧酸二酐、萘-2,3,5,6-四羧酸二酐、萘-2,3,6,7-四羧酸二酐、萘-1,4,5,8-四羧酸二酐、蒽-1,2,3,4-四羧酸二酐、蒽-1,2,5,6-四羧酸二酐、蒽-1,2,6,7-四羧酸二酐、蒽-1,2,7,8-四羧酸二酐、蒽-2,3,6,7-四羧酸二酐、菲-1,2,3,4-四羧酸二酐、菲-1,2,5,6-四羧酸二酐、菲-1,2,6,7-四羧酸二酐、菲-1,2,7,8-四羧酸二酐、菲-1,2,9,10-四羧酸二酐、菲-2,3,5,6-四羧酸二酐、菲-2,3,6,7-四羧酸二酐、菲-2,3,9,10-四羧酸二酐、菲-3,4,5,6~四羧酸二酐、菲-3,4,9,10-四羧酸二酐等，此等亦可單獨或組合2種以上使用。 　　[0023] 於本發明所用的聚醯胺酸中，四羧酸成分中的聯苯基四羧酸二酐之量，若考慮從上述基體的易剝離性及對於樹脂基板的密著性之兼備，則較佳為70莫耳%以上，更佳為80莫耳%以上，尤佳90莫耳%以上，尤更佳為95莫耳%以上，最佳為100莫耳%。 　　[0024] 另一方面，作為給予上述Y之具有氟原子的芳香族二胺之具體例，可舉出5-三氟甲基苯-1,3-二胺、5-三氟甲基苯-1,2-二胺、3,5-雙(三氟甲基)苯-1,2-二胺、2,2’-雙(三氟甲基)-4,4’-二胺基聯苯(2,2’-雙(三氟甲基)聯苯胺)、3,3’-雙(三氟甲基)-4,4’-二胺基聯苯(3,3’-雙(三氟甲基)聯苯胺)、2,2-雙(3-胺基苯基)-1,1,1,3,3,3-六氟丙烷、2,2-雙(4-胺基苯基)-1,1,1,3,3,3-六氟丙烷、3,3’-雙(三氟甲基)聯苯基-4,4’-二胺、3,3’,5,5’-四氟聯苯基-4,4’-二胺、4,4’-二胺基八氟聯苯等，此等係可單獨使用，也可2種以上組合使用。 　　[0025] 於此等之中，若考慮從上述基體的易剝離性及對於樹脂基板的密著性之兼備，則較佳為2,2’-雙(三氟甲基)-4,4’-二胺基聯苯(2,2’-雙(三氟甲基)聯苯胺)、3,3’-雙(三氟甲基)-4,4’-二胺基聯苯(3,3’-雙(三氟甲基)聯苯胺)，更佳為2,2’-雙(三氟甲基)-4,4’-二胺基聯苯(2,2’-雙(三氟甲基)聯苯胺)。 　　因此，作為式(1)中合適的Y，可舉出以式(3)及(4)所示的2價之芳香族基。 　　[0026]
Figure 02_image017
[0027]
Figure 02_image019
[0028] 又，於本發明中，除了上述具有氟原子的芳香族二胺之外，還可使用其他的二胺。 　　作為其具體例，可舉出1,4-二胺基苯(對苯二胺)、1,3-二胺基苯(間苯二胺)、1,2-二胺基苯(鄰苯二胺)、2,4-二胺基甲苯、2,5-二胺基甲苯、2,6-二胺基甲苯、4,6-二甲基間苯二胺、2,5-二甲基對苯二胺、2,6-二甲基對苯二胺、2,4,6-三甲基-1,3-苯二胺、2,3,5,6-四甲基對苯二胺、間苯二甲基二胺、對苯二甲基二胺等之苯核為1個的二胺；1,2-萘二胺、1,3-萘二胺、1,4-萘二胺、1,5-萘二胺、1,6-萘二胺、1,7-萘二胺、1,8-萘二胺、2,3-萘二胺、2,6-萘二胺、4,4’-聯苯基二胺、3,3’-二甲基-4,4’-二胺基二苯基甲烷、3,3’-二羧基-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、4,4’-二胺基苯甲醯苯胺、3,3’-二氯聯苯胺、3,3’-二甲基聯苯胺、2,2’-二甲基聯苯胺、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、2,2-雙(3-胺基苯基)丙烷、2,2-雙(4-胺基苯基)丙烷、3,3’-二胺基二苯基亞碸、3,4’-二胺基二苯基亞碸、4,4’-二胺基二苯基亞碸、2-(3-胺基苯基)-5-胺基苯并咪唑、2-(4-胺基苯基)-5-胺基苯并
Figure 106145941-A0304-12-0015-1
唑等之苯核為2個的二胺；1,5-二胺基蒽、2,6-二胺基蒽、9,10-二胺基蒽、1,8-二胺基菲、2,7-二胺基菲、3,6-二胺基菲、9,10-二胺基菲、1,3-雙(3-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、1,4-雙(3-胺基苯基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(3-胺基苯基硫化物)苯、1,3-雙(4-胺基苯基硫化物)苯、1,4-雙(4-胺基苯基硫化物)苯、1,3-雙(3-胺基苯基碸)苯、1,3-雙(4-胺基苯基碸)苯、1,4-雙(4-胺基苯基碸)苯、1,3-雙[2-(4-胺基苯基)異丙基]苯、1,4-雙[2-(3-胺基苯基)異丙基]苯、1,4-雙[2-(4-胺基苯基)異丙基]苯、4,4”-二胺基對聯三苯、4,4”-二胺基間聯三苯等之苯核為3個的二胺等，此等係可單獨使用，也可組合2種以上使用。 　　[0029] 於本發明所用的聚醯胺酸中，二胺成分中之具有氟原子的芳香族二胺之量，若考慮從上述基體的易剝離性及對於樹脂基板的密著性之兼備，則較佳為70莫耳%以上，更佳為80莫耳%以上，尤佳90莫耳%以上，尤更佳為95莫耳%以上，最佳為100莫耳%。 　　[0030] 藉由使以上說明的二胺成分與四羧酸二酐成分在有機溶劑中反應，可得到本發明之基板保護層形成用組成物中所包含的聚醯胺酸。 　　此反應所用的有機溶劑，只要不對於反應造成不良影響，則沒有特別的限定，作為其具體例，可舉出間甲酚、2-吡咯啶酮、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-乙烯基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、3-甲氧基-N,N-二甲基丙基醯胺、3-乙氧基-N,N-二甲基丙基醯胺、3-丙氧基-N,N-二甲基丙基醯胺、3-異丙氧基-N,N-二甲基丙基醯胺、3-丁氧基-N,N-二甲基丙基醯胺、3-第二丁氧基-N,N-二甲基丙基醯胺、3-第三丁氧基-N,N-二甲基丙基醯胺、g-丁內酯等。再者，有機溶劑係可1種單獨或組合2種以上使用。 　　[0031] 二胺成分與四羧酸二酐成分之饋入比(莫耳比)，由於係考慮目的之分子量或分子量分布、二胺之種類或四羧酸二酐之種類等而適宜決定，不能一概地規定，但相對於四羧酸二酐成分1，二胺成分為0.7～1.3左右，較佳為0.8～1.2左右，更佳為0.9～1.1左右。 　　[0032] 反應溫度只要是在所用的溶劑之熔點～沸點之範圍中適宜設定即可，通常為0～100℃左右，但為了防止所得之聚醯胺酸在溶液中的醯亞胺化，維持聚醯胺酸單位的高含量，較佳為0～70℃左右，更佳為0～60℃左右，尤佳為0～50℃左右。 　　[0033] 反應時間由於係依賴於反應溫度或原料物質之反應性，不能一概地規定，但通常為1～100小時左右。 　　[0034] 如此所得之聚醯胺酸的重量平均分子量通常為5,000～500,000左右，但從提高所得之膜作為基板保護層之機能的觀點來看，較佳為10,000～200,000左右，更佳為30,000～150,000左右。再者，於本發明中，重量平均分子量係凝膠滲透層析法(GPC)測定之聚苯乙烯換算值。 　　[0035] 再者，本發明所用之聚醯胺酸係可使其聚合物鏈末端的一者或兩者更與具有錨基的胺或具有錨基的酸酐反應。 　　作為如此的錨基，可舉出羧酸基、矽基(例如，烷基矽基、烷氧基矽基、乙烯基矽基及烯丙基矽基等)、乙烯基、馬來醯亞胺基、酚性羥基等，其中較佳為羧酸基、矽基(尤其由烷氧基、乙烯基及烯丙基所選出的基係1個以上鍵結於矽原子之矽基)。 　　又，於由二胺成分及四羧酸二酐成分所得的聚醯胺酸與錨基之間，碳數1～10左右之不使剝離性或耐熱性顯著降低之碳數的烷基、芳基等之間隔基係可存在。 　　[0036] 作為具有錨基的胺之具體例，可舉出4-胺基苯氧基三甲基矽烷、4-胺基苯氧基二甲基乙烯基矽烷、4-胺基苯氧基甲基二乙烯基矽烷、4-胺基苯氧基三乙烯基矽烷、4-胺基苯氧基二甲基烯丙基矽烷、4-胺基苯氧基甲基二烯丙基矽烷、4-胺基苯氧基三烯丙基矽烷、4-胺基苯氧基二甲基苯基矽烷、4-胺基苯氧基甲基二苯基矽烷、4-胺基苯氧基三苯基矽烷、4-胺基苯氧基三甲氧基矽烷、4-胺基苯氧基二甲氧基乙烯基矽烷、4-胺基苯氧基甲氧基二乙烯基矽烷、4-胺基苯氧基三乙烯基矽烷、4-胺基苯氧基二甲氧基烯丙基矽烷、4-胺基苯氧基甲氧基二烯丙基矽烷、4-胺基苯氧基二甲氧基苯基矽烷、4-胺基苯氧基甲氧基二苯基矽烷、4-胺基苯氧基三乙氧基矽烷、4-胺基苯氧基二乙氧基乙烯基矽烷、4-胺基苯氧基乙氧基二乙烯基矽烷、4-胺基苯氧基三乙烯基矽烷、4-胺基苯氧基二乙氧基烯丙基矽烷、4-胺基苯氧基乙氧基二烯丙基矽烷、4-胺基苯氧基二乙氧基苯基矽烷、4-胺基苯氧基乙氧基二苯基矽烷、3-胺基苯氧基三甲基矽烷、3-胺基苯氧基二甲基乙烯基矽烷、3-胺基苯氧基甲基二乙烯基矽烷、2-胺基苯氧基三乙烯基矽烷、2-胺基苯氧基三甲基矽烷、2-胺基苯氧基二甲基乙烯基矽烷、2-胺基苯氧基甲基二乙烯基矽烷、2-胺基苯氧基三乙烯基矽烷、3-胺基丙基三乙基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽基丙基三伸乙三胺、N-三甲氧基矽基丙基三伸乙三胺、2-胺基苯酚、3-胺基苯酚、4-胺基苯酚等，惟不受此等所限定。 　　[0037] 作為具有錨基的酸酐之具體例，可舉出偏苯三酸酐、乙烯基馬來酸酐、4-乙烯基萘-1,2-二羧酸酐、馬來酸酐、2,3-二甲基馬來酸酐、4-羥基鄰苯二甲酸酐、3-羥基鄰苯二甲酸酐等，惟不受此等所限定。 　　[0038] 再者，具有錨基的胺及具有錨基的酸酐之量係以莫耳比表示，相對於四羧酸二酐成分1，具有錨基的胺為0.01～0.6左右，較佳為0.05～0.4左右，更佳為0.1～0.2左右，或相對於二胺成分1，具有錨基的酸酐為0.01～0.52左右，較佳為0.05～0.32左右，更佳為0.1～0.2左右。 　　[0039] 本發明之基板保護層形成用組成物係除了上述之聚醯胺酸之外，還包含有機溶劑。作為此有機溶劑，並沒有特別的限定，但較佳為由下述選出的溶劑。 　　[0040]
Figure 02_image021
(式中，R1 ～R8 互相獨立地表示氫原子或碳數1～10的烷基，R9 及R10 互相獨立地表示氫原子、碳數1～10的烷基或碳數1～10的醯基，b及m表示自然數)。 　　[0041] b及m表示自然數，但較佳為1～3，更佳為1或2。 　　作為碳數1～10的烷基，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基等。此等之中，較佳為碳數1～3的烷基，更佳為碳數1或2的烷基。 　　作為碳數1～10的醯基，可舉出碳數1～8的烷醯基(例如，甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、三甲基乙醯基等)、碳數3～6的環烷基羰基(例如，環丙基羰基、環戊基羰基、環己基羰基等)、苯甲醯基等，較佳為乙醯基。 　　[0042] 其中，從良好地溶解聚醯胺酸，容易調製均勻性高的組成物來看，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、1,3-二甲基-2-咪唑啉酮、N-乙基-2-吡咯啶酮、g-丁內酯，更佳為N-甲基-2-吡咯啶酮。 　　[0043] 再者，即使單獨為不溶解聚醯胺酸的溶劑，也只要在聚醯胺酸不析出的範圍內，可使用於組成物之調製。特別是，可使乙基溶纖劑、丁基溶纖劑、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸正丁酯、乳酸異戊酯等之具有低表面張力的溶劑適度地混合存在。藉此，已知在對於基板的塗佈時塗膜均勻性升高，亦可適用於本發明。 　　[0044] 本發明之基板保護層形成用組成物之調製方法為任意。作為調製方法之較佳一例，可舉出將包含藉由上述所說明的方法所得之目的之聚醯胺酸的反應溶液予以過濾之方法。此時，若目的為需要濃度調整等，則可將濾液稀釋或濃縮。藉由採用如此的方法，不僅可減低能成為由所得之組成物所製造的基板保護層之密著性、剝離性等惡化的原因之雜質的混入，而且可高效率地得到基板保護層形成用組成物。作為用於稀釋的溶劑，並沒有特別的限定，作為其具體例，可舉出與上述反應的反應溶劑之具體例同樣者。用於稀釋的溶劑係可為單獨1種或組合2種以上使用。 　　[0045] 本發明之基板保護層形成用組成物中的聚醯胺酸之濃度，雖然係考慮所製作的基板保護層之厚度、組成物之黏度等而適宜設定，但通常為1～30質量%左右，較佳為1～20質量%左右。藉由成為如此的濃度，可再現性良好地得到0.05～5μm左右的厚度之基板保護層。聚醯胺酸之濃度係可調整作為聚醯胺酸的原料之二胺與四羧酸二酐之使用量，並於使經分離的聚醯胺酸溶解於溶劑中時，調整其量。 　　[0046] 本發明之基板保護層形成用組成物的黏度，雖然係考慮所製作的基板保護層之厚度等而適宜設定，但特別在以再現性良好地得到0.05～5μm左右的厚度之膜為目的時，通常在25℃為10～10,000mPa・s左右，較佳為20～5,000mPa・s左右。 　　[0047] 此處，黏度係使用市售的液體之黏度測定用黏度計，例如，可參照JIS K7117-2中記載的程序，於組成物的溫度25℃之條件下測定。作為黏度計，較佳為使用圓錐平板型(錐板型)旋轉黏度計，較佳可在同型的黏度計中使用1°34’´R24作為標準錐形轉子，於組成物的溫度25℃之條件下測定。作為如此的旋轉黏度計，例如可舉出東機產業(股)製TVE-25L。 　　[0048] 再者，本發明之基板保護層形成用組成物係除了聚醯胺酸與有機溶劑之外，例如為了提高膜強度，還可包含交聯劑等。 　　[0049] 將以上說明的剝離層形成用組成物塗佈於基體上後，以包含最高溫度500℃以上的燒成步驟之燒成法，將聚醯胺酸予以熱醯亞胺化，可得到具有與基體的易剝離性及與樹脂基板之優異的密著性之由聚醯亞胺膜所構成的樹脂基板保護層。 　　於本發明中，只要上述燒成時的最高溫度為500℃以上且聚醯亞胺的耐熱溫度以下之範圍，則沒有特別的限定。又，其上限通常為550℃左右，較佳為520℃，更佳為510℃左右。由於將加熱溫度設為上述範圍，亦可一邊防止所得之膜的脆弱化，一邊使醯亞胺化反應充分地進行。 　　加熱時間由於隨著加熱溫度而不同，不能一概地規定，但通常為5分鐘～5小時。又，醯亞胺化率只要是50～100%之範圍即可。 　　[0050] 又，上述燒成時之溫度只要最高溫度為上述範圍，則亦可包含在其以下之溫度進行燒成之步驟。 　　作為本發明中的加熱態樣之較佳一例，可舉出以50～150℃加熱後，直接階段地使加熱溫度上升，最終以500℃以上加熱之手法。特別是，作為加熱態樣之更佳一例，可舉出以50～100℃加熱，以超過100℃～未達500℃加熱，以500℃以上加熱之手法。再者，作為加熱態樣之更佳的另一例，可舉出以50～100℃加熱後，以200～300℃加熱，以超過300℃～未達500℃加熱，最後以500～510℃加熱之手法。 　　[0051] 另外，作為考慮燒成時間時的加熱態樣之較佳一例，可舉出以50～150℃加熱1分鐘～2小時後，直接階段地使加熱溫度上升，最終以500℃以上加熱30分鐘～4小時之手法。特別是，作為加熱態樣之更佳一例，可舉出以50～100℃加熱1分鐘～2小時，以超過100℃～未達500℃加熱5分鐘～2小時，以500℃以上加熱30分鐘～4小時之手法。再者，作為加熱態樣之更佳的另一例，可舉出以50～100℃加熱1分鐘～2小時後，以200～300℃加熱5分鐘～2小時，以超過300℃～未達500℃加熱5分鐘～2小時，最後以500～510℃加熱1分鐘～2小時之手法。 　　[0052] 將如此的本發明之基板保護層形成在基體上時，基板保護層係可形成在基體的一部分表面，也可形成在全面。作為在基體的一部分表面上形成基板保護層之態樣，有在基體表面之中僅於指定之範圍形成基板保護層之態樣，於基體表面全面上以點圖型、線與間隙圖型等之圖型狀形成基板保護層之態樣等。再者，於本發明中，所謂的基體，是意指在其表面塗佈本發明的基板保護層形成用組成物，用於可撓性電子裝置等之製造者。 　　[0053] 作為基體(基材)，例如可舉出玻璃、塑膠(聚碳酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚酯、聚烯烴、環氧樹脂、三聚氰胺、三乙醯基纖維素、ABS、AS、降莰烯系樹脂等)、金屬(矽晶圓等)、木材、紙、石板等，特別是從本發明之基板保護層對於其具有充分的密著性來看，較佳為玻璃。再者，基體表面係可以單一的材料所構成，也可以2種以上的材料所構成。作為以2種以上的材料構成基體表面之態樣，有在基體表面之中某範圍以某材料構成，其餘的表面以其他的材料構成之態樣，於基體表面全體上以點圖型、線與間隙圖型等之圖型狀的材料存在於其他的材料中之態樣等。 　　[0054] 作為將本發明之基板保護層形成用組成物塗佈於基體之方法，並沒有特別的限定，例如可舉出澆鑄塗佈法、旋轉塗佈法、刮刀塗佈法、浸塗法、輥塗法、棒塗法、模塗法、噴墨法、印刷法(凸版、凹版、平版、網版印刷等)等。 　　[0055] 用於加熱的器具例如可舉出熱板、烘箱等。加熱環境可為空氣下，也可為惰性氣體下，還有可為常壓下，也可為減壓下。 　　[0056] 基板保護層之厚度通常為0.01～50μm左右，從生產性之觀點來看，較佳為0.05～20μm左右。再者，所欲之厚度係藉由調整加熱前的塗膜之厚度而實現。 　　[0057] 以上說明的基板保護層係具有與基體尤其玻璃的基體之適度的密著性和適度的剝離性及與樹脂基板優異的密著性。因此，本發明之基板保護層係於可撓性電子裝置之製程中，不對於該裝置的樹脂基板造成損傷，可適用於將該樹脂基板連同在該樹脂基板上所形成的電路等從基體剝離。 　　[0058] 上述基板保護層上所形成的樹脂基板係沒有特別的限定，但從耐熱性之觀點來看，宜熱重量分析中的1%重量減少溫度為500℃以上者。 　　作為如此的樹脂基板，可舉出使用如全芳香族系聚醯亞胺、聚苯并
Figure 106145941-A0304-12-0015-1
唑、聚苯并噻唑、聚苯并咪唑、全芳香族系聚合物之樹脂基板。又，亦可為在上述聚合物中添加有矽溶膠、二氧化鈦溶膠等之混成薄膜。 　　[0059] 以下，說明使用本發明之基板保護層的可撓性電子裝置之製造方法的一例。 　　使用本發明之基板保護層形成用組成物，藉由上述之方法，在玻璃基體上形成基板保護層。於此基板保護層之上，塗佈用於形成樹脂基板的樹脂基板形成用溶液，將此塗膜予以燒成，藉此形成隔著本發明之基板保護層而固定於玻璃基體的樹脂基板。 　　[0060] 上述塗膜之燒成溫度係可按照樹脂之種類等而適宜設定，但於本發明中，較佳為將此燒成時的最高溫度設為500℃以上。又，其上限通常為550℃左右，較佳為520℃，更佳為510℃左右。 　　由於將樹脂基板製作之際的燒成時之最高溫度設為此範圍，可進一步提高基底的保護層與基體之剝離性，或進一步提高基板保護層與樹脂基板之適度的密著性及剝離性。 　　[0061] 此時亦只要最高溫度成為上述範圍，則可包含在其以下之溫度進行燒成之步驟。 　　作為樹脂基板製作時的加熱態樣之較佳一例，可舉出以50～150℃加熱後，直接階段地使加熱溫度上升，最終以500℃以上加熱之手法。特別是，作為加熱態樣之更佳一例，可舉出以50～100℃加熱，以超過100℃～未達500℃加熱，以500℃以上加熱之手法。再者，作為加熱態樣之更佳的另一例，可舉出以50～100℃加熱後，以超過100℃～200℃加熱，以超過200℃～300℃加熱，以超過300℃～未達500℃加熱，最後以500～510℃加熱之手法。 　　[0062] 又，作為考慮燒成時間時的加熱態樣之較佳一例，可舉出以50～150℃加熱1分鐘～2小時後，直接階段地使加熱溫度上升，最終以500℃以上加熱30分鐘～4小時之手法。特別是，作為加熱態樣之更佳一例，可舉出以50～100℃加熱1分鐘～2小時，以超過100℃～未達500℃加熱5分鐘～2小時，以500℃以上加熱30分鐘～4小時之手法。再者，作為加熱態樣之更佳的另一例，可舉出以50～100℃加熱1分鐘～2小時後，以超過100℃～200℃加熱5分鐘～2小時，以超過200℃～300℃加熱5分鐘～2小時，以超過300℃～未達500℃加熱5分鐘～2小時，最後以500～510℃加熱30分鐘～4小時之手法。 　　[0063] 接著，在隔著本發明之基板保護層固定於基體之該樹脂基板之上，形成所欲的電路，然後例如沿著基板保護層切割樹脂基板，將樹脂基板及基板保護層連同此電路從基體剝離，而分離樹脂基板及基板保護層與基體。此時，亦可將基體之一部分與基板保護層一起切割。 　　[0064] 再者，於日本特開2013-147599號公報中，報告將高亮度LED或三次元半導體封裝等之製造中所使用的雷射掀離法(LLO法)應用於可撓性顯示器之製造。上述LLO法之特徵為從形成有電路等之面的相反面，將特定波長的光線，例如波長308nm的光線從玻璃基體側來照射。所照射的光線係穿透玻璃基體，僅玻璃基體附近的聚合物(聚醯亞胺)吸收此光線而蒸發(昇華)。結果，對於決定顯示器之性能的設於樹脂基板上的電路等，不造成影響，可從玻璃基體選擇地剝離基板保護層。 　　[0065] 本發明之基板保護層形成用組成物由於具有能充分吸收上述LLO法之可適用的特定波長(例如308nm)之光線的特徵，可作為LLO法之犧牲層使用。因此，於隔著使用本發明的組成物所形成的基板保護層而固定於玻璃基體的樹脂基板之上，形成所欲的電路，然後實施LLO法，照射308nm的光線時，僅該基板保護層吸收此光線而蒸發(昇華)。藉此，上述基板保護層成為犧牲(作為犧牲層作用)，可從玻璃基體選擇地剝離樹脂基板。 [實施例] 　　[0066] 以下，舉出實施例來更詳細地說明本發明，惟本發明不受此等實施例所限定。 　　[0067] [1]化合物之縮寫符號 　　p-PDA：對苯二胺 　　TFMB：2,2’-雙(三氟甲基)聯苯胺 　　BPDA：3,3’,4,4’-聯苯基四羧酸二酐 　　PMDA：苯均四酸二酐 　　CBDA：1,2,3,4-環丁烷四羧酸二酐 　　NMP：N-甲基-2-吡咯啶酮 　　BCS：丁基溶纖劑 　　PGME：丙二醇單甲基醚 　　[0068] [2]重量平均分子量及分子量分布之測定方法 　　聚合物之重量平均分子量(以下簡稱Mw)及分子量分布之測定係使用日本分光(股)製GPC裝置(管柱：Shodex製KD801及KD805；洗提液：二甲基甲醯胺/LiBr・H2 O(29.6mM)/H3 PO4 (29.6mM)/THF(0.1wt%)；流量：1.0mL/分鐘；管柱溫度：40℃；Mw：標準聚苯乙烯換算值)進行。 　　[0069] [3]聚合物之合成 　　藉由以下之方法，合成聚醯胺酸。 　　再者，不從所得之含有聚合物的反應液中分離出聚合物，如後述，藉由將反應液稀釋，而調製樹脂基板形成用組成物或基板保護層形成用組成物。 　　[0070] ＜合成例S1　聚醯胺酸(S1)之合成＞ 　　將p-PDA 3.176g(0.02937莫耳)溶解於NMP 88.2g中，添加BPDA 8.624g(0.02931莫耳)後，於氮氣環境下，在23℃反應24小時。所得之聚合物的Mw為107,300，分子量分布為4.6。 　　[0071] ＜合成例L1　聚醯胺酸(L1)之合成＞ 　　使TFMB 23.7g(74.2mmol)溶解於NMP 352g中。於所得之溶液中，添加BPDA 24.2g(82.5mmol)，於氮氣環境下，在23℃反應24小時。所得之聚合物的Mw為76,400，分子量分布為2.2。所得之溶液係可溶於PGME中。 　　[0072] ＜合成例L2　聚醯胺酸(L2)之合成＞ 　　使TFMB 9.89g(30.9mmol)溶解於PGME 380g中。於所得之溶液中，添加BPDA 10.0g(34.3mmol)，於氮氣環境下，在50℃反應72小時。所得之聚合物的Mw為76,400，分子量分布為2.2。 　　[0073] ＜比較合成例HL1　聚醯胺酸(HL1)之合成＞ 　　使TFMB 2.73g(8.53mmol)溶解於NMP 38.5g中。於所得之溶液中，添加PMDA 2.06g(9.47mmol)，於氮氣環境下，在23℃反應24小時。所得之聚合物的Mw為76,400，分子量分布為2.2。所得之溶液係可溶於PGME中。 　　[0074] ＜比較合成例HL2　聚醯胺酸(HL2)之合成＞ 　　使TFMB 2.86g(8.91mmol)溶解於NMP 35.2g中。於所得之溶液中，添加CBDA 1.94g(9.91mmol)，於氮氣環境下，在23℃反應24小時。所得之聚合物的Mw為69,200，分子量分布為2.2。所得之溶液係可溶於PGME中。 　　[0075] [4]樹脂基板形成用組成物之調製 [調製例1] 　　將合成例S1所得之反應液直接使用作為樹脂基板形成用組成物。 　　[0076] [5]基板保護層形成用組成物之調製 [實施例1-1] 　　於合成例L1所得之反應液中，添加BCS與NMP，以聚合物濃度成為5wt%、BCS成為20質量%之方式稀釋，得到基板保護層形成用組成物。 　　[0077] [實施例1-2] 　　將合成例L2所得之反應溶液直接當作基板保護層形成用組成物。 　　[0078] [比較例1-1] 　　於比較合成例HL1所得之反應液中，添加BCS與NMP，以聚合物濃度成為5wt%、BCS成為20質量%之方式稀釋，得到基板保護層形成用組成物。 　　[0079] [比較例1-2] 　　於比較合成例HL2所得之反應液中，添加BCS與NMP，以聚合物濃度成為5wt%、BCS成為20質量%之方式稀釋，得到基板保護層形成用組成物。 　　[0080] [6]基板保護層及樹脂基板之製作 [實施例2-1] 　　使用旋轉塗佈機(條件：旋轉數3,000rpm、約30秒)，將實施例1-1所得之基板保護層形成用組成物塗佈在作為玻璃基體的100mm´100mm玻璃基板(以下同樣)之上。 　　然後，使用熱板，將所得之塗膜以80℃加熱10分鐘，其後使用烘箱，以300℃加熱30分鐘，以400℃加熱30分鐘後，更以500℃加熱10分鐘，而在玻璃基板上形成厚度約0.1μm的基板保護層，得到附基板保護層的玻璃基板。再者，各加熱溫度間之升溫速度為5℃/分鐘，於升溫之間，不從烘箱中取出附膜的基板，而在烘箱內加熱。 　　[0081] 使用棒塗機(間隙：250μm)，於上述所得之玻璃基板上的基板保護層(樹脂薄膜)之上，塗佈樹脂基板形成用組成物。然後，使用熱板，將所得之塗膜以80℃加熱40分鐘，其後使用烘箱，以140℃、210℃、300℃及400℃分別加熱30分鐘後，更以500℃加熱60分鐘，而在基板保護層上形成厚度約10μm的聚醯亞胺樹脂基板，得到附樹脂基板・基板保護層的玻璃基板。再者，各加熱溫度間之升溫速度為2℃/分鐘，於升溫之間，不從烘箱中取出附膜的基板，而在烘箱內加熱。 　　[0082] [實施例2-2] 　　除了代替實施例1-1所得之基板保護層形成用組成物，使用實施例1-2所得之基板保護層形成用組成物以外，以與實施例2-1同樣之方法，形成基板保護層及聚醯亞胺樹脂基板，得到附基板保護層的玻璃基板及附樹脂基板・基板保護層的玻璃基板。 　　[0083] [比較例2-1～2-2] 　　除了代替實施例1-1所得之基板保護層形成用組成物，分別使用比較例1-1～1-2所得之基板保護層形成用組成物以外，以與實施例2-1同樣之方法，形成基板保護層及聚醯亞胺樹脂基板，得到附基板保護層的玻璃基板及附樹脂基板・基板保護層的玻璃基板。 　　[0084] [7]剝離性之評價 　　使用刀具，將實施例2-1～2-2及比較例2-1～2-2所得之附樹脂基板・基板保護層的玻璃基板之樹脂基板及基板保護層切割成寬度2cm、長度5cm之長方形狀。然後，於經切割的樹脂基板之端部，貼附黏著膠帶，將此當作試驗片。對於此試驗片，使用(股)ATTONIC製推拉試驗機，以剝離角度成為170°之方式進行剝離試驗，根據下述之基準，評價剝離性。表1中顯示結果。 ＜玻璃基板與基板保護層之剝離性　評價基準＞ 　　○：基板保護層係從玻璃基體完全地剝離。 　　△：能剝離樹脂基板，但是一部分基板保護層殘留在玻璃基體上。 　　×：無法從玻璃基體剝離樹脂基板及基板保護層。 　　又，以刀具切削經剝離的部位之玻璃面的表面，根據以下之基準，評價殘膜性。表1中顯示結果。 ＜基板保護層對於玻璃基板的殘膜性　評價基準＞ 　　○：基板保護層無殘膜。 　　△：一部分基板保護層殘留。 　　×：基板保護層殘留。 　　－：由於樹脂基板不剝離，無法評價。 　　[0085]
Figure 02_image023
[0086] 如表1中所示，可確認實施例2-1～2-2之基板保護層係容易與樹脂基板一起剝離，在玻璃基板上基板保護層不殘膜。另一方面，比較例2-1～2-2之樹脂基板係隔著基板保護層而強固地貼附於玻璃基板，無法從玻璃基體剝離。 　　[0087] [9]樹脂膜之物性 　　測定實施例2-1所得之樹脂基板的機械特性。再者，在不形成基板保護層的情況下，將樹脂基板形成用組成物S1直接塗佈於基體上，進行燒成，製作樹脂基板作為比較。此時，將基體從玻璃基板變更為矽基板，其以外係以與實施例2-1同樣之方法形成樹脂基板。將所得之樹脂膜當作SF1。 　　[0088] ＜線膨脹係數＞ 　　從上述所得之薄膜，製作20mm´5mm的長方形狀之試驗片，使用TMA-4000SA(Bruker AXS(股)製)，測定從50℃到500℃的線膨脹係數。表2中顯示結果。 　　[0089] ＜重量減少＞ 　　從上述所得之薄膜，製作20mm´3mm的長方形狀之試驗片，使用TGA-DTA-2000SR(Bruker AXS(股)製) ，測定從50℃到600℃的重量減少，確認看到1%的重量減少之溫度。表2中顯示結果。 　　[0090]
Figure 02_image025
[0091] 如表2中所示，可確認於實施例所製作之附基板保護層的樹脂基板與未形成基板保護層而製作的樹脂基板中，在機械特性上無差異。由以上之結果可確認，基板保護層係對於所製作之樹脂基板之機械特性不造成影響。[Mode for Carrying Out the Invention] [0015] Hereinafter, the present invention will be described in more detail. The composition for forming a substrate protective layer of the present invention contains a polyamic acid and an organic solvent. Here, the so-called substrate protective layer in the present invention is a layer disposed just above the glass substrate for a specified purpose. As a typical example, in the manufacturing process of flexible electronic devices, the substrate and the polyamide A layer provided between resin substrates of a flexible electronic device made of resin such as imine to fix the resin substrates in a predetermined procedure. In addition, this board|substrate protective layer differs from the conventional peeling layer by forming an electronic circuit etc. on the said resin board|substrate, together with the point where this resin board|substrate peels from this base|substrate. As the diamine component and the acid dianhydride component used in the manufacture of polyamide acid, as long as it is after the above-mentioned process, it can be given the property of being peeled off from the substrate together with the resin substrate, that is, it has easy peelability from the substrate, In addition, the polyimide film having adhesion to the resin substrate is not particularly limited, but from the viewpoint of sufficiently exerting properties such as easy peelability from the above-mentioned substrate and adhesion to the resin substrate, Preferably, it is a polyamic acid obtained by reacting a diamine component containing an aromatic diamine and an acid dianhydride component containing an aromatic tetracarboxylic dianhydride, and it is particularly preferably used as represented by the following formula (1). A polyamide acid obtained from biphenyltetracarboxylic dianhydride and an aromatic diamine having a fluorine atom. [0017]
Figure 02_image011
In formula (1), X represents the aromatic group from biphenyl tetracarboxylic acid shown in following formula (2), Y represents from the bivalent containing fluorine atom of the aromatic diamine with fluorine atom the aromatic group. n represents a natural number, and is preferably an integer of 2 or more. [0019]
Figure 02_image013
As the biphenyl tetracarboxylic dianhydride to which the divalent group derived from biphenyl tetracarboxylic acid represented by the above formula (2) is given, those represented by the following formulas (C1) to (C3) can be mentioned. However, in the present invention, 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by formula (C1) is particularly suitable. In addition, (C1)-(C3) may be used independently, respectively, and may be used in combination of 2 or more types. [0021]
Figure 02_image015
Also, in the present invention, in addition to the above-mentioned biphenyl tetracarboxylic dianhydride, other tetracarboxylic dianhydrides can also be used. Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, and naphthalene-1 ,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene-2,3 ,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, anthracene-1,2,3 ,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2,6,7-tetracarboxylic dianhydride, anthracene-1,2,7,8 -Tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,3,4-tetracarboxylic dianhydride, phenanthrene-1,2,5,6-tetra Carboxylic acid dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic acid Dianhydride, phenanthrene-2,3,5,6-tetracarboxylic dianhydride, phenanthrene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-2,3,9,10-tetracarboxylic dianhydride , phenanthrene-3,4,5,6-tetracarboxylic dianhydride, phenanthrene-3,4,9,10-tetracarboxylic dianhydride, etc., these can also be used alone or in combination of two or more. In the polyamide acid used in the present invention, the amount of biphenyl tetracarboxylic dianhydride in the tetracarboxylic acid component, if considering both the ease of peeling from the above-mentioned matrix and the adhesion to the resin substrate , it is preferably 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, and most preferably 100 mol%. On the other hand, as the specific example of the aromatic diamine with fluorine atom that gives above-mentioned Y, can enumerate 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene- 1,2-diamine, 3,5-bis(trifluoromethyl)benzene-1,2-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-bis(trifluoromethyl)benzidine), 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (3,3'-bis(trifluoromethyl) Methyl)benzidine), 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 3,3'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 3,3',5,5'-Tetrafluorobiphenyl-4,4'-diamine,4,4'-diamino octafluorobiphenyl, etc., these can be used individually or in combination of 2 or more types. Among these, if considering both the ease of peeling from the above-mentioned base and the adhesion to the resin substrate, it is preferably 2,2'-bis(trifluoromethyl)-4,4' -Diaminobiphenyl (2,2'-bis(trifluoromethyl)benzidine), 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (3,3 '-bis(trifluoromethyl)benzidine), more preferably 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-bis(trifluoromethyl) base) benzidine). Therefore, as Y suitable for formula (1), the divalent aromatic group represented by formula (3) and (4) is mentioned. [0026]
Figure 02_image017
[0027]
Figure 02_image019
Also, in the present invention, in addition to the above-mentioned aromatic diamine having a fluorine atom, other diamines can also be used. Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), and 1,2-diaminobenzene (o-phenylenediamine). amine), 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethylm-phenylenediamine, 2,5-dimethylparaben Phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, Diamines with one benzene nucleus such as m-xylylenediamine and p-xylylenediamine; 1,2-naphthalene diamine, 1,3-naphthalene diamine, 1,4-naphthalene diamine, 1,5-Naphthalenediamine, 1,6-Naphthalenediamine, 1,7-Naphthalenediamine, 1,8-Naphthalenediamine, 2,3-Naphthalenediamine, 2,6-Naphthalenediamine, 4, 4'-biphenyldiamine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenyl Methane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminobenzylaniline, 3,3'-dichlorodiphenylmethane Aniline, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 3,3'-diamine Diphenylene, 3,4'-diaminodiphenylene, 4,4'-diaminodiphenylene, 2-(3-aminophenyl)-5-amino Benzimidazole, 2-(4-aminophenyl)-5-aminobenzo
Figure 106145941-A0304-12-0015-1
Diamines such as azoles whose benzene nucleus is 2; 7-Diaminophenanthrene, 3,6-Diaminophenanthrene, 9,10-Diaminophenanthrene, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenanthrene) Phenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(3-aminophenyl sulfide) Benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfide) Benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis[2-(4-aminophenyl) Isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 4,4"-diamino-p-terphenyl, 4,4"-diamine-m-t-terphenyl, etc., diamines with three benzene cores, etc., these can be used alone or in combination of two or more . In the polyamide acid used in the present invention, the amount of the aromatic diamine having a fluorine atom in the diamine component, if considering both the ease of peeling from the above-mentioned substrate and the adhesion to the resin substrate, It is preferably 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 95 mol% or more, and most preferably 100 mol%. [0030] The polyamic acid contained in the composition for forming a substrate protective layer of the present invention can be obtained by reacting the above-described diamine component and tetracarboxylic dianhydride component in an organic solvent. The organic solvent used in this reaction is not particularly limited as long as it does not adversely affect the reaction, and specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 3-methoxy- N,N-dimethylpropylamide, 3-ethoxy-N,N-dimethylpropylamide, 3-propoxy-N,N-dimethylpropylamide, 3- Isopropoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-dimethylpropylamide, 3-second butoxy-N,N-dimethylamide Propylamide, 3-tert-butoxy-N,N-dimethylpropylamide, g-butyrolactone, etc. In addition, an organic solvent system can be used individually by 1 type or in combination of 2 or more types. The feed-in ratio (mol ratio) of the diamine component and the tetracarboxylic dianhydride component is suitably determined by considering the molecular weight or molecular weight distribution of purpose, the kind of diamine or the kind of tetracarboxylic dianhydride, etc., Although it cannot be prescribed|regulated uniformly, the diamine component is about 0.7-1.3 with respect to the tetracarboxylic dianhydride component 1, Preferably it is about 0.8-1.2, More preferably, it is about 0.9-1.1. The reaction temperature can be appropriately set in the range of the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ° C, but in order to prevent the imidization of the obtained polyamic acid in the solution, it is maintained. The high content of the polyamide unit is preferably about 0 to 70°C, more preferably about 0 to 60°C, and particularly preferably about 0 to 50°C. [0033] Since the reaction time depends on the reaction temperature or the reactivity of the raw material, it cannot be uniformly specified, but it is usually about 1 to 100 hours. The weight-average molecular weight of the thus obtained polyamide acid is usually about 5,000 to 500,000, but from the viewpoint of improving the function of the obtained film as a substrate protective layer, it is preferably about 10,000 to 200,000, more preferably about 30,000 ~150,000 or so. In addition, in this invention, the weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography (GPC). [0035] Furthermore, the polyamide used in the present invention can make one or both of the ends of its polymer chain more reactive with an amine having an anchor group or an acid anhydride having an anchor group. Examples of such an anchor group include a carboxylic acid group, a silicon group (for example, an alkylsilyl group, an alkoxysilyl group, a vinylsilyl group, an allylsilyl group, etc.), a vinyl group, and a maleimide. group, phenolic hydroxyl group, etc., among them, a carboxylic acid group and a silicon group (especially a group selected from an alkoxy group, a vinyl group and an allyl group are one or more silicon groups bonded to a silicon atom). In addition, between the polyamic acid obtained from the diamine component and the tetracarboxylic dianhydride component and the anchor group, an alkyl group having a carbon number of about 1 to 10 that does not significantly reduce the peeling property or heat resistance, an aromatic Spacers such as bases may be present. As a specific example of the amine having an anchor group, 4-aminophenoxytrimethylsilane, 4-aminophenoxydimethylvinylsilane, 4-aminophenoxymethyl can be enumerated Divinylsilane, 4-aminophenoxytrivinylsilane, 4-aminophenoxydimethylallylsilane, 4-aminophenoxymethyldiallylsilane, 4- Aminophenoxytriallylsilane, 4-aminophenoxydimethylphenylsilane, 4-aminophenoxymethyldiphenylsilane, 4-aminophenoxytriphenylsilane , 4-aminophenoxytrimethoxysilane, 4-aminophenoxydimethoxyvinylsilane, 4-aminophenoxymethoxydivinylsilane, 4-aminophenoxy Trivinylsilane, 4-aminophenoxydimethoxyallylsilane, 4-aminophenoxymethoxydiallylsilane, 4-aminophenoxydimethoxyphenyl Silane, 4-aminophenoxymethoxydiphenylsilane, 4-aminophenoxytriethoxysilane, 4-aminophenoxydiethoxyvinylsilane, 4-aminobenzene Oxyethoxydivinylsilane, 4-aminophenoxytrivinylsilane, 4-aminophenoxydiethoxyallylsilane, 4-aminophenoxyethoxydiene Propylsilane, 4-aminophenoxydiethoxyphenylsilane, 4-aminophenoxyethoxydiphenylsilane, 3-aminophenoxytrimethylsilane, 3-aminophenoxy Phenoxydimethylvinylsilane, 3-aminophenoxymethyldivinylsilane, 2-aminophenoxytrivinylsilane, 2-aminophenoxytrimethylsilane, 2-aminophenoxytrivinylsilane Aminophenoxydimethylvinylsilane, 2-aminophenoxymethyldivinylsilane, 2-aminophenoxytrivinylsilane, 3-aminopropyltriethylsilane, 3 -aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2- Aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-ethoxycarbonyl-3 -aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N-trimethoxy Silicon propyl triethylenetriamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, etc., but not limited thereto. As a specific example of the acid anhydride having an anchor group, trimellitic anhydride, vinyl maleic anhydride, 4-vinylnaphthalene-1,2-dicarboxylic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride can be enumerated leic anhydride, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, etc., but not limited thereto. Furthermore, the amount of the amine with an anchor group and the acid anhydride with an anchor group is expressed in molar ratio, and relative to the tetracarboxylic dianhydride component 1, the amine with an anchor group is about 0.01 to 0.6, preferably About 0.05 to 0.4, more preferably about 0.1 to 0.2, or about 0.01 to 0.52, preferably about 0.05 to 0.32, more preferably about 0.1 to 0.2, relative to the diamine component 1, the acid anhydride having an anchor group. [0039] The composition for forming a substrate protective layer of the present invention contains an organic solvent in addition to the above-mentioned polyamic acid. Although it does not specifically limit as this organic solvent, Preferably it is a solvent selected from the following. [0040]
Figure 02_image021
(wherein, R 1 to R 8 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 9 and R 10 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. 10's base, b and m represent natural numbers). [0041] b and m represent natural numbers, but preferably 1 to 3, more preferably 1 or 2. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl base, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable. Examples of the acyl group having 1 to 10 carbon atoms include alkanoyl groups having 1 to 8 carbon atoms (for example, a methyl group, an acetyl group, a propionyl group, a butyl group, an isobutyl group, a pentamyl group, a trimethylethyl group) Acetyl, etc.), cycloalkylcarbonyl having 3 to 6 carbon atoms (for example, cyclopropylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, etc.), benzyl and the like, preferably acetyl. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylacetamide, N,N-dimethylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, g-butyrolactone, more preferably N-methyl- 2-pyrrolidone. [0043] Furthermore, even if it is a solvent that does not dissolve the polyamic acid alone, it can be used for the preparation of the composition as long as the polyamic acid does not precipitate. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol can be used , 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1- Monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate Solvents having low surface tension, such as ester, n-propyl lactate, n-butyl lactate, and isoamyl lactate, are appropriately mixed and present. Thereby, it is known that the uniformity of the coating film increases at the time of coating to a substrate, and it is also applicable to the present invention. [0044] The preparation method of the composition for forming a substrate protective layer of the present invention is arbitrary. As a preferable example of a preparation method, the method of filtering the reaction solution containing the objective polyamic acid obtained by the method demonstrated above is mentioned. At this time, the filtrate may be diluted or concentrated if the purpose is to adjust the concentration or the like. By adopting such a method, not only can the contamination of impurities which can cause deterioration of adhesion, peelability, etc. of the substrate protective layer produced from the obtained composition be reduced, but also the substrate protective layer can be formed efficiently. composition. It does not specifically limit as a solvent used for dilution, As the specific example, the thing similar to the specific example of the reaction solvent of the said reaction can be mentioned. The solvent system used for dilution can be used individually by 1 type or in combination of 2 or more types. The concentration of the polyamic acid in the composition for forming a substrate protective layer of the present invention is appropriately set in consideration of the thickness of the substrate protective layer to be produced, the viscosity of the composition, etc., but is usually 1 to 30% by mass. %, preferably about 1 to 20% by mass. By having such a concentration, a substrate protective layer having a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. The concentration of the polyamic acid can adjust the amount of diamine and tetracarboxylic dianhydride used as raw materials of the polyamic acid, and when the isolated polyamic acid is dissolved in the solvent, the amount can be adjusted. The viscosity of the composition for forming a substrate protective layer of the present invention is appropriately set in consideration of the thickness of the substrate protective layer to be produced, etc., but in particular, a film having a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. For the purpose, it is usually about 10 to 10,000 mPa·s at 25°C, preferably about 20 to 5,000 mPa·s. [0047] Here, the viscosity is a commercially available viscometer for measuring the viscosity of a liquid. For example, it can be measured under the condition of the temperature of the composition at 25°C with reference to the procedure described in JIS K7117-2. As a viscometer, it is better to use a conical-plate type (cone-plate type) rotational viscometer, and it is better to use a 1°34'´R24 as a standard conical rotor in a viscometer of the same type. measured under conditions. As such a rotational viscometer, TVE-25L made by Toki Sangyo Co., Ltd. is mentioned, for example. [0048] Furthermore, the composition for forming a substrate protective layer of the present invention may contain a crosslinking agent and the like in addition to the polyamic acid and the organic solvent, for example, in order to improve the film strength. After applying the above-described composition for forming a release layer on a substrate, the polyamic acid is thermally imidized by a firing method including a firing step at a maximum temperature of 500° C. or higher to obtain A resin substrate protective layer composed of a polyimide film having easy peelability from the substrate and excellent adhesion to the resin substrate. In the present invention, there is no particular limitation as long as the maximum temperature at the time of firing is within the range of 500° C. or higher and the heat-resistant temperature of the polyimide. Moreover, the upper limit is normally about 550 degreeC, Preferably it is 520 degreeC, More preferably, it is about 510 degreeC. By making the heating temperature into the above-mentioned range, the imidization reaction can be sufficiently advanced while preventing the weakening of the obtained film. The heating time varies depending on the heating temperature and cannot be uniformly specified, but is usually 5 minutes to 5 hours. In addition, the imidization rate should just be in the range of 50 to 100%. [0050] In addition, the temperature during the above-mentioned firing may include a step of firing at a temperature lower than that as long as the maximum temperature is within the above-mentioned range. As a preferable example of the heating aspect in this invention, after heating at 50-150 degreeC, the method of raising the heating temperature step by step directly, and finally heating at 500 degreeC or more is mentioned. In particular, as a more preferable example of the heating aspect, a method of heating at 50 to 100°C, heating at more than 100°C to less than 500°C, and heating at 500°C or higher is exemplified. Furthermore, as another more preferable example of the heating mode, after heating at 50-100°C, heating at 200-300°C, heating at more than 300°C to less than 500°C, and finally heating at 500-510°C can be mentioned. method. In addition, as a preferred example of the heating state when considering the firing time, after heating at 50 to 150 ° C for 1 minute to 2 hours, the heating temperature is directly increased in stages, and finally heated at 500 ° C or more. 30 minutes to 4 hours of technique. In particular, as a more preferable example of the heating mode, heating at 50°C to 100°C for 1 minute to 2 hours, heating at more than 100°C to less than 500°C for 5 minutes to 2 hours, and heating at 500°C or higher for 30 minutes ~4 hour approach. Furthermore, as another more preferable example of the heating mode, after heating at 50-100°C for 1 minute to 2 hours, heating at 200-300°C for 5 minutes to 2 hours, and heating at 300°C to less than 500°C The method of heating at ℃ for 5 minutes to 2 hours, and finally heating at 500 to 510°C for 1 minute to 2 hours. [0052] When the substrate protective layer of the present invention is formed on the substrate, the substrate protective layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface. As an aspect of forming the substrate protective layer on a part of the surface of the substrate, there are aspects in which the substrate protective layer is formed only in a predetermined range on the surface of the substrate, dot pattern, line and space pattern, etc. are formed on the entire surface of the substrate. The pattern shape forms the state of the substrate protective layer, etc. In addition, in the present invention, the term "substrate" means a substrate coating the composition for forming a substrate protective layer of the present invention on the surface thereof, and is used for a manufacturer of a flexible electronic device or the like. As the substrate (substrate), for example, glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine, triacetin , ABS, AS, norbornene-based resin, etc.), metal (silicon wafer, etc.), wood, paper, slate, etc., especially from the viewpoint of the sufficient adhesion of the substrate protective layer of the present invention, it is preferred for glass. In addition, the surface of the base body may be composed of a single material, or may be composed of two or more kinds of materials. As an aspect in which the substrate surface is composed of two or more kinds of materials, there is an aspect in which a certain range of the substrate surface is composed of a certain material, and the rest of the surface is composed of other materials. A state in which pattern-shaped materials such as gap patterns exist in other materials, and the like. As the method that the substrate protective layer forming composition of the present invention is coated on the substrate, there is no particular limitation, such as casting coating method, spin coating method, blade coating method, dip coating method can be enumerated , roller coating method, bar coating method, die coating method, inkjet method, printing method (relief, gravure, lithography, screen printing, etc.). [0055] For example, a heating device includes a hot plate, an oven, and the like. The heating environment can be under air, or under inert gas, or under normal pressure or under reduced pressure. [0056] The thickness of the substrate protective layer is usually about 0.01 to 50 μm, and preferably about 0.05 to 20 μm from the viewpoint of productivity. Furthermore, the desired thickness is realized by adjusting the thickness of the coating film before heating. [0057] The substrate protective layer described above has moderate adhesion and moderate releasability to a substrate, particularly a glass substrate, and excellent adhesion to a resin substrate. Therefore, the substrate protective layer of the present invention is used in the manufacturing process of the flexible electronic device, does not cause damage to the resin substrate of the device, and is suitable for peeling the resin substrate together with the circuit formed on the resin substrate from the substrate. . [0058] The resin substrate formed on the substrate protective layer is not particularly limited, but from the viewpoint of heat resistance, the 1% weight reduction temperature in thermogravimetric analysis is preferably 500°C or higher. As such a resin substrate, for example, the use of wholly aromatic polyimide, polybenzoyl
Figure 106145941-A0304-12-0015-1
azoles, polybenzothiazoles, polybenzimidazoles, and resin substrates of wholly aromatic polymers. In addition, a hybrid film obtained by adding a silica sol, a titanium dioxide sol, or the like to the above-mentioned polymer may also be used. [0059] Hereinafter, an example of a manufacturing method of a flexible electronic device using the substrate protective layer of the present invention will be described. Using the composition for forming a substrate protective layer of the present invention, a substrate protective layer is formed on a glass substrate by the method described above. On the substrate protective layer, a resin substrate forming solution for forming a resin substrate is applied, and the coating film is fired to form a resin substrate fixed to a glass substrate via the substrate protective layer of the present invention. [0060] The firing temperature of the above-mentioned coating film can be appropriately set according to the type of resin, etc., but in the present invention, it is preferable that the maximum temperature at the time of firing is set to 500° C. or more. Moreover, the upper limit is normally about 550 degreeC, Preferably it is 520 degreeC, More preferably, it is about 510 degreeC. By setting the maximum temperature at the time of firing in the production of the resin substrate to this range, the peelability between the protective layer of the base and the base can be further improved, or the appropriate adhesion and peelability between the substrate protective layer and the resin substrate can be further improved . [0061] In this case, as long as the maximum temperature is within the above-mentioned range, the step of firing at a temperature below it can be included. As a preferable example of the heating aspect at the time of resin substrate manufacture, after heating at 50-150 degreeC, the method of raising the heating temperature step by step directly, and finally heating at 500 degreeC or more is mentioned. In particular, as a more preferable example of the heating aspect, a method of heating at 50 to 100°C, heating at more than 100°C to less than 500°C, and heating at 500°C or higher is exemplified. Furthermore, as another more preferable example of the heating mode, after heating at 50 to 100°C, heating at more than 100°C to 200°C, heating at more than 200°C to 300°C, and heating at more than 300°C to less than Heating at 500°C, and finally heating at 500-510°C. In addition, as a preferred example of the heating state when considering the firing time, after heating at 50 to 150 ° C for 1 minute to 2 hours, the heating temperature is directly increased in stages, and finally heated at 500 ° C or more. 30 minutes to 4 hours of technique. In particular, as a more preferable example of the heating mode, heating at 50°C to 100°C for 1 minute to 2 hours, heating at more than 100°C to less than 500°C for 5 minutes to 2 hours, and heating at 500°C or higher for 30 minutes ~4 hour approach. Furthermore, as another more preferable example of the heating mode, after heating at 50 to 100°C for 1 minute to 2 hours, heating at over 100°C to 200°C for 5 minutes to 2 hours, and heating at over 200°C to 300°C The method of heating at ℃ for 5 minutes to 2 hours, heating at more than 300℃ to less than 500℃ for 5 minutes to 2 hours, and finally heating at 500 to 510℃ for 30 minutes to 4 hours. Next, on the resin substrate fixed on the base body through the substrate protective layer of the present invention, a desired circuit is formed, then for example, the resin substrate is cut along the substrate protective layer, and the resin substrate and the substrate protective layer are combined with this. The circuit is peeled off from the base, and the resin substrate and the substrate protective layer are separated from the base. At this time, a part of the base body can also be cut together with the substrate protective layer. Furthermore, in Japanese Patent Laid-Open No. 2013-147599, it is reported that the laser lift-off method (LLO method) used in the manufacture of high-brightness LEDs or three-dimensional semiconductor packages is applied to flexible displays. manufacture. The above-mentioned LLO method is characterized by irradiating light with a specific wavelength, for example, light with a wavelength of 308 nm, from the glass substrate side from the surface opposite to the surface on which the circuit and the like are formed. The irradiated light penetrates the glass substrate, and only the polymer (polyimide) near the glass substrate absorbs the light and evaporates (sublimates). As a result, the substrate protective layer can be selectively peeled off from the glass substrate without affecting the circuit or the like provided on the resin substrate which determines the performance of the display. [0065] The composition for forming a substrate protective layer of the present invention can be used as a sacrificial layer of the LLO method because it can fully absorb light of a specific wavelength (eg, 308 nm) applicable to the above-mentioned LLO method. Therefore, when the substrate protective layer formed using the composition of the present invention is fixed on the resin substrate of the glass base, a desired circuit is formed, and then the LLO method is carried out to irradiate light of 308 nm with only the substrate protective layer. It absorbs this light and evaporates (sublimates). Thereby, the said board|substrate protective layer becomes sacrificial (functions as a sacrificial layer), and a resin substrate can be selectively peeled off from a glass substrate. [Examples] [0066] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. [1] Abbreviation symbol of compound p-PDA: p-phenylenediamine TFMB: 2,2'-bis(trifluoromethyl)benzidine BPDA: 3,3',4,4'-biphenyltetramine Carboxylic dianhydride PMDA: pyromellitic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve PGME: propylene glycol Monomethyl ether [0068] [2] Measurement method of weight average molecular weight and molecular weight distribution The weight average molecular weight (hereinafter referred to as Mw) and molecular weight distribution of the polymer were measured using a GPC apparatus (column: Shodex) manufactured by Nippon Shoko Co., Ltd. Prepare KD801 and KD805; eluent: dimethylformamide/LiBr·H 2 O (29.6mM)/H 3 PO 4 (29.6mM)/THF (0.1wt%); flow rate: 1.0mL/min; tube Column temperature: 40°C; Mw: standard polystyrene conversion value). [3] Synthesis of polymer Polyamic acid was synthesized by the following method. In addition, without isolating the polymer from the obtained polymer-containing reaction liquid, the composition for forming a resin substrate or a composition for forming a substrate protective layer is prepared by diluting the reaction liquid as described later. <Synthesis of Synthesis Example S1 Polyamide (S1)> 3.176 g (0.02937 mol) of p-PDA was dissolved in 88.2 g of NMP, 8.624 g (0.02931 mol) of BPDA was added, and the mixture was placed in a nitrogen atmosphere. , at 23 °C for 24 hours. The Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6. <Synthesis Example L1 Polyamide (L1) Synthesis> 23.7 g (74.2 mmol) of TFMB was dissolved in 352 g of NMP. To the obtained solution, 24.2 g (82.5 mmol) of BPDA was added, and the reaction was carried out at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 76,400, and the molecular weight distribution was 2.2. The resulting solution was soluble in PGME. <Synthesis Example L2 Polyamide (L2) Synthesis> 9.89 g (30.9 mmol) of TFMB was dissolved in 380 g of PGME. To the obtained solution, 10.0 g (34.3 mmol) of BPDA was added, and the reaction was carried out at 50° C. for 72 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 76,400, and the molecular weight distribution was 2.2. <Comparative Synthesis Example HL1 Synthesis of Polyamic Acid (HL1)> 2.73 g (8.53 mmol) of TFMB was dissolved in 38.5 g of NMP. To the obtained solution, 2.06 g (9.47 mmol) of PMDA was added, and the reaction was carried out at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 76,400, and the molecular weight distribution was 2.2. The resulting solution was soluble in PGME. <Comparative Synthesis Example HL2 Synthesis of Polyamic Acid (HL2)> 2.86 g (8.91 mmol) of TFMB was dissolved in 35.2 g of NMP. To the obtained solution, 1.94 g (9.91 mmol) of CBDA was added, and the reaction was carried out at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 69,200, and the molecular weight distribution was 2.2. The resulting solution was soluble in PGME. [4] Preparation of the composition for forming a resin substrate [Preparation Example 1] The reaction solution obtained in Synthesis Example S1 was used as it was as a composition for forming a resin substrate. [5] Preparation of the composition for forming a substrate protective layer [Example 1-1] To the reaction solution obtained in Synthesis Example L1, BCS and NMP were added, and the polymer concentration was 5 wt % and BCS was 20 mass % It was diluted in such a way to obtain a composition for forming a substrate protective layer. [Example 1-2] The reaction solution obtained in Synthesis Example L2 was directly used as a composition for forming a substrate protective layer. [Comparative Example 1-1] To the reaction solution obtained in Comparative Synthesis Example HL1, BCS and NMP were added and diluted so that the polymer concentration was 5 wt % and BCS was 20 mass % to obtain a composition for forming a substrate protective layer. thing. [Comparative Example 1-2] In the reaction solution obtained in Comparative Synthesis Example HL2, BCS and NMP were added and diluted so that the polymer concentration was 5 wt % and BCS was 20 mass % to obtain a composition for forming a substrate protective layer. thing. [6] Preparation of substrate protective layer and resin substrate [Example 2-1] Using a spin coater (conditions: rotation number 3,000 rpm, about 30 seconds), the substrate protective layer obtained in Example 1-1 was applied The composition for formation was applied on a 100 mm×100 mm glass substrate (the same applies hereinafter) as a glass substrate. Then, using a hot plate, the obtained coating film was heated at 80°C for 10 minutes, then heated at 300°C for 30 minutes using an oven, then heated at 400°C for 30 minutes, and further heated at 500°C for 10 minutes, and the glass substrate was placed on the glass substrate. A substrate protective layer with a thickness of about 0.1 μm is formed thereon to obtain a glass substrate with a substrate protective layer. In addition, the temperature increase rate between each heating temperature was 5 degreeC/min, and the board|substrate with a film|membrane was not taken out from the oven, but heated in the oven during the temperature increase. [0081] Using a bar coater (gap: 250 μm), on the substrate protective layer (resin film) on the glass substrate obtained above, the composition for forming a resin substrate was applied. Then, using a hot plate, the obtained coating film was heated at 80°C for 40 minutes, then heated at 140°C, 210°C, 300°C, and 400°C for 30 minutes using an oven, and further heated at 500°C for 60 minutes, and A polyimide resin substrate with a thickness of about 10 μm was formed on the substrate protective layer to obtain a glass substrate with a resin substrate and a substrate protective layer. In addition, the heating rate between each heating temperature was 2 degreeC/min, and the board|substrate with a film|membrane was not taken out from the oven, but was heated in the oven during the heating period. [Example 2-2] In addition to replacing the substrate protective layer-forming composition obtained in Example 1-1, the substrate protective layer-forming composition obtained in Example 1-2 was used, as in Example 2- 1 In the same way, a substrate protective layer and a polyimide resin substrate are formed, and a glass substrate with a substrate protective layer and a glass substrate with a resin substrate and a substrate protective layer are obtained. [Comparative Examples 2-1 to 2-2] In addition to replacing the composition for forming a substrate protective layer obtained in Example 1-1, the compositions for forming a protective substrate layer obtained in Comparative Examples 1-1 to 1-2 were respectively used A substrate protective layer and a polyimide resin substrate were formed in the same manner as in Example 2-1, except that a glass substrate with a substrate protective layer and a glass substrate with a resin substrate and a substrate protective layer were obtained. [7] Evaluation of peelability Using a cutter, the resin substrates and substrates of the glass substrates with resin substrates and substrate protective layers obtained in Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-2 were The protective layer was cut into a rectangular shape with a width of 2cm and a length of 5cm. Then, an adhesive tape was attached to the edge of the cut resin substrate, and this was used as a test piece. With respect to this test piece, a peeling test was performed using a push-pull tester manufactured by ATTONIC so that the peeling angle would be 170°, and the peelability was evaluated according to the following criteria. The results are shown in Table 1. <Evaluation Criteria of Peelability Between Glass Substrate and Substrate Protective Layer> ○: The substrate protective layer was completely peeled off from the glass base. Δ: The resin substrate can be peeled off, but a part of the substrate protective layer remains on the glass substrate. ×: The resin substrate and the substrate protective layer could not be peeled off from the glass substrate. Moreover, the surface of the glass surface of the peeled part was cut with a cutter, and the residual film property was evaluated according to the following criteria. The results are shown in Table 1. <Evaluation Criteria of Residual Film Properties of Substrate Protective Layer with respect to Glass Substrate> ○: No residual film of the substrate protective layer. △: Part of the substrate protective layer remains. ×: The substrate protective layer remains. -: Since the resin substrate did not peel, the evaluation could not be performed. [0085]
Figure 02_image023
[0086] As shown in Table 1, it was confirmed that the substrate protective layers of Examples 2-1 to 2-2 were easily peeled off together with the resin substrates, and the substrate protective layers did not remain on the glass substrates. On the other hand, the resin substrates of Comparative Examples 2-1 to 2-2 were firmly attached to the glass substrate via the substrate protective layer, and could not be peeled off from the glass substrate. [9] Physical properties of resin film The mechanical properties of the resin substrate obtained in Example 2-1 were measured. In addition, when a board|substrate protective layer was not formed, the composition S1 for resin board|substrate formation was apply|coated directly on a base|substrate, it baked, and the resin board|substrate was produced as a comparison. At this time, a resin substrate was formed in the same manner as in Example 2-1 except that the substrate was changed from a glass substrate to a silicon substrate. The obtained resin film was called SF1. <Coefficient of Linear Expansion> From the film obtained above, a test piece having a rectangular shape of 20 mm × 5 mm was prepared, and the coefficient of linear expansion from 50°C to 500°C was measured using TMA-4000SA (manufactured by Bruker AXS). The results are shown in Table 2. <Weight reduction> From the film obtained above, a 20mm×3mm rectangular test piece was prepared, and the weight loss from 50°C to 600°C was measured using TGA-DTA-2000SR (manufactured by Bruker AXS Co., Ltd.). Confirm the temperature at which a 1% weight reduction is seen. The results are shown in Table 2. [0090]
Figure 02_image025
[0091] As shown in Table 2, it can be confirmed that there is no difference in mechanical properties between the resin substrate with the substrate protective layer produced in the example and the resin substrate produced without the substrate protective layer. From the above results, it can be confirmed that the substrate protective layer does not affect the mechanical properties of the produced resin substrate.

Claims (7)

一種附保護層的樹脂基板之製造方法，其特徵係在基體上塗佈包含以下述式(1)所示的聚醯胺酸與有機溶劑之基板保護層形成用組成物，以最高溫度500℃以上燒成而形成基板保護層後，於該基板保護層之上塗佈樹脂基板形成用組成物，以最高溫度500℃以上燒成，形成樹脂基板後，將上述樹脂基板連同上述基板保護層從基體剝離，
Figure 106145941-A0305-02-0035-1
 (式中，X表示以下述式(2)所示的芳香族基，Y表示具有氟原子的2價之芳香族基，n表示自然數)
Figure 106145941-A0305-02-0035-2
 A method for producing a resin substrate with a protective layer, which is characterized in that a composition for forming a substrate protective layer comprising a polyamic acid represented by the following formula (1) and an organic solvent is coated on a substrate, and the maximum temperature is 500° C. After the above firing to form a substrate protective layer, the resin substrate forming composition is applied on the substrate protective layer, and fired at a maximum temperature of 500° C. or higher to form a resin substrate, and the resin substrate and the substrate protective layer are removed from the resin substrate. Matrix peeling,
Figure 106145941-A0305-02-0035-1
 (In the formula, X represents an aromatic group represented by the following formula (2), Y represents a divalent aromatic group having a fluorine atom, and n represents a natural number)
Figure 106145941-A0305-02-0035-2
 如請求項1之附保護層的樹脂基板之製造方法，其中上述Y係以下述式(3)所示的芳香族基；
Figure 106145941-A0305-02-0035-3
 The method for producing a resin substrate with a protective layer according to claim 1, wherein Y is an aromatic group represented by the following formula (3);
Figure 106145941-A0305-02-0035-3
 如請求項1或2之附保護層的樹脂基板之製造方法，其中上述Y係以下述式(4)所示的芳香族基；
Figure 106145941-A0305-02-0036-4
 The method for producing a resin substrate with a protective layer according to claim 1 or 2, wherein Y is an aromatic group represented by the following formula (4);
Figure 106145941-A0305-02-0036-4
 如請求項1或2之附保護層的樹脂基板之製造方法，其中上述有機溶劑係由具有以下述式(S1)~(S7)所示的構造者選出的至少1種；
Figure 106145941-A0305-02-0036-5
 (式中，R1~R8互相獨立地表示氫原子或碳數1~10的烷基，R9及R10互相獨立地表示氫原子、碳數1~10的烷基或碳數1~10的醯基，b及n表示自然數)。 The method for producing a resin substrate with a protective layer as claimed in claim 1 or 2, wherein the organic solvent is at least one selected from the group having a structure represented by the following formulae (S1) to (S7);
Figure 106145941-A0305-02-0036-5
 (wherein, R 1 to R 8 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 9 and R 10 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. 10 is an acyl group, and b and n represent natural numbers). 如請求項1或2之附保護層的樹脂基板之製造方法，其中上述樹脂基板為聚醯亞胺樹脂基板。 The method for producing a resin substrate with a protective layer according to claim 1 or 2, wherein the resin substrate is a polyimide resin substrate. 一種可撓性電子裝置之製造方法，其特徵為包含： 在基體上塗佈包含以下述式(1)所示的聚醯胺酸與有機溶劑之基板保護層形成用組成物，以最高溫度500℃以上燒成而形成具有從上述基體的易剝離性之基板保護層之步驟，於該基板保護層之上塗佈樹脂基板形成用組成物，以最高溫度500℃以上燒成而形成樹脂基板之步驟，於此樹脂基板上製作電子裝置之步驟，與將上述電子裝置連同上述基板保護層及上述樹脂基板從上述基體剝離之步驟
Figure 106145941-A0305-02-0037-6
 (式中，X表示以下述式(2)所示的芳香族基，Y表示具有氟原子的2價之芳香族基，n表示自然數)
Figure 106145941-A0305-02-0037-7
 A method for manufacturing a flexible electronic device, comprising: coating a substrate with a composition for forming a protective layer for a substrate comprising a polyamic acid represented by the following formula (1) and an organic solvent, at a maximum temperature of 500 ℃ The step of forming a substrate protective layer having easy peelability from the above-mentioned substrate by firing at ℃ or higher, coating the resin substrate forming composition on the substrate protective layer, and firing at a maximum temperature of 500 ℃ or higher to form a resin substrate. Steps, the step of fabricating the electronic device on the resin substrate, and the step of peeling the electronic device together with the substrate protective layer and the resin substrate from the base body
Figure 106145941-A0305-02-0037-6
 (In the formula, X represents an aromatic group represented by the following formula (2), Y represents a divalent aromatic group having a fluorine atom, and n represents a natural number)
Figure 106145941-A0305-02-0037-7
 如請求項6之可撓性電子裝置之製造方法，其中上述樹脂基板為聚醯亞胺樹脂基板。 The manufacturing method of a flexible electronic device according to claim 6, wherein the resin substrate is a polyimide resin substrate.
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