TWI737781B - Composition for forming peeling layer and peeling layer - Google Patents

Composition for forming peeling layer and peeling layer Download PDF

Info

Publication number
TWI737781B
TWI737781B TW106126261A TW106126261A TWI737781B TW I737781 B TWI737781 B TW I737781B TW 106126261 A TW106126261 A TW 106126261A TW 106126261 A TW106126261 A TW 106126261A TW I737781 B TWI737781 B TW I737781B
Authority
TW
Taiwan
Prior art keywords
composition
forming
resin substrate
peeling layer
substrate
Prior art date
Application number
TW106126261A
Other languages
Chinese (zh)
Other versions
TW201817775A (en
Inventor
江原和也
進藤和也
Original Assignee
日商日產化學工業股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商日產化學工業股份有限公司 filed Critical 日商日產化學工業股份有限公司
Publication of TW201817775A publication Critical patent/TW201817775A/en
Application granted granted Critical
Publication of TWI737781B publication Critical patent/TWI737781B/en

Links

Classifications

    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • 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
    • C08G73/1003—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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

提供一種包含下述式(1)所表示之聚醯胺酸、與有機溶劑的剝離層形成用組成物。 Provided is a composition for forming a release layer comprising polyamide represented by the following formula (1) and an organic solvent.

Figure 106126261-A0305-02-0001-1
(式中，X係表示下述式(2a)或(2b)所表示之芳香族基，Y係表示具有氟原子的2價的芳香族基，當X為式(2a)時，Z係相互獨立表示下述式(3a)或(4a)所表示之芳香族基，當X為式(2b)時，Z係相互獨立表示下述式(3b)或(4b)所表示之芳香族基，m係表示自然數)。
Figure 106126261-A0305-02-0001-1
 (In the formula, X is an aromatic group represented by the following formula (2a) or (2b), Y is a divalent aromatic group having a fluorine atom, and when X is a formula (2a), Z is mutually Independently represents the aromatic group represented by the following formula (3a) or (4a), and when X is the formula (2b), Z represents the aromatic group represented by the following formula (3b) or (4b) independently of each other, The m system represents a natural number).

Figure 106126261-A0305-02-0001-2
Figure 106126261-A0305-02-0001-2

Description

剝離層形成用組成物及剝離層Composition for forming peeling layer and peeling layer

[0001] 本發明為關於剝離層形成用組成物及剝離層。[0001] The present invention relates to a composition for forming a release layer and a release layer.

[0002] 近年，對於電子裝置除了要求薄型化及輕量化之類的特性外，亦要求著賦予可彎折之類的機能。因此，要求著使用輕量的可撓性塑膠基板，來取代以往的重、脆弱且無法彎折的玻璃基板。 　　特以，新世代顯示器係要求開發使用輕量、可撓性塑膠基板(以下表記為樹脂基板)的主動陣列型全彩TFT顯示器面板。有關於該新世代顯示器之技術，期待被應用於可撓性顯示器、或可撓性智慧型手機、反射鏡顯示器(mirror display)等的各式各樣的領域。 　　[0003] 在此，已開始對於將樹脂薄膜作為基板的電子裝置之製造方法進行各種檢討，並進行著能將既有的TFT顯示器面板製造用設備應用於新世代顯示器之製程檢討。又，在觸控式面板式顯示器方面，對組合於顯示器面板並使用的觸控式面板的透明電極用的樹脂基板等，已檢討用來有效率地製造該樹脂基板之對策。一般而言，使用於觸控式面板的樹脂基板，與TFT顯示器面板等為相同地，係使用具有與玻璃為同等程度的透明性的聚醯亞胺樹脂基板或丙烯酸樹脂基板、聚對苯二甲酸乙二酯(PET)樹脂基板、環烯烴樹脂基板等的薄膜基板。 　　[0004] 作為可撓性顯示器之製作方法，已知主要為直接法(非專利文獻1)。作為直接法具有下述之方法：將已事先製作好的樹脂基板透過接著劑層貼附於玻璃基板上，於該基板上直接形成包含TFT之像素電路與有機EL之方法；於玻璃基板上製作樹脂基板，於該基板上直接形成包含TFT之像素電路與有機EL之方法。 　　[0005] 然後，該直接法時，將於玻璃基板上為形成有像素電路等的樹脂基板，以後述的各種方法來進行剝離，提供於作為顯示器面板等的目的之電子裝置之製作。 　　[0006] 例如，專利文獻1、2及3揭示著一種方法，其係於玻璃基板上形成非晶矽薄膜層，將塑膠基板形成於該薄膜層上後，從玻璃基板側照射雷射來使非晶矽予以結晶化，藉由伴隨於該結晶化所產生的氫氣，將塑膠基板從玻璃基板上剝離。 　　[0007] 又，專利文獻4揭示著一種方法，其係使用專利文獻1~3所揭示之技術將被剝離層(專利文獻4中記載為「被轉印層」)貼附於塑膠薄膜來完成液晶顯示裝置。 　　[0008] 然而，以專利文獻1~4所揭示之方法，特別是專利文獻4所揭示之方法時，具有下述之問題：為了使雷射光穿透，必須使用透光性高的基板；為了使穿過基板並進一步使非晶矽中所包含的氫釋出，必須是充分且相對大能量的雷射光之照射；因雷射光之照射而有造成被剝離層損傷之情形。 　　而且，當被剝離層為大面積時，雷射處理需花費長時間，故難以提高裝置製作之生產性。 　　[0009] 作為解決如此般的問題，專利文獻5係採用下述製造步驟：使用現行的玻璃基板來作為基體(以下稱為玻璃基體)，於該玻璃基體上使用如環狀烯烴共聚物般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，以真空製程於該薄膜上形成ITO透明電極或TFT等並密封後，最終將玻璃基體進行剝離·除去。 　　[0010] 另一方面，新世代顯示器由於對應於大畫面或產率之提升等的需求，故被要求著基板的大面積化。為了使樹脂組成物均勻地塗佈於大面積的塗佈面，一般以使用狹縫塗佈機(slit coater)等的狹縫塗佈方式為適合。狹縫塗佈方式為使用狹縫噴嘴的塗佈方式，無須如以往的旋轉塗佈方式般地使基板旋轉之必要性，因而就樹脂組成物之使用量之刪減與步驟安全性之觀點而言，被廣泛採用著。然而，如此般的狹縫塗佈方式，就生產性提升之觀點而言，期望著塗佈步驟的高速化。為了實現狹縫塗佈方式的高速化，必須抑制塗佈時的條紋不勻(streaky irregularity)等的產生，因此必須使最重要的參數之一的溶液的黏度降低。 　　[0011] 例如，專利文獻6及7揭示著，使用丙二醇單甲基醚乙酸酯或丙二醇單甲基醚等所謂的低黏度溶劑而成的組成物，來作為適合於狹縫塗佈方式的光阻用組成物。然而，剝離層形成用組成物中一般所使用的聚醯亞胺樹脂等的樹脂(或是該前驅體)無法溶解於該等低黏度溶劑中，故剝離層之形成難以採用狹縫塗佈方式。因此，只要是可將剝離層形成用組成物中所使用的樹脂(或是該前驅體)溶解於上述低黏度溶劑中，不僅可提升使用以往的旋轉塗佈方式時之塗佈性，亦可成為適合使用於狹縫塗佈方式之剝離層形成用組成物。 [先前技術文獻] [專利文獻] 　　[0012] 　　[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] 國際公開第2011/030744號 　　[專利文獻7] 日本特開2008-70480號公報 [非專利文獻] 　　[0013] [非專利文獻1] NHK技研 R＆D/No.145/2014.5[0002] In recent years, in addition to characteristics such as thinning and weight reduction, electronic devices are also required to provide functions such as bendability. Therefore, it is required to use a lightweight flexible plastic substrate to replace the heavy, fragile and unbendable glass substrate in the past.　　Specially, the new-generation display system requires the development of an active array type full-color TFT display panel using a lightweight, flexible plastic substrate (hereinafter referred to as a resin substrate). The technology of this new-generation display is expected to be applied to various fields such as flexible displays, flexible smartphones, and mirror displays.　　[0003] Here, various reviews have been conducted on the manufacturing methods of electronic devices using resin films as substrates, and process reviews that can apply existing TFT display panel manufacturing equipment to new-generation displays are being conducted. In addition, in the touch panel display, the resin substrate for the transparent electrode of the touch panel used in combination with the display panel, etc., has been reviewed to efficiently manufacture the resin substrate. Generally speaking, resin substrates used in touch panels are the same as TFT display panels. Polyimide resin substrates or acrylic resin substrates and polyterephthalene resin substrates with the same degree of transparency as glass are used. Film substrates such as ethylene formate (PET) resin substrates and cycloolefin resin substrates.　　 [0004] As a manufacturing method of a flexible display, the direct method is mainly known (Non-Patent Document 1). As the direct method, there are the following methods: a prefabricated resin substrate is attached to a glass substrate through an adhesive layer, and a pixel circuit including TFT and organic EL are directly formed on the substrate; fabricated on the glass substrate A resin substrate is a method of directly forming pixel circuits containing TFTs and organic EL on the substrate.　　[0005] Then, in the direct method, a resin substrate on which pixel circuits are formed on a glass substrate is peeled off by various methods described later, and it is provided for the production of electronic devices for the purpose of display panels and the like. [0006] For example, Patent Documents 1, 2 and 3 disclose a method of forming an amorphous silicon thin film layer on a glass substrate, forming a plastic substrate on the thin film layer, and irradiating a laser from the glass substrate side to make The amorphous silicon is crystallized, and the plastic substrate is peeled from the glass substrate by the hydrogen gas generated during the crystallization. [0007] In addition, Patent Document 4 discloses a method that uses the techniques disclosed in Patent Documents 1 to 3 to attach a peeled layer (described as "transferred layer" in Patent Document 4) to a plastic film. Liquid crystal display device. [0008] 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 laser light, a substrate with high light transmittance must be used; To pass through the substrate and further release the hydrogen contained in the amorphous silicon, it must be irradiated with sufficient and relatively high-energy laser light; the laser light may cause damage to the peeling layer.　　 Moreover, when the peeled layer has a large area, the laser processing takes a long time, so it is difficult to improve the productivity of device manufacturing. [0009] In order to solve such problems, Patent Document 5 adopts the following manufacturing steps: using an existing glass substrate as a substrate (hereinafter referred to as a glass substrate), and using a cyclic olefin copolymer on the glass substrate Polymer is used to form a peeling layer. After forming a heat-resistant resin film (resin substrate) such as a polyimide film on the peeling layer, a vacuum process is used to form ITO transparent electrodes or TFTs on the film and seal the glass. The substrate is peeled and removed.　　[0010] On the other hand, new-generation displays are required to increase the area of the substrate due to the requirements for large screens or increased productivity. In order to uniformly apply the resin composition to a large-area coating surface, a slit coating method using a slit coater or the like is generally suitable. The slit coating method is a coating method using a slit nozzle. There is no need to rotate the substrate as in the conventional spin coating method. Therefore, from the viewpoint of the reduction of the amount of resin composition used and the safety of the step Language, is widely adopted. However, such a slit coating method is expected to increase the speed of the coating process from the viewpoint of productivity improvement. In order to increase the speed of the slit coating method, it is necessary to suppress the occurrence of streaky irregularities during coating. Therefore, it is necessary to reduce the viscosity of the solution, which is one of the most important parameters. [0011] For example, Patent Documents 6 and 7 disclose the use of so-called low-viscosity solvents such as propylene glycol monomethyl ether acetate or propylene glycol monomethyl ether as a composition suitable for the slit coating method. Composition for photoresist. However, resins such as polyimide resins (or the precursors) generally used in the composition for the release layer formation cannot be dissolved in these low-viscosity solvents, so it is difficult to form the release layer by slit coating. . Therefore, as long as the resin (or the precursor) used in the composition for forming a release layer can be dissolved in the above-mentioned low-viscosity solvent, not only can the coating performance when using the conventional spin coating method be improved, but also It becomes a composition for forming a release layer suitable for use in a slit coating method. [Prior Art Document] [Patent Document] 　　[0012] 　　 [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] International Publication No. 2011/030744 [Patent Document 7] Japanese Patent Laid-Open No. 2008-70480 Bulletin [Non-Patent Document] 　　[0013] [Non-Patent Document 1] NHK Giken R&D/No.145/2014.5

本發明為有鑑於上述情事之發明，目的為提供一種剝離層形成用組成物，其亦可溶解於丙二醇單甲基醚等所謂的低黏度溶劑中，亦可容易適用於狹縫塗佈方式，並可賦予不損傷於其上方所形成的可撓性電子裝置的樹脂基板(特別是以聚醯亞胺樹脂、或丙烯酸樹脂、環烯烴聚合物樹脂等所形成的薄膜基板)而剝離的剝離層。 The present invention is an invention in view of the above circumstances, and its object is to provide a composition for forming a release layer, which can also be dissolved in so-called low-viscosity solvents such as propylene glycol monomethyl ether, and can be easily applied to a slit coating method. It can also be provided with a peeling layer that does not damage the resin substrate of the flexible electronic device formed on it (especially the film substrate formed of polyimide resin, or acrylic resin, cycloolefin polymer resin, etc.) .

本發明人為了解決上述課題經深入研究之結果發現，具有特定構造的聚醯胺酸可容易地溶解於低黏度溶劑中，同時發現，包含該聚醯胺酸與有機溶劑的組成物可賦予一剝離層，其具有：與玻璃基板等的基體為優異的密著性、及與可撓性電子裝置中所使用的樹脂基板(特別是波長400nm的光穿透率為80%以上的樹脂基板)為適度的密著性和適度的剝離性，因而完成本發明。 In order to solve the above-mentioned problems, the inventors of the present invention have conducted in-depth studies and found that a polyamide with a specific structure can be easily dissolved in a low-viscosity solvent. A peeling layer, which has: excellent adhesion to a substrate such as a glass substrate, and a resin substrate used in flexible electronic devices (especially a resin substrate with a light transmittance of 80% or more at a wavelength of 400 nm) For moderate adhesion and moderate peelability, the present invention has been completed.

因此，本發明為提供下述的剝離層形成用組成物及剝離層。 Therefore, the present invention is to provide the following release layer forming composition and release layer.

[1].一種剝離層形成用組成物，其特徵係包含下述式(1)所表示之聚醯胺酸、與有機溶劑，

Figure 106126261-A0305-02-0007-3
(式中，X係表示下述式(2a)或(2b)所表示之芳香族基，Y係表示具有氟原子的2價的芳香族基，當X為式(2a)所表示之芳香族基時，Z係相互獨立表示下述式(3a)或(4a)所表示之芳香族基，當X為式(2b)所表示之芳香族基時，Z係相互獨立表示下述式(3b)或(4b)所表示之芳香族基，m係表示自然數) [1]. A composition for forming a release layer, characterized by comprising a polyamide acid represented by the following formula (1) and an organic solvent,
Figure 106126261-A0305-02-0007-3
 (In the formula, X represents an aromatic group represented by the following formula (2a) or (2b), Y represents a divalent aromatic group having a fluorine atom, when X is an aromatic group represented by formula (2a) In the case of a group, Z systems independently represent an aromatic group represented by the following formula (3a) or (4a), and when X is an aromatic group represented by a formula (2b), Z systems independently represent the following formula (3b) ) Or (4b) represents the aromatic group, m is a natural number)

Figure 106126261-A0305-02-0008-4
Figure 106126261-A0305-02-0008-4

Figure 106126261-A0305-02-0008-5
Figure 106126261-A0305-02-0008-5

[2].如上述[1]之剝離層形成用組成物，其中，上述Y為下述式(5)所表示之芳香族基，

Figure 106126261-A0305-02-0008-6
[2]. The composition for forming a release layer according to the above [1], wherein the Y is an aromatic group represented by the following formula (5),
Figure 106126261-A0305-02-0008-6

[3].如上述[2]之剝離層形成用組成物，其中，上述Y為下述式(6)所表示之芳香族基，

Figure 106126261-A0305-02-0008-7
[3]. The composition for forming a release layer according to the above [2], wherein the Y is an aromatic group represented by the following formula (6),
Figure 106126261-A0305-02-0008-7

[4].如上述[1]~[3]中任一項之剝離層形成用組成物，其中，上述X中，上述式(2a)所表示之芳香族基為下述式(7a)或(8a)所表示之芳香族基，上述Z係相互獨立為下述式(9a)或式(10a)所表示之芳香族基，

Figure 02_image009
。 　　[5].如上述[1]~[3]中任一項之剝離層形成用組成物，其中，上述X中，上述式(2b)所表示之芳香族基為下述式(7b)或(8b)所表示之芳香族基，上述Z係相互獨立為下述式(9b)或式(10b)所表示之芳香族基，
Figure 02_image011
。 　　[6].如上述[1]~[5]中任一項之剝離層形成用組成物，其中，上述有機溶劑為選自具有下述式(S1)~(S7)所表示之構造之有機溶劑之至少1種，
Figure 02_image013
。 (式中，R1 ~R8 係相互獨立表示氫原子、或碳數1~10的烷基，R9 及R10 係相互獨立表示氫原子、碳數1~10的烷基、或碳數1~10的醯基，b及n係表示自然數)。 　　[7].如上述[6]之剝離層形成用組成物，其中，上述有機溶劑為丙二醇單甲基醚或丙二醇單甲基醚乙酸酯。 　　[8].一種剝離層，其係使用上述[1]~[7]中任一項之剝離層形成用組成物而形成。 　　[9].一種樹脂基板之製造方法，其係使用上述[8]之剝離層。 　　[10].如上述[9]之製造方法，其中，上述樹脂基板為聚醯亞胺樹脂基板或波長400nm的光穿透率為80%以上的樹脂基板。[4]. The composition for forming a release layer according to any one of the above [1] to [3], wherein in the above X, the aromatic group represented by the above formula (2a) is the following formula (7a) or (8a) The aromatic group represented by the above-mentioned Z system independently of each other is an aromatic group represented by the following formula (9a) or formula (10a),
Figure 02_image009
. [5]. The composition for forming a release layer according to any one of the above [1] to [3], wherein in the above X, the aromatic group represented by the above formula (2b) is the following formula (7b) or (8b) The aromatic group represented by the above-mentioned Z system independently of each other is an aromatic group represented by the following formula (9b) or formula (10b),
Figure 02_image011
. [6]. The composition for forming a release layer according to any one of [1] to [5] above, wherein the organic solvent is selected from organic solvents having structures represented by the following formulas (S1) to (S7) At least one of the solvents,
Figure 02_image013
. (In the formula, R 1 to R 8 independently represent a hydrogen atom, or an alkyl group with 1 to 10 carbons, and R 9 and R 10 independently represent a hydrogen atom, an alkyl group with 1 to 10 carbons, or a carbon number. The base of 1~10, b and n represent natural numbers). [7]. The composition for forming a release layer according to [6] above, wherein the organic solvent is propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate. [8]. A peeling layer formed using the composition for forming a peeling layer according to any one of [1] to [7] above. [9]. A method of manufacturing a resin substrate using the release layer of [8] above. [10]. The manufacturing method according to the above [9], wherein the resin substrate is a polyimide resin substrate or a resin substrate with a light transmittance of 80% or more at a wavelength of 400 nm.

[0017] 藉由使用本發明的剝離層形成用組成物，可再現性良好地得到一剝離層，其具有：與基體為優異的密著性、及與樹脂基板為適度的密著性和適度的剝離性。特別是，本發明中所使用的聚醯胺酸，對於低黏度溶劑之溶解性為優異，故可輕易藉由使用低黏度溶劑來調製亦能適用於狹縫塗佈方式的組成物，均勻地塗佈於大面積的塗佈面將變得容易。更，在可撓性電子裝置之製造製程中，不會造成形成於基體上的樹脂基板、或進而設置於該樹脂基板上的電路等之損傷，並可將該樹脂基板與該電路等同時地從該基體進行分離。因此，本發明的剝離層形成用組成物可貢獻於具備樹脂基板的可撓性電子裝置之製造製程的高速化或該產率的提升等。 [0017] By using the composition for forming a release layer of the present invention, a release layer can be obtained with good reproducibility, which has excellent adhesion to the substrate, and moderate adhesion to the resin substrate. The peelability. In particular, the polyamide acid used in the present invention has excellent solubility in low-viscosity solvents, so it can be easily prepared by using low-viscosity solvents and can also be applied to the composition of the slit coating method, uniformly It will be easy to apply on a large-area coating surface. Furthermore, in the manufacturing process of the flexible electronic device, the resin substrate formed on the substrate or the circuit provided on the resin substrate will not be damaged, and the resin substrate and the circuit etc. can be simultaneously Separation from the substrate. Therefore, the composition for forming a peeling layer of the present invention can contribute to the speeding up of the manufacturing process of the flexible electronic device provided with the resin substrate, the improvement of the yield, and the like.

[實施發明之最佳形態] [Best form to implement the invention]

以下對於本發明進行更詳細之說明。 The present invention will be described in more detail below.

本發明的剝離層形成用組成物為包含下述式(1)所表示之聚醯胺酸、與有機溶劑。 The composition for forming a release layer of the present invention contains a polyamide acid represented by the following formula (1) and an organic solvent.

在本發明中，所謂的剝離層係設置於將形成樹脂基板的基體(玻璃基體等)之正上方之層。作為該典型例可舉例如，在可撓性電子裝置之製造製程中，在上述基體、與聚醯亞胺樹脂或丙烯酸樹脂等所形成的可撓性電子裝置的樹脂基板之間為了使該樹脂基板於指定的製程中為固定所設置，且，於該樹脂基板上形成電子電路等之後，為了使該樹脂基板可容易從該基體剝離所設置的剝離層。 In the present invention, the so-called peeling layer is a layer provided directly above the substrate (glass substrate, etc.) that will form the resin substrate. As a typical example, for example, in the manufacturing process of a flexible electronic device, between the above-mentioned matrix and the resin substrate of a flexible electronic device formed of polyimide resin or acrylic resin, in order to make the resin The substrate is fixedly installed in a specified manufacturing process, and after an electronic circuit or the like is formed on the resin substrate, the release layer provided in order to allow the resin substrate to be easily peeled from the base.

Figure 106126261-A0305-02-0012-8
Figure 106126261-A0305-02-0012-8

式(1)中，X係下述式(2a)或(2b)所表示之芳香族基，Y係具有氟原子的2價的芳香族基，若X為式(2a)時，Z係相互獨立為下述式(3a)或(4a)所表示之芳香族基，若X為式(2b)時，則其相互獨立為下述式(3b)或(4b)所表示之芳香族基，m係表示自然數。 In formula (1), X is an aromatic group represented by the following formula (2a) or (2b), Y is a divalent aromatic group having a fluorine atom, and if X is a formula (2a), Z is mutually They are independently an aromatic group represented by the following formula (3a) or (4a), and if X is the formula (2b), they are mutually independently an aromatic group represented by the following formula (3b) or (4b), The m series represents a natural number.

Figure 106126261-A0305-02-0012-9
Figure 106126261-A0305-02-0012-9

Figure 106126261-A0305-02-0012-10
Figure 106126261-A0305-02-0012-10

上述X中，上述式(2a)所表示之芳香族基係以下述式(7a)或(8a)所表示之芳香族基為較佳，上述式(2b)所表示之芳香族基係以下述式(7b)或(8b)所表示之芳香族基為較佳。 In the above X, the aromatic group represented by the above formula (2a) is preferably an aromatic group represented by the following formula (7a) or (8a), and the aromatic group represented by the above formula (2b) is preferably as follows The aromatic group represented by formula (7b) or (8b) is preferable.

[0023]

Figure 02_image019
[0024] 又，上述Z中，上述式(3a)或(4a)所表示之芳香族基係以下述式(9a)或(10a)所表示之芳香族基為較佳，上述式(3b)或(4b)所表示之芳香族基係以下述式(9b)或(10b)所表示之芳香族基為較佳。 　　[0025]
Figure 02_image021
[0026] 上述Y係以具有氟原子、且包含1~5個苯環的芳香族基為較佳，以選自下述式(5)之芳香族基為又較佳，以選自下述式(6)之芳香族基為更佳。 　　[0027]
Figure 02_image023
[0028]
Figure 02_image025
[0029] 上述m只要是自然數即可，以100以下的自然數為較佳，以2~100的自然數為又較佳。 　　[0030] 上述式(1)所表示之聚醯胺酸係藉由使指定的四羧酸二酐成分與二胺成分進行反應而得者。 　　作為上述四羧酸二酐成分，係使用苯均四酸二酐或聯苯基四羧酸二酐。作為上述二胺成分，只要是具有氟原子者可以是脂鏈、脂環、芳香族、芳香脂環族中任一者，但本發明中，特別是就對於低黏度溶劑之溶解性提升之同時，提升作為所得到之膜的剝離層的機能之觀點而言，以使上述苯均四酸二酐或聯苯基四羧酸二酐、與包含上述芳香族二胺的二胺成分進行反應而得到之聚醯胺酸為較佳，以使上述四羧酸二酐與芳香族二胺進行反應而得到之全芳香族聚醯胺酸為又較佳。 　　以下，對於可使用於合成具有上述式(1)所表示之構造的聚醯胺酸時之苯均四酸二酐成分、聯苯基四羧酸二酐及二胺成分來進行詳述。 　　[0031] 作為苯均四酸二酐，只要在分子內具有2個二羧酸酐部位，且具有苯環則不特別限定。作為其具體例，可舉出焦蜜石酸二酐、苯-1,2,3,4-四羧酸二酐等，本發明中係以焦蜜石酸二酐為較佳。該等係可單獨1種來使用、亦可組合2種以上來使用。 　　[0032] 作為聯苯基四羧酸二酐，只要在分子內具有2個二羧酸酐部位，且具有聯苯基則不特別限定。作為其具體例，可舉出2,2’,3,3’-聯苯四羧酸二酐、2,3,3’,4’-聯苯四羧酸二酐、3,3’,4,4’-聯苯四羧酸二酐等，本發明中係以3,3’,4,4’-聯苯四羧酸二酐為較佳。該等係可單獨1種來使用、亦可組合2種以上來使用。 　　[0033] 另一方面，作為芳香族二胺，只要是具有氟原子、且在分子內具有與芳香環直接鍵結的2個胺基即可，並無特別限定，以1~5個苯環、特別是以1~2個、進而以包含2個芳香族的二胺為較佳。又，以具有氟烷基或全氟烷基者為又較佳，以全氟烷基為更佳。作為上述全氟烷基，可舉例如三氟甲基、五氟乙基、n-七氟丙基及i-七氟丙基等。 　　[0034] 作為上述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、2,2’-雙(三氟甲基)-4,4’-二胺基聯苯及3,3’-雙(三氟甲基)聯苯基-4,4’-二胺等，但並非被限定於該等中。本發明，即使是該等之中，特別可適合使用2,2’-雙(三氟甲基)-4,4’-二胺基聯苯。該等係可單獨1種來使用、亦可組合2種以上來使用。 　　[0035] 由於二胺成分與四羧酸二酐成分的饋入比，係考慮目標的分子量或分子量分布、二胺或四羧酸二酐的種類等來做適當決定，因而無法一概地規定，但為了得到上述式(1)之聚醯胺酸，相對於二胺成分的莫耳數，以增加四羧酸二酐成分的莫耳數為較佳。作為具體的莫耳比，相對於二胺成分1莫耳，以四羧酸二酐成分1.05~2.5莫耳為較佳，以1.07~1.5莫耳為又較佳，以1.1~1.3莫耳為進一步較佳。 　　[0036] 藉由以上說明之四羧酸二酐成分與二胺成分進行反應，而可得到本發明的剝離層形成用組成物中所包含的聚醯胺酸。 　　[0037] 合成聚醯胺酸中使用的有機溶劑，只要是不會對反應帶來不良影響則並無特別限定，作為其具體例，可舉出m-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-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丙氧基-N,N-二甲基丙醯胺、3-異丙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、3-sec-丁氧基-N,N-二甲基丙醯胺、3-tert-丁氧基-N,N-二甲基丙醯胺、γ-丁內酯、丙二醇單甲基醚及丙二醇單甲基醚乙酸酯等。尚，有機溶劑係可單獨1種単獨或亦可組合2種以上來使用。 　　[0038] 合成聚醯胺酸時之反應溫度只要是在使用之溶劑的熔點至沸點的範圍內來做適當設定即可，通常為0~100℃左右，但就為了防止所得到之聚醯胺酸在溶液中的醯亞胺化而維持聚醯胺酸單位的高含有量觀點而言，較佳為0~70℃左右，又較佳為0~60℃左右，更佳為0~50℃左右。由於反應時間係取決於反應溫度或原料物質之反應性，故無法一概地規定，通常為1~100小時左右。 　　[0039] 以如此般之方式所得到之聚醯胺酸之重量平均分子量係通常為5,000~500,000左右，但就提升作為所得到之膜的剝離層的機能之觀點而言，較佳為10,000~ 200,000左右，又較佳為10,000~150,000左右。尚，在本發明中，重量平均分子量係藉由凝膠滲透層析法(GPC)測定所得到之聚苯乙烯換算值。 　　[0040] 作為本發明中可適合使用的聚醯胺酸之具體例，可舉出下述式所表示者，但並非被限定於此中。 　　[0041]
Figure 02_image027
(式中，m1及m2係表示重複單位的數量，m1與m2之合計係與上述m相同) 　　[0042]
Figure 02_image029
(式中，m1及m2係表示重複單位的數量，m1與m2之合計係與上述m相同) 　　[0043] 本發明的剝離層形成用組成物係包含有機溶劑。作為該有機溶劑，能使用與上述反應的反應溶劑之具體例相同者，由於充分溶解本發明的聚醯胺酸，而易於調製均勻性為高的組成物，故以選自由醯胺類、醇類、酯類、醚類及酮類所成之群之有機溶劑為較佳，特別是以包含具有下述式(S1)~(S7)所表示之構造之至少1種為較佳。 　　[0044]
Figure 02_image031
[0045] 上述式中，R1 ~R8 係相互獨立為氫原子、或碳數1~10，較佳為表示1~5的烷基。R9 及R10 係相互獨立為氫原子、碳數1~10，較佳為1~5的烷基、或碳數1~10，較佳為表示1~5的醯基。b係表示自然數以1~5的自然數為較佳，以1~3的自然數為又較佳。n係表示自然數以1~5的自然數為較佳，以1~3的自然數為又較佳。 　　[0046] 作為碳數1~10的烷基之具體例，直鏈狀、分支鏈狀、環狀中任一皆可，可舉出甲基、乙基、n-丙基、異丙基、環丙基、n-丁基、異丁基、s-丁基、t-丁基、n-戊基、1-甲基-n-丁基、2-甲基-n-丁基、3-甲基-n-丁基、1,1-二甲基-n-丙基、1,2-二甲基-n-丙基、2,2-二甲基-n-丙基、1-乙基-n-丙基、環戊基、n-己基、1-甲基-n-戊基、2-甲基-n-戊基、3-甲基-n-戊基、4-甲基-n-戊基、1,1-二甲基-n-丁基、1,2-二甲基-n-丁基、1,3-二甲基-n-丁基、2,2-二甲基-n-丁基、2,3-二甲基-n-丁基、3,3-二甲基-n-丁基、1-乙基-n-丁基、2-乙基-n-丁基、1,1,2-三甲基-n-丙基、1,2,2-三甲基-n-丙基、1-乙基-1-甲基-n-丙基、1-乙基-2-甲基-n-丙基、環己基、n-庚基、n-辛基、n-壬基及n-癸基等。 　　[0047] 作為碳數1~10的醯基之具體例，可舉出甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、異戊醯基、己醯基、異己醯基、庚醯基、異庚醯基、辛醯基、異辛醯基、壬醯基、異壬醯基、癸醯基、異癸醯基及苯甲醯基等。 　　[0048] 作為上述式(S1)~(S7)所表示之有機溶劑之具體例，可舉出以下者。 　　式(S1)：3-甲氧基-N,N-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丙氧基-N,N-二甲基丙醯胺、3-異丙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、3-sec-丁氧基-N,N-二甲基丙醯胺、3-tert-丁氧基-N,N-二甲基丙醯胺 　　式(S2)：2-吡咯啶酮、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮 　　式(S3)：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基丙醯胺、N,N-二甲基丁醯胺 　　式(S4)：γ-丁內酯 　　式(S5)：環戊酮、環己酮、環庚酮 　　式(S6)：乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯、2-羥基異丁酸甲酯、2-羥基異丁酸乙酯、2-羥基異丁酸丙酯、2-羥基異丁酸丁酯 　　式(S7)：乙基溶纖劑、丁基溶纖劑、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、丙二醇單甲基醚、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯 　　[0049] 本發明中，即使是該等之中，亦以N-甲基-2-吡咯啶酮、丁基溶纖劑、丙二醇單甲基醚及丙二醇單甲基醚乙酸酯為較佳，以丙二醇單甲基醚及丙二醇單甲基醚乙酸酯為又較佳，以丙二醇單甲基醚為更佳。該等之有機溶劑係可單獨1種或亦可組合2種以上來使用。 　　[0050] 特別是作為上述有機溶劑，使用丙二醇單甲基醚及丙二醇單甲基醚乙酸酯之類(意即，低黏度溶劑)之情形時，可得到亦能適合適用於狹縫塗裝之低黏度的剝離層形成用組成物。尚，若將本發明的剝離層形成用組成物使用於狹縫塗裝之情形時，溶劑全體中所占的上述低黏度溶劑的比例係以60質量%以上為較佳，以70質量%以上為又較佳，以80質量%以上為最佳。 　　[0051] 尚，即使是單獨使用時為無法溶解聚醯胺酸的溶劑，只要是聚醯胺酸不析出的範圍，可使用於組成物的調製。特別是可適度混摻乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇等的具有低表面張力的溶劑。據此，已知於塗佈至基板時可提升塗膜均勻性，於本發明中亦可適合使用。 　　[0052] 本發明的剝離層形成用組成物係可依通常之方法來調製。作為調製方法的較佳之一例，將藉由上述所說明之方法而得到之包含作為目標的聚醯胺酸的反應溶液進行過濾，並使用上述之有機溶劑來將所得到之濾液的濃度設為指定的濃度即可。藉由採用如此般之方法，不僅可降低能成為由所得到之組成物所製造的剝離層之密著性、剝離性等的惡化的原因之雜質的混入，並可有效地得到剝離層形成用組成物。 　　[0053] 本發明的剝離層形成用組成物中之聚醯胺酸的濃度係參酌所製作的剝離層的厚度、組成物的黏度等來做適當設定，通常為1~30質量%左右，較佳為1~20質量%左右。藉由設定如此般的濃度，可再現性良好地得到0.05~5μm左右的厚度的剝離層。聚醯胺酸的濃度係可調整作為聚醯胺酸的原料之二胺成分與四羧酸二酐成分及芳香族單胺的使用量，或於離析之聚醯胺酸溶解於溶劑中時調整其量等來進行調節。 　　[0054] 又，本發明的剝離層形成用組成物的黏度係參酌所製作的剝離層的厚度等來做適當設定，特別是將再現性良好得到0.05~5μm左右的厚度的膜作為目標之情形時，通常以25℃下10~10,000mPa·s左右，較佳為20~5,000 mPa·s左右。又，若本發明的剝離層形成用組成物使用於狹縫塗裝方式之情形時，其黏度係以2~100mPa·s左右為佳，就生產性之觀點而言，以2~25mPa·s左右為較佳。 　　[0055] 於此，黏度係可使用市售的液體的黏度測定用黏度計，參考例如JIS K7117-2所記載之程序，並藉由組成物的溫度25℃之條件下來進行測定。較佳的是作為黏度計係使用圓錐平板型(Cone-and-plate型)旋轉黏度計，且較佳為能以同型的黏度計，使用1°34’×R24來作為標準錐形轉子，並藉由組成物的溫度25℃之條件下來進行測定。作為如此般的旋轉黏度計，係可舉例如東機產業股份有限公司製TVE-25L。 　　[0056] 尚，本發明的剝離層形成用組成物，除聚醯胺酸及有機溶劑之外，為了提升例如膜強度亦可包含交聯劑等。 　　[0057] 藉由將以上說明之本發明的剝離層形成用組成物塗佈於基體，並加熱所得之塗膜來將聚醯胺酸熱醯亞胺化，可得到具有與基體為優異的密著性及與樹脂基板為適度的密著性和適度的剝離性之由聚醯亞胺膜所成之剝離層。 　　[0058] 若將如此般的本發明的剝離層形成於基體上之情形時，剝離層係可形成於基體的一部分表面、亦可形成於整面。作為於基體的一部分表面形成剝離層之樣態，係有僅在基體表面之中指定的範圍來形成剝離層之樣態、於基體表面的整面將剝離層形成為點(dot)圖型、線和間隙(line and space)圖型等的圖型形狀之樣態等。尚，在本發明中，所謂基體係指可在其表面塗佈本發明的剝離層形成用組成物者，意味可使用於可撓性電子裝置等的製造者。 　　[0059] 作為基體(基材)，可舉例如玻璃、塑膠(聚碳酸酯、聚甲基丙烯酯、聚苯乙烯、聚酯、聚烯烴、環氧、三聚氰胺、三乙醯纖維素、ABS、AS、降莰烯系樹脂等)、金屬(矽晶圓等)、木材、紙、石板等。本發明中，特別是由於剝離層具有充分的密著性，故可適合使用玻璃基體。尚，基體表面係可以單一的材料所構成、亦可以2以上的材料所構成。作為以2以上的材料來構成基體表面之樣態，係有基體表面之中的某範圍以某種的材料所構成，其餘的範圍則以其他的材料所構成之樣態，在基體表面的全體某種材料以點(dot)圖型、線和間隙(line and space)圖型等的圖型形狀來存在於其他的材料中之樣態等。 　　[0060] 將本發明的剝離層形成用組成物塗佈於基體之方法並無特別限定，可舉例如澆鑄塗佈法、旋轉塗佈法、狹縫塗佈法、刮刀塗佈法、浸漬塗佈法、輥塗佈法、桿塗佈法、模塗佈法、噴墨法、印刷法(凸版、凹版、平版、網板印刷等)等。 　　[0061] 用以醯亞胺化的加熱溫度係通常為50~550℃的範圍內來做適當決定，較佳為超過150℃~510℃。藉由如此設定加熱溫度，可防止所得到之膜的脆弱化，同時可充分地進行醯亞胺化反應。加熱時間係因依加熱溫度而異，故無法一概地規定，通常為5分鐘~5小時。又，醯亞胺化率只要是在50~100%的範圍內即可。 　　[0062] 作為本發明中之加熱樣態的較佳之一例，可舉出於以50~150℃下加熱5分鐘~2小時後，直接階段性的提升加熱溫度，最終的在超過150℃~510℃下加熱30分鐘~4小時的手法。特別是以於50~150℃下加熱5分鐘~2小時後，在超過150℃~350℃下加熱5分鐘~2小時、最後在超過350℃~450℃下加熱30分鐘~4小時為較佳。 　　[0063] 加熱中使用的器具係可舉例如加熱板、烘箱等。加熱環境下係可為空氣下亦可為惰性氣體下，又，可為常壓下亦可為減壓下。 　　[0064] 剝離層的厚度係通常為0.01~50μm左右，就生產性之觀點而言較佳為0.05~20μm左右。尚，所期望的厚度係可藉由調整加熱前之塗膜的厚度來實現。 　　[0065] 以上說明之剝離層係具有與基體(特別是玻璃基體)為優異的密著性及與樹脂基板為適度的密著性和適度的剝離性。因此，本發明的剝離層係可適用於在可撓性電子裝置之製造製程中，在不對該裝置的樹脂基板造成損傷下，將該樹脂基板與形成於該樹脂基板上的電路等同時從基體進行剝離。 　　[0066] 以下，對於使用本發明的剝離層之可撓性電子裝置之製造方法之一例來進行說明。 　　使用本發明的剝離層形成用組成物，並依據上述之方法於玻璃基體上形成剝離層。藉由於該剝離層之上塗佈用以形成樹脂基板的樹脂溶液，並加熱該塗膜，從而形成介隔著本發明的剝離層而被固定於玻璃基體的樹脂基板。此時，為了覆蓋剝離層全體，而以比剝離層的面積更大的面積來形成基板。作為樹脂基板，可舉出以作為可撓性電子裝置之樹脂基板為代表性的由聚醯亞胺樹脂或丙烯酸樹脂、環烯烴聚合物樹脂所成之基板，作為用以形成其之樹脂溶液，可舉出聚醯亞胺溶液、聚醯胺酸溶液、丙烯酸聚合物溶液及環烯烴聚合物溶液等。該樹脂基板之形成方法只要依據常用方法即可。又，作為透明性高的樹脂基板係可示例以丙烯酸樹脂或環烯烴聚合物樹脂所形成的樹脂基板，特別是以波長400nm的光穿透率為80%以上者為較佳。 　　[0067] 接下來，於介隔著本發明的剝離層而被固定於基體的該樹脂基板之上形成所期望的電路，之後，例如沿著剝離層切割樹脂基板，連同該電路將樹脂基板從剝離層進行剝離，從而將樹脂基板與基體分離。此時，亦可以連同剝離層來切割基體的一部分。 　　[0068] 尚，日本特開2013-147599號公報中報告將迄今高輝度LED或三維半導體封裝等的製造中廣泛使用的雷射剝離法(LLO法)適用於可撓性顯示器之製造。上述LLO法係以從形成有電路等的面之相反的面，自玻璃基體側照射特定波長的光線，例如波長308nm的光線來作為特徵。所照射的光線係可穿透玻璃基體，僅有玻璃基體附近的聚合物(聚醯亞胺樹脂)吸收此光線而蒸發(昇華)。其結果，將可在不對決定顯示器之性能而被設置於樹脂基板上的電路等造成影響下，可選擇性地將樹脂基板從玻璃基體進行剝離。 　　[0069] 本發明的剝離層形成用組成物由於具有所謂可適用上述LLO法之能充分吸收特定波長(例如308nm)的光線之特徵，故可使用作為LLO法的犠牲層。因此，於介隔著使用本發明之組成物所形成的剝離層而被固定於玻璃基體的樹脂基板之上，形成所期望的電路，之後，實施LLO法照射308nm的光線時，僅該剝離層吸收此光線而蒸發(昇華)。據此，上述剝離層將成為犠牲(發揮作為犠牲層之作用)，將可從玻璃基體來選擇性的剝離樹脂基板。 [實施例] 　　[0070] 以下，舉出實施例來進而詳細地說明本發明，但本發明並非被限定於該等實施例。 [1]化合物之縮寫 　　p-PDA：p-苯二胺 　　TPDA：4,4”-二胺基-p-三聯苯 　　TFMB：2,2’-雙(三氟甲基)聯苯胺 　　BPDA：3,3’,4,4’-聯苯四羧酸二酐 　　PMDA：焦蜜石酸二酐 　　DMCBDA：1,3-二甲基環丁酸二酐 　　CBDA：環丁酸二酐 　　MMA：甲基丙烯酸甲酯 　　MAA：甲基丙烯酸 　　HEMA：甲基丙烯酸2-羥基乙酯 　　AIBN：偶氮雙異丁腈 　　CHMI：環己基馬來醯亞胺 　　EPOLEAD GT-401：丁烷四羧酸、四(3,4-環氧基環己基甲基)、修飾ε-己內酯、DAICEL(股)製 　　CELOXIDE 2021P：3’,4’-環氧基環己基甲基 3,4-環氧基環己烷羧酸酯、DAICEL(股)製 　　VESTAGON B 1530：Evonik Japan(股)製 　　NMP：N-甲基-2-吡咯啶酮 　　BCS：丁基溶纖劑 　　PGME：丙二醇單甲基醚 　　PGMEA：丙二醇單甲基醚乙酸酯 　　[0071] [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(以下簡稱為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；溶離液：二甲基甲醯胺/LiBr·H2 O(29.6mM)/H3 PO4 (29.6mM)/THF(0.1質量%)；流量：1.0mL/分；管柱溫度：40℃；Mw：標準聚苯乙烯換算值)來進行。 　　[0072] [3]聚合物之合成 　　依據以下之方法來合成實施例及比較例中使用的各種聚合物。 　　尚，從所得到之含有聚合物的反應液中不會離析聚合物，而是如後述般，藉由稀釋反應液從而可調製樹脂基板形成用組成物或剝離層形成用組成物。 　　[0073] ＜合成例S1 聚醯胺酸(S1)之合成＞ 　　將p-PDA3.218g(30m mol)溶解於NMP88.2g中。於所得到之溶液中加入BPDA8.581g(29m mol)，於氮環境下以23℃使其反應24小時。所得到之聚合物的Mw為107,300、分子量分布為4.6。 　　[0074] ＜合成例S2 聚醯胺酸(S2)之合成＞ 　　將p-PDA20.261g(0.1875 mol)與TPDA12.206g(0.0469 mol)溶解於NMP617.4g中，並冷卻至15℃後添加PMDA50.112g(0.2298 mol)，於氮環境下以50℃使其反應48小時。所得到之聚合物的Mw為82,100、分子量分布為2.7。 　　[0075] ＜合成例S3 丙烯酸聚合物(S3)之合成＞ 　　將MMA7.20g(0.0719 mol)、HEMA7.20g(0.0553 mol)、CHMI10.8g(0.0603 mol)、MAA4.32g(0.0502 mol)、AIBN2.46g(0.0150 mol)溶解於PGMEA46.9g中，藉由以60~100℃使其反應20小時從而可得到丙烯酸聚合物溶液(固形分濃度40質量%)。所得到之丙烯酸聚合物的Mn為3,800、Mw為7,300。 　　[0076] ＜合成例L1 聚醯胺酸(L1)之合成＞ 　　將TFMB2.73g(8.53m mol)溶解於NMP38.5g中。於所得到之溶液中加入PMDA2.06g(9.47m mol)，於氮環境下以23℃使其反應24小時。所得到之聚合物的Mw為17,100、分子量分布為1.7。將所得到之聚合物溶液1g添加至PGME10g之結果，未特別發現有析出。 　　[0077] ＜合成例L2 聚醯胺酸(L2)之合成＞ 　　將TFMB2.73g(8.53m mol)溶解於PGME40g。於所得到之溶液中，加入PMDA2.06g(9.47m mol)，於氮環境下以23℃使其反應24小時。所得到之聚合物的Mw為20,100、分子量分布為1.8。 　　[0078] ＜合成例L3 聚醯胺酸(L3)之合成＞ 　　將TFMB23.7g(74.2m mol)溶解於NMP352g中。於所得到之溶液中，加入BPDA24.2g(82.5m mol)，於氮環境下以23℃使其反應24小時。所得到之聚合物的Mw為16,500、分子量分布為1.7。將所得到之聚合物溶液1g添加至PGME10g之結果，未特別發現有析出。 　　[0079] ＜合成例L4 聚醯胺酸(L4)之合成＞ 　　將TFMB9.89g(30.9m mol)溶解於PGME380g中。於所得到之溶液中，加入BPDA10.0g(34.3m mol)，於氮環境下以50℃使其反應72小時。所得到之聚合物的Mw為14,700、分子量分布為1.7。 　　[0080] ＜比較合成例HL1 聚醯胺酸(HL1)之合成＞ 　　將p-PDA3.90g(3.60m mol)溶解於NMP35.2g中。於所得到之溶液中，加入DMCBDA9.27g(4.00m mol)，於氮環境下以23℃使其反應24小時。所得到之聚合物的Mw為45,000、分子量分布為3.9。將所得到之聚合物溶液1g添加至PGME10g之結果，析出聚醯胺酸。 　　[0081] ＜比較合成例HL2 聚醯胺酸(HL2)之合成＞ 　　將TFMB2.86g(8.91m mol)溶解於NMP35.2g中。於所得到之溶液中，加入CBDA1.94g(9.91m mol)，於氮環境下以23℃使其反應24小時。所得到之聚合物的Mw為69,200、分子量分布為2.2。將所得到之聚合物溶液1g添加至PGME10g之結果，未特別發現有析出。 　　[0082] [4]樹脂基板形成用組成物之調製 　　依據以下之方法來調製樹脂基板形成用組成物。 　　[0083] ＜調製例1 樹脂基板形成用組成物F1＞ 　　將合成例S1所得到之反應液直接使用作為樹脂基板形成用組成物F1。 　　[0084] ＜調製例2 樹脂基板形成用組成物F2＞ 　　將合成例S2所得到之反應液直接使用作為樹脂基板形成用組成物F2。 　　[0085] ＜調製例3 樹脂基板形成用組成物F3＞ 　　於合成例S3所得到之反應液10g中，添加EPOLEADGT-401 0.60g與PGMEA11.8g，以23℃攪拌24小時來調製樹脂基板形成用組成物F3。 　　[0086] ＜調製例4 樹脂基板形成用組成物F4＞ 　　於合成例S3所得到之反應液10g中，添加CELOXIDE 2021P 0.80g與PGMEA11.8g，以23℃攪拌24小時來調製樹脂基板形成用組成物F4。 　　[0087] ＜調製例5 樹脂基板形成用組成物F5＞ 　　於合成例S3所得到之反應液10g中，添加VESTAGON B 1530 0.60g與PGMEA11.8g，以23℃攪拌24小時來調製樹脂基板形成用組成物F5。 　　[0088] ＜調製例6 樹脂基板形成用組成物F6＞ 　　於放入四氯化碳100g的茄型燒瓶中，添加Zeonor(註冊商標)1020R(日本Zeon(股)製、環烯烴聚合物樹脂)10g及GT-401 3g。將該溶液於氮環境下攪拌24小時並溶解，來調製樹脂基板形成用組成物F6。 　　[0089] ＜調製例7 樹脂基板形成用組成物F7＞ 　　於放入四氯化碳100g的茄型燒瓶中，添加Zeonor(註冊商標)1060R(日本Zeon(股)製、環烯烴聚合物樹脂)10g。將該溶液於氮環境下攪拌24小時並溶解，來調製樹脂基板形成用組成物F7。 　　[0090] [5]剝離層形成用組成物之調製 [實施例1-1] 　　於合成例L1所得到之反應液中，加入BCS與NMP，以使聚合物濃度成為5質量%、BCS成為20質量%之方式來做稀釋，從而得到剝離層形成用組成物。 　　[0091] [實施例1-2] 　　將合成例L2所得到之反應溶液直接作為剝離層形成用組成物。 　　[0092] [實施例1-3] 　　於合成例L3所得到之反應液中，加入BCS與NMP，以使聚合物濃度成為5質量%、BCS成為20質量%之方式來做稀釋，從而得到剝離層形成用組成物。 　　[0093] [實施例1-4] 　　將合成例L4所得到之反應溶液直接作為剝離層形成用組成物。 　　[0094] [比較例1-1] 　　於比較合成例HL1所得到之反應液中，加入BCS與NMP，以使聚合物濃度成為5質量%、BCS成為20質量%之方式來做稀釋，從而得到剝離層形成用組成物。 　　[0095] [比較例1-2] 　　於比較合成例HL2所得到之反應液中，加入BCS與NMP，以使聚合物濃度成為5質量%、BCS成為20質量%之方式來做稀釋，從而得到剝離層形成用組成物。 　　[0096] [6]剝離層及樹脂基板之製作 [實施例2-1] 　　使用旋轉塗佈機(條件：以旋轉數3,000rpm下約30秒)，將實施例1-1所得到之剝離層形成用組成物L1塗佈於作為玻璃基體之100mm×100mm玻璃基板(以下相同)之上。 　　然後，使用加熱板以80℃將所得到之塗膜加熱10分鐘，之後，使用烘箱以300℃加熱30分鐘，並將加熱溫度昇溫至400℃為止(10℃/分，進而以400℃加熱30分鐘，於玻璃基板上形成厚度約0.1μm的剝離層，而得到附有剝離層的玻璃基板。尚，於昇溫之間，不從烘箱中取出附有膜的基板，而是在烘箱內加熱。 　　[0097] 使用棒塗佈機(間隙：250μm)，將樹脂基板形成用組成物F1塗佈於上述所得到之玻璃基板上的剝離層(樹脂薄膜)之上。然後，使用加熱板以80℃將所得到之塗膜加熱30分鐘，之後，使用烘箱以140℃加熱30分鐘，將加熱溫度昇溫至210℃為止(2℃/分、以下相同)，並以210℃加熱30分鐘，將加熱溫度昇溫至300℃為止，再以300℃加熱30分鐘，將加熱溫度昇溫至400℃為止，以400℃加熱60分鐘，於剝離層上形成厚度約20μm的樹脂基板，而得到附有樹脂基板·剝離層的玻璃基板。於昇溫之間，不從烘箱中取出附有膜的基板，而是在烘箱內加熱。 　　[0098] [實施例2-2] 　　除了使用樹脂基板形成用組成物F2來替代實施例2-1使用的樹脂基板形成用組成物F1以外，以與實施例2-1相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0099] [實施例2-3] 　　除了使用實施例1-2所得到之剝離層形成用組成物L2來替代實施例1-1所得到之剝離層形成用組成物L1以外，以與實施例2-1相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0100] [實施例2-4] 　　作為剝離層形成用組成物係使用實施例1-2所得到之剝離層形成用組成物L2，作為樹脂基板形成用組成物係使用實施例2-2中所利用的樹脂基板形成用組成物F2，並以與實施例2-1相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0101] [實施例2-5] 　　作為剝離層形成用組成物係使用實施例1-1所得到之剝離層形成用組成物L1，作為樹脂基板形成用組成物係使用樹脂基板形成用組成物F4，並以與實施例2-1相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃板。 　　[0102] [實施例2-6] 　　作為剝離層形成用組成物係使用實施例1-1所得到之剝離層形成用組成物L1，作為樹脂基板形成用組成物係使用樹脂基板形成用組成物F5，並以與實施例2-1相同之方法來製作剝離層及樹脂基板，而可得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0103] [實施例2-7] 　　作為剝離層形成用組成物係使用實施例1-2所得到之剝離層形成用組成物L2，作為樹脂基板形成用組成物係使用樹脂基板形成用組成物F5，並以與實施例2-1相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0104] [實施例2-8] 　　使用實施例1-1所得到之剝離層形成用組成物L1，並以與實施例2-1相同之方法來形成剝離層，而得到附有剝離層的玻璃基板。 　　之後，立即使用旋轉塗佈機(條件：以旋轉數200rpm下約15秒)，將樹脂基板形成用組成物F6塗佈於前述玻璃基板上的剝離層(樹脂薄膜)之上。使用加熱板以80℃將所得到之塗膜加熱2分鐘，之後，使用加熱板以230℃加熱30分鐘，於剝離層上形成厚度約3μm的樹脂基板，而得到附有樹脂基板•剝離層的玻璃基板。之後，使用紫外可視分光光度計(島津製作所(股)製UV-2600)來測定光穿透率之結果，樹脂基板係顯示於400nm下為80%以上的穿透率。 　　[0105] [實施例2-9] 　　除了使用實施例1-2所得到之剝離層形成用組成物L2來替代實施例1-1所得到之剝離層形成用組成物L1以外，以與實施例2-8相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0106] [實施例2-10] 　　使用實施例1-1所得到之剝離層形成用組成物L1，以與實施例2-1相同之方法來形成剝離層，而得到附有剝離層的玻璃基板。 　　之後，立即使用旋轉塗佈機(條件：以旋轉數200rpm下約15秒)，將樹脂基板形成用組成物F7塗佈於前述玻璃基板上的剝離層(樹脂薄膜)之上。使用加熱板以80℃將所得到之塗膜加熱2分鐘，之後，使用加熱板以230℃加熱30分鐘，於剝離層上形成厚度約3μm的樹脂基板，而得到附有樹脂基板•剝離層的玻璃基板。之後，使用紫外可視分光光度計(島津製作所(股)製UV-2600)來測定光穿透率之結果，樹脂基板係顯示於400nm下為80%以上的穿透率。 　　[0107] [實施例2-11] 　　除了使用實施例1-2所得到之剝離層形成用組成物L2來替代實施例1-1所得到之剝離層形成用組成物L1以外，以與實施例2-10相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0108] [比較例2-1~2-4] 　　除了使用比較例1-1~1-2所得到之剝離層形成用組成物來替代實施例1-1所得到之剝離層形成用組成物以外，以與上述實施例相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。剝離層與樹脂基板之組合係如表1所表示般。 　　[0109] [實施例2-12] 　　使用旋轉塗佈機(條件：以旋轉數3,000rpm下約30秒)，將實施例1-3所得到之剝離層形成用組成物L3塗佈於作為玻璃基體之100mm×100mm玻璃基板(以下相同)之上。 　　然後，使用加熱板以80℃將所得到之塗膜加熱10分鐘，之後，使用烘箱以300℃加熱30分鐘，並將加熱溫度昇溫至400℃為止(10℃/分，進而以400℃加熱30分鐘，於玻璃基板上形成厚度約0.1μm的剝離層，而得到附有剝離層的玻璃基板。尚，於昇溫之間，不從烘箱中取出附有膜的基板，而是在烘箱內加熱。 　　[0110] 使用旋轉塗佈機(條件：以旋轉數800rpm下約10秒)，將樹脂基板形成用組成物F3塗佈於上述所得到之玻璃基板上的剝離層(樹脂薄膜)之上。然後，使用加熱板以80℃將所得到之塗膜加熱30分鐘，之後，使用烘箱以230℃加熱30分鐘，於剝離層上形成厚度約3μm的丙烯酸基板。於昇溫之間，不從烘箱中取出附有膜的基板，而是在烘箱內加熱。 　　[0111] [實施例2-13] 　　除了使用樹脂基板形成用組成物F4來替代實施例2-12所利用的樹脂基板形成用組成物F3以外，以與實施例2-12相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0112] [實施例2-14] 　　除了使用樹脂基板形成用組成物F5來替代實施例2-12所利用的樹脂基板形成用組成物F3以外，以與實施例2-12相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0113] [實施例2-15] 　　除了使用實施例1-4所得到之剝離層形成用組成物L4來替代實施例1-3所得到之剝離層形成用組成物L3以外，以與實施例2-12相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0114] [實施例2-16] 　　作為剝離層形成用組成物係使用實施例1-4所得到之剝離層形成用組成物L4，作為樹脂基板形成用組成物係使用實施例2-14所利用的樹脂基板形成用組成物F5，並以與實施例2-12相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0115] [實施例2-17] 　　使用實施例1-3所得到之剝離層形成用組成物L3，以與實施例2-12相同之方法來形成剝離層，而得到附有剝離層的玻璃基板。 　　之後，立即使用旋轉塗佈機(條件：以旋轉數200rpm下約15秒)，將樹脂基板形成用組成物F6塗佈於前述玻璃基板上的剝離層(樹脂薄膜)之上。使用加熱板以80℃將所得到之塗膜加熱2分鐘，之後，使用加熱板以230℃加熱30分鐘，於剝離層上形成厚度約3μm的樹脂基板，而得到附有樹脂基板•剝離層的玻璃基板。之後，使用紫外可視分光光度計(島津製作所(股)製UV-2600)來測定光穿透率之結果，樹脂基板係顯示於400nm下為80%以上的穿透率。 　　[0116] [實施例2-18] 　　除了使用實施例1-4所得到之剝離層形成用組成物L4來替代實施例1-3所得到之剝離層形成用組成物L3以外，以與實施例2-17相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0117] [實施例2-19] 　　使用實施例1-3所得到之剝離層形成用組成物L3，以與實施例2-12相同之方法來形成剝離層，而得到附有剝離層的玻璃基板。 　　之後，立即使用旋轉塗佈機(條件：以旋轉數200rpm下約15秒)，將樹脂基板形成用組成物F7塗佈於前述玻璃基板上的剝離層(樹脂薄膜)之上。使用加熱板以80℃將所得到之塗膜加熱2分鐘，之後，使用加熱板以230℃加熱30分鐘，於剝離層上形成厚度約3μm的樹脂基板，而得到附有樹脂基板•剝離層的玻璃基板。之後，使用紫外可視分光光度計(島津製作所(股)製UV-2600)來測定光穿透率之結果，樹脂基板係顯示於400nm下為80%以上的穿透率。 　　[0118] [實施例2-20] 　　除了使用實施例1-4所得到之剝離層形成用組成物L4來替代實施例1-3所得到之剝離層形成用組成物L3以外，以與實施例2-19相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0119] [比較例2-5] 　　除了使用比較例1-1所得到之剝離層形成用組成物HL1來替代實施例1-3所得到之剝離層形成用組成物L3以外，以與實施例2-12相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。將剝離層與樹脂基板之組合係表示於表2般。 　　[0120] [比較例2-6] 　　作為剝離層形成用組成物係使用比較例1-2所得到之剝離層形成用組成物HL2，作為樹脂基板形成用組成物係使用實施例2-13所利用的樹脂基板形成用組成物F4，以與實施例2-12相同之方法來製作剝離層及樹脂基板，而得到附有剝離層的玻璃基板及附有樹脂基板•剝離層的玻璃基板。 　　[0121] [7]剝離層之溶劑耐性之評估 　　使用吸管將NMP與PGME以0.1ml滴入至所得到之實施例2-1~2-20、比較例2-1~2-6所製作的附有剝離層的玻璃基板之剝離層上。1分鐘後，利用純水洗淨該剝離層後，以目視來觀察滴入溶劑部分的剝離層之狀態，來評估剝離層之溶劑耐性。判定基準係如以下般。將結果表示於表1及表2。 ＜判定基準＞ 　　○：未特別發現液滴的痕跡、未發現溶解。 　　△：有發現液滴的痕跡但發現殘膜。 　　×：呈現溶解。 　　所謂剝離層未溶解於滴入的溶劑中，係指於剝離層上形成樹脂基板時，未溶解在樹脂基板形成用組成物中所包含的有機溶劑之意，且從玻璃基板將不損傷樹脂基板而可剝離之意。 　　[0122] [8]剝離性之評估 　　對於上述實施例2-1~2-20及比較例2-1~2-6所得到之附有樹脂基板•剝離層的玻璃基板，藉由下述方法來確認剝離層與玻璃基板之剝離性。尚，下述之試驗係以相同的玻璃基板來進行。 　　[0123] ＜剝離層與玻璃基板之剝離性評估＞ 　　將實施例2-1~2-20及比較例2-1~2-6所得到之附有剝離層的玻璃基板上的剝離層交叉切割(縱橫1mm間隔、以下相同)，並進行100格的塊切。即，藉由此交叉切割，形成100個1mm見方的方格目。 　　然後，將黏著膠帶貼附於此100格塊切部分，並剝除該膠帶基於以下之基準(5B~0B、B、A、AA)來評估剝離之程度。 　　進而，於全部為經剝離的基板之中，使用實施例2-5~2-20所製作的附有樹脂基板•剝離層的玻璃基板來實施剝離力評估試驗。試驗方法係使用刀片以貫穿之方式切入至樹脂基板的背面，來使附有樹脂基板•剝離層的玻璃基板的樹脂基板成為25mm×50mm寬的長方形，以製成長條。進而，於製作的長條上黏貼賽珞凡膠帶(NichibanCT-24)後，使用Autograph AG-500N(島津製作所(股)製)，相對於基板的面以90度，即，朝垂直方向進行剝離來測定剝離力，並將100%剝離(全部剝離)、尚且剝離力為未滿0.1N/25mm者設為AAA。 　　將以上之結果表示於表1及表2。 ＜判定基準＞ 　　5B：0%剝離(無剝離) 　　4B：未滿5%的剝離 　　3B：5~未滿15%的剝離 　　2B：15~未滿35%的剝離 　　1B：35~未滿65%的剝離 　　0B：65%~未滿80%的剝離 　　B：80%~未滿95%的剝離 　　A：95%~未滿100%的剝離 　　AA：100%剝離(全部剝離) 　　AAA：100%剝離且剝離力為未滿0.1N/25mm 　　[0124] ＜剝離層與樹脂基板之剝離性評估＞ 　　對於實施例2-1~2-20及比較例2-1~2-6所得到之附有樹脂基板•剝離層的玻璃基板，依據與上述之剝離性評估相同之程序來評估其剝離性。將結果表示於表1及表2。 　　[0125]
Figure 02_image033
[0126]
Figure 02_image035
[0127] 如表1及表2所表示般，可確認實施例2-1~2-20的剝離層係與玻璃基板之密著性為優異，且與樹脂膜為輕易剝落。又，從溶解性試驗之結果亦可確認，亦未溶解於樹脂基板形成用組成物中所包含的有機溶劑中。 　　另一方面，可確認比較例2-1~2-6的剝離層雖與玻璃基板之密著性為優異，但與樹脂基板之剝離性為差。[0023]
Figure 02_image019
[0024] Furthermore, in the above-mentioned Z, the aromatic group represented by the above formula (3a) or (4a) is preferably an aromatic group represented by the following formula (9a) or (10a), and the above formula (3b) Or the aromatic group represented by (4b) is preferably an aromatic group represented by the following formula (9b) or (10b). [0025]
Figure 02_image021
[0026] The above-mentioned Y is preferably an aromatic group having a fluorine atom and containing 1 to 5 benzene rings, and more preferably an aromatic group selected from the following formula (5), and is selected from the following The aromatic group of formula (6) is more preferable. [0027]
Figure 02_image023
[0028]
Figure 02_image025
[0029] The above-mentioned m may be a natural number, and a natural number of 100 or less is preferable, and a natural number of 2 to 100 is more preferable. [0030] The polyamide represented by the above formula (1) is obtained by reacting a specified tetracarboxylic dianhydride component and a diamine component. As the tetracarboxylic dianhydride component, pyromellitic dianhydride or biphenyltetracarboxylic dianhydride is used. As the above-mentioned diamine component, as long as it has a fluorine atom, it can be any of aliphatic chain, alicyclic, aromatic, and aromatic alicyclic. However, in the present invention, especially the solubility to low-viscosity solvents is improved while at the same time From the viewpoint of improving the function of the release layer of the obtained film, the above-mentioned pyromellitic dianhydride or biphenyltetracarboxylic dianhydride is reacted with the diamine component containing the above-mentioned aromatic diamine. The obtained polyamide acid is preferable, and the wholly aromatic polyamide acid obtained by reacting the above-mentioned tetracarboxylic dianhydride and aromatic diamine is more preferable. Hereinafter, the pyromellitic dianhydride component, biphenyltetracarboxylic dianhydride, and diamine component that can be used for synthesizing the polyamide acid having the structure represented by the above formula (1) will be described in detail. [0031] Pyromellitic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has a benzene ring. As specific examples thereof, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, etc. may be mentioned, and pyromellitic dianhydride is preferred in the present invention. These systems may be used individually by 1 type, and may be used in combination of 2 or more types. [0032] The biphenyl tetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has a biphenyl group. Specific examples include 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4 , 4'-biphenyltetracarboxylic dianhydride, etc., in the present invention, 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferred. These systems may be used individually by 1 type, and may be used in combination of 2 or more types. [0033] On the other hand, as the aromatic diamine, as long as it has a fluorine atom and has two amine groups directly bonded to the aromatic ring in the molecule, it is not particularly limited, and it has 1 to 5 benzene rings. Especially, it is preferable to use 1 to 2, and further preferably contain 2 aromatic diamines. Furthermore, those having a fluoroalkyl group or a perfluoroalkyl group are more preferable, and a perfluoroalkyl group is more preferable. Examples of the perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl, i-heptafluoropropyl, and the like. [0034] As specific examples of the above-mentioned aromatic diamines, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 2,2'-Bis(trifluoromethyl)-4,4'-diaminobiphenyl and 3,3'-bis(trifluoromethyl)biphenyl-4,4'-diamine, etc., but not limited to Such in. In the present invention, even among these, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl can be particularly suitably used. These systems may be used individually by 1 type, and may be used in combination of 2 or more types. [0035] Since the feed ratio of the diamine component and the tetracarboxylic dianhydride component is appropriately determined in consideration of the target molecular weight or molecular weight distribution, the type of diamine or tetracarboxylic dianhydride, etc., it cannot be specified uniformly. However, in order to obtain the polyamide acid of the above formula (1), it is preferable to increase the number of moles of the tetracarboxylic dianhydride component relative to the number of moles of the diamine component. As a specific molar ratio, relative to 1 mol of the diamine component, 1.05 to 2.5 mol of the tetracarboxylic dianhydride component is preferred, 1.07 to 1.5 mol is more preferred, and 1.1 to 1.3 mol is preferred Further better. [0036] By reacting the tetracarboxylic dianhydride component and the diamine component described above, the polyamide acid contained in the composition for forming a release layer of the present invention can be obtained. [0037] The organic solvent used in the synthesis of polyamide acid is not particularly limited as long as it does not adversely affect the reaction. Specific examples thereof include m-cresol, 2-pyrrolidone, and N -Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Formamide, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-propoxy-N,N-dimethyl Propyl propionamide, 3-isopropoxy-N,N-dimethyl propionamide, 3-butoxy-N,N-dimethyl propionamide, 3-sec-butoxy-N, N-dimethylpropanamide, 3-tert-butoxy-N,N-dimethylpropanamide, γ-butyrolactone, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, etc. Moreover, the organic solvent system may be used individually by 1 type or in combination of 2 or more types. [0038] The reaction temperature when synthesizing polyamide acid can be appropriately set within the range of the melting point to the boiling point of the solvent used, and it is usually about 0 to 100°C, but it is to prevent the obtained polyamide From the viewpoint of maintaining the high content of polyamic acid units by imidization of the acid in the solution, it is preferably about 0 to 70°C, more preferably about 0 to 60°C, and more preferably 0 to 50°C about. Since the reaction time depends on the reaction temperature or the reactivity of the raw materials, it cannot be specified uniformly, and is usually about 1 to 100 hours. [0039] The weight average molecular weight of the polyamide obtained in such a manner is usually about 5,000 to 500,000, but from the viewpoint of improving the function of the release layer of the obtained film, it is preferably 10,000 to 10,000. It is about 200,000, and preferably about 10,000 to 150,000. In the present invention, the weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography (GPC) measurement. [0040] As a specific example of the polyamide acid that can be suitably used in the present invention, one represented by the following formula can be given, but it is not limited to this. [0041]
Figure 02_image027
(In the formula, m1 and m2 represent the number of repeating units, and the total of m1 and m2 is the same as the above m) [0042]
Figure 02_image029
(In the formula, m1 and m2 represent the number of repeating units, and the total of m1 and m2 is the same as the above-mentioned m) [0043] The composition for forming a release layer of the present invention contains an organic solvent. As the organic solvent, the same as the specific examples of the reaction solvent of the above-mentioned reaction can be used. Since the polyamide acid of the present invention is sufficiently dissolved and a composition with high uniformity is easy to prepare, it is selected from the group consisting of amides and alcohols. Organic solvents of the group consisting of ketones, esters, ethers, and ketones are preferred, and particularly preferably include at least one of the structures represented by the following formulas (S1) to (S7). [0044]
Figure 02_image031
[0045] In the above formula, R 1 to R 8 are independently a hydrogen atom or a carbon number of 1 to 10, and preferably represent an alkyl group of 1 to 5. R 9 and R 10 are independently a hydrogen atom, an alkyl group having 1 to 10 carbons, preferably 1 to 5, or an acyl group having 1 to 10 carbons, preferably 1 to 5. The b series means that the natural number is preferably from 1 to 5, and the natural number from 1 to 3 is more preferred. The n system indicates that the natural number is preferably from 1 to 5, and the natural number from 1 to 3 is more preferred. [0046] As specific examples of the alkyl group having 1 to 10 carbon atoms, any of linear, branched, and cyclic may be used, and examples include methyl, ethyl, n-propyl, isopropyl, Cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3- Methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl -N-propyl, cyclopentyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl- n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl Base-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n- Butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1- Ethyl-2-methyl-n-propyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl, etc. [0047] Specific examples of the acyl group having 1 to 10 carbon atoms include formyl, acetyl, propionyl, butyryl, isobutyryl, pentyl, isopentyl, hexyl, and isohexyl. Heptanyl, heptanoyl, isoheptanoyl, octanoyl, isooctanoyl, nonanoyl, isononanoyl, decanoyl, isodecanoyl, benzyl and the like. [0048] As specific examples of the organic solvents represented by the above formulas (S1) to (S7), the following can be cited. Formula (S1): 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-propoxy-N,N-di Methylpropionamide, 3-isopropoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 3-sec-butoxy-N ,N-dimethylpropanamide, 3-tert-butoxy-N,N-dimethylpropanamide Formula (S2): 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone formula (S3): N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, N, N-dimethylbutyramide formula (S4): γ-butyrolactone formula (S5): cyclopentanone, cyclohexanone, cycloheptanone formula (S6): methyl lactate, ethyl lactate, lactate n- Propyl ester, n-butyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, propyl 2-hydroxyisobutyrate, butyl 2-hydroxyisobutyrate (S7): ethyl cellosolve, butyl cellosolve, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol , Propylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate [0049] In the present invention, even among these, N-methyl-2-pyrrolidone, butyl cellosolve, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are also preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred. It is still more preferable, and propylene glycol monomethyl ether is more preferable. These organic solvents can be used individually by 1 type or in combination of 2 or more types. [0050] Especially when using propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (that is, a low-viscosity solvent) as the above-mentioned organic solvent, it is available and suitable for slit coating. The low-viscosity release layer forming composition. However, when the composition for forming a release layer of the present invention is used for slit coating, the ratio of the low-viscosity solvent in the total solvent is preferably 60% by mass or more, and 70% by mass or more To be more preferable, 80% by mass or more is most preferable. [0051] Even if it is a solvent that cannot dissolve polyamic acid when used alone, it can be used for the preparation of a composition as long as it is in a range where polyamic acid does not precipitate. Especially it can be mixed with ethyl carbitol, butyl carbitol, ethyl carbitol acetate, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, Solvents with low surface tension such as dipropylene glycol and 2-(2-ethoxypropoxy)propanol. According to this, it is known that the uniformity of the coating film can be improved when it is applied to a substrate, and it can also be suitably used in the present invention. [0052] The composition system for forming a release layer of the present invention can be prepared by a usual method. As a preferable example of the preparation method, the reaction solution containing the target polyamic acid obtained by the method described above is filtered, and the above-mentioned organic solvent is used to set the concentration of the obtained filtrate to a specified value. The concentration can be. By adopting such a method, it is possible not only to reduce the mixing of impurities that can cause deterioration of the adhesion, peelability, etc. of the peeling layer produced from the obtained composition, but also to effectively obtain the peeling layer formation. Composition. [0053] The concentration of polyamide acid in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, etc., and is usually about 1 to 30% by mass. Preferably, it is about 1-20% by mass. By setting such a concentration, a release layer with a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. The concentration of polyamide can be adjusted when the diamine component, tetracarboxylic dianhydride component and aromatic monoamine used as the raw material of polyamide acid are used, or adjusted when the isolated polyamide acid is dissolved in a solvent The amount and so on can be adjusted. [0054] In addition, the viscosity of the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, especially when a film with a thickness of about 0.05 to 5 μm with good reproducibility is targeted. It is usually about 10 to 10,000 mPa·s at 25°C, preferably about 20 to 5,000 mPa·s. In addition, when the composition for forming a release layer of the present invention is used in a slit coating method, its viscosity is preferably about 2 to 100 mPa·s, and from the viewpoint of productivity, it is 2 to 25 mPa·s Left and right are better. [0055] Here, the viscosity can be measured using a commercially available viscometer for measuring the viscosity of liquids, referring to, for example, the procedure described in JIS K7117-2, and measuring the temperature of the composition under the condition of 25°C. It is preferable to use a cone-and-plate rotary viscometer as a viscometer, and it is preferable to use the same type of viscometer, using 1°34'×R24 as the standard cone rotor, and The measurement is performed under the condition of the temperature of the composition at 25°C. As such a rotational viscometer, TVE-25L manufactured by Toki Sangyo Co., Ltd. can be mentioned, for example. [0056] In addition, the composition for forming a release layer of the present invention may include a crosslinking agent and the like in addition to polyamide acid and an organic solvent in order to improve film strength, for example. [0057] By applying the composition for forming a release layer of the present invention described above to a substrate, and heating the resulting coating film to thermally imidize polyamide acid, it is possible to obtain an excellent density with the substrate. A peeling layer made of polyimide film with moderate adhesion and moderate peelability to the resin substrate. [0058] When such a release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface. As an aspect in which a release layer is formed on a part of the surface of the substrate, there is an aspect in which the release layer is formed only in a specified range on the surface of the substrate, and the release layer is formed in a dot pattern on the entire surface of the substrate, Line and space (line and space) graphics and other graphic shapes, etc. In addition, in the present invention, the so-called base system refers to those that can coat the release layer forming composition of the present invention on the surface thereof, and means that it can be used for manufacturers of flexible electronic devices and the like. [0059] As the substrate (substrate), for example, glass, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resins, etc.), metals (silicon wafers, etc.), wood, paper, slate, etc. In the present invention, in particular, since the peeling layer has sufficient adhesiveness, a glass substrate can be suitably used. Furthermore, the surface of the substrate can be composed of a single material or more than 2 materials. As the case where the surface of the substrate is composed of 2 or more materials, a certain range of the substrate surface is constituted by a certain material, and the rest of the range is constituted by other materials, covering the entire surface of the substrate A certain kind of material exists in other materials in pattern shapes such as dot pattern, line and space pattern, etc. [0060] The method of applying the composition for forming a release layer of the present invention to a substrate is not particularly limited, and examples thereof include casting coating, spin coating, slit coating, knife coating, and dip coating. Cloth method, roll coating method, rod coating method, die coating method, inkjet method, printing method (relief, gravure, lithography, screen printing, etc.), etc. [0061] The heating temperature for imidization is usually in the range of 50 to 550°C for appropriate determination, and preferably exceeds 150°C to 510°C. By setting the heating temperature in this way, the fragility of the obtained film can be prevented, and at the same time, the imidization reaction can proceed sufficiently. The heating time varies depending on the heating temperature, so it cannot be specified uniformly, and it is usually 5 minutes to 5 hours. In addition, the imidization rate may be in the range of 50 to 100%. [0062] As a preferable example of the heating aspect of the present invention, it can be cited as heating at 50~150°C for 5 minutes~2 hours, and then directly increasing the heating temperature step by step, and the final temperature is more than 150°C~510°C. Heating at ℃ for 30 minutes to 4 hours. Especially after heating at 50~150℃ for 5 minutes~2 hours, heating at over 150℃~350℃ for 5 minutes~2 hours, and finally heating at over 350℃~450℃ for 30 minutes~4 hours . [0063] Examples of appliances used for heating include hot plates, ovens, and the like. The heating environment can be under air or inert gas, and can be under normal pressure or under reduced pressure. [0064] The thickness of the release layer is usually about 0.01 to 50 μm, and preferably about 0.05 to 20 μm from the viewpoint of productivity. Still, the desired thickness can be achieved by adjusting the thickness of the coating film before heating. [0065] The peeling layer described above has excellent adhesion to the substrate (especially a glass substrate) and moderate adhesion and moderate peelability to the resin substrate. Therefore, the peeling layer of the present invention can be applied to the flexible electronic device manufacturing process, without causing damage to the resin substrate of the device, the resin substrate and the circuit formed on the resin substrate can be removed from the substrate at the same time. Perform peeling. [0066] Hereinafter, an example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described. Using the composition for forming a peeling layer of the present invention, a peeling layer is formed on a glass substrate according to the above-mentioned method. The resin solution for forming the resin substrate is applied on the release layer and the coating film is heated to form a resin substrate fixed to the glass substrate via the release layer of the present invention. At this time, in order to cover the entire release layer, the substrate is formed with an area larger than the area of the release layer. As the resin substrate, a substrate made of polyimide resin, acrylic resin, or cycloolefin polymer resin, which is representative of a resin substrate for flexible electronic devices, is used as a resin solution for forming the resin substrate. Examples include polyimide solutions, polyamide acid solutions, acrylic polymer solutions, and cycloolefin polymer solutions. The method of forming the resin substrate may be based on a common method. In addition, as a resin substrate system with high transparency, a resin substrate formed of an acrylic resin or a cycloolefin polymer resin can be exemplified. In particular, a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm is preferable. [0067] Next, a desired circuit is formed on the resin substrate fixed to the base via the peeling layer of the present invention, and then, for example, the resin substrate is cut along the peeling layer, and the resin substrate is removed from the circuit together with the peeling layer. The peeling layer is peeled to separate the resin substrate from the base. At this time, it is also possible to cut a part of the substrate together with the release layer. [0068] Still, Japanese Patent Application Laid-Open No. 2013-147599 reports that the laser lift-off method (LLO method), which has been widely used in the manufacture of high-brightness LEDs or three-dimensional semiconductor packages, has been applied to the manufacture of flexible displays. 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 side of the glass substrate from the surface opposite to the surface on which the circuit or the like is formed. The irradiated light can penetrate the glass substrate, and only the polymer (polyimide resin) near the glass substrate absorbs the light and evaporates (sublimates). As a result, it is possible to selectively peel the resin substrate from the glass substrate without affecting the circuit or the like provided on the resin substrate that determines the performance of the display. [0069] Since the composition for forming a release layer of the present invention has a feature of being applicable to the above-mentioned LLO method and capable of sufficiently absorbing light of a specific wavelength (for example, 308 nm), it can be used as an LLO method. Therefore, when the desired circuit is formed by fixing on the resin substrate of the glass substrate through the release layer formed using the composition of the present invention, and then the LLO method is irradiated with light of 308 nm, only the release layer It absorbs this light and evaporates (sublimates). According to this, the above-mentioned peeling layer will become a protective layer (playing a role as a protective layer), and the resin substrate can be selectively peeled from the glass substrate. [Examples] [0070] Hereinafter, examples are given to further illustrate the present invention in detail, but the present invention is not limited to these examples. [1] Compound abbreviation p-PDA: p-phenylenediamine TPDA: 4,4"-diamino-p-terphenyl TFMB: 2,2'-bis(trifluoromethyl)benzidine BPDA: 3, 3',4,4'-Biphenyltetracarboxylic dianhydride PMDA: Pyromellitic dianhydride DMCBDA: 1,3-Dimethylcyclobutyric dianhydride CBDA: Cyclobutyric dianhydride MMA: Methyl methacrylate Ester MAA: methacrylate HEMA: 2-hydroxyethyl methacrylate AIBN: azobisisobutyronitrile CHMI: cyclohexyl maleimide EPOLEAD GT-401: butane tetracarboxylic acid, tetrakis (3,4- Epoxy cyclohexyl methyl), modified ε-caprolactone, CELOXIDE 2021P made by DAICEL (stock): 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate , DAICEL (stock) VESTAGON B 1530: Evonik Japan (stock) NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate [0071] [2] Method for measuring weight average molecular weight and molecular weight distribution KD805; Eluent: Dimethylformamide/LiBr·H 2 O (29.6mM)/H 3 PO 4 (29.6mM)/THF (0.1% by mass); Flow rate: 1.0mL/min; Column temperature: 40 ℃; Mw: standard polystyrene conversion value). [0072] [3] The synthesis of the polymer was performed according to the following method to synthesize various polymers used in the examples and comparative examples. The polymer does not isolate in the reaction solution of the compound, but as described later, the composition for forming a resin substrate or the composition for forming a release layer can be prepared by diluting the reaction solution. [0073] <Synthesis Example S1 Polyamide acid (S1) Synthesis> Dissolve 3.218g (30m mol) of p-PDA in 88.2g of NMP. Add 8.581g (29m mol) of BPDA to the resulting solution, and react at 23°C for 24 hours in a nitrogen environment The Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6. [0074] <Synthesis Example S2 Synthesis of Polyamide Acid (S2)> 20.261 g (0.1875 mol) of p-PDA and 12.206 g (0.0469 mol) of p-PDA ) Was dissolved in NMP617.4g, cooled to 15°C, PMDA50.112g (0.2298 mol) was added, and reacted at 50°C for 48 hours in a nitrogen environment. The Mw of the obtained polymer was 82,100 and the molecular weight distribution was 2.7 . [0075] <Synthesis Example S3 Synthesis of acrylic polymer (S3)> MMA 7.20 g (0.0719 mol), HEMA 7.20 g (0.0553 mol), CHMI 10.8 g (0.0603 mol), MAA4.32 g (0.0502 mol), AIBN2 .46 g (0.0150 mol) is dissolved in 46.9 g of PGMEA, and an acrylic polymer solution (solid content concentration 40% by mass) can be obtained by reacting at 60-100°C for 20 hours. The Mn of the obtained acrylic polymer was 3,800 and the Mw was 7,300. [0076] <Synthesis Example L1 Synthesis of Polyamide (L1)> 2.73 g (8.53 mmol) of TFMB was dissolved in 38.5 g of NMP. PMDA2.06g (9.47m mol) was added to the obtained solution, and it was allowed to react at 23°C for 24 hours in a nitrogen environment. The Mw of the obtained polymer was 17,100 and the molecular weight distribution was 1.7. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, precipitation was not particularly observed. [0077] <Synthesis Example L2: Synthesis of Polyamide (L2)> 2.73 g (8.53 mmol) of TFMB was dissolved in 40 g of PGME. 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 in a nitrogen environment. The Mw of the obtained polymer was 20,100 and the molecular weight distribution was 1.8. [0078] <Synthesis Example L3 Synthesis of Polyamide (L3)> 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 in a nitrogen environment. The Mw of the obtained polymer was 16,500 and the molecular weight distribution was 1.7. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, precipitation was not particularly observed. [0079] <Synthesis Example L4 Synthesis of Polyamide (L4)> 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 in a nitrogen environment. The Mw of the obtained polymer was 14,700, and the molecular weight distribution was 1.7. [0080] <Comparative Synthesis Example HL1 Synthesis of Polyamide Acid (HL1)> 3.90 g (3.60 mmol) of p-PDA was dissolved in 35.2 g of NMP. To the obtained solution, 9.27 g (4.00 m mol) of DMCBDA was added, and the reaction was carried out at 23° C. for 24 hours in a nitrogen environment. The Mw of the obtained polymer was 45,000 and the molecular weight distribution was 3.9. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, polyamide acid was deposited. [0081] <Comparative Synthesis Example HL2 Synthesis of Polyamide 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 in a nitrogen environment. The Mw of the obtained polymer was 69,200, and the molecular weight distribution was 2.2. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, precipitation was not particularly observed. [0082] [4] Preparation of the composition for forming a resin substrate The composition for forming a resin substrate was prepared according to the following method. [0083] <Preparation Example 1 Composition F1 for Forming Resin Substrate> The reaction solution obtained in Synthesis Example S1 was used as it was as composition F1 for forming a resin substrate. [0084] <Preparation Example 2 Composition F2 for Forming a Resin Substrate> The reaction liquid obtained in Synthesis Example S2 was used as it was as a composition F2 for forming a resin substrate. <Preparation Example 3 Composition F3 for Forming Resin Substrate> To 10 g of the reaction solution obtained in Synthesis Example S3, 0.60 g of EPOLEADGT-401 and 11.8 g of PGMEA were added and stirred at 23°C for 24 hours to prepare resin substrate formation Composition F3. [0086] <Preparation Example 4 Composition F4 for Forming Resin Substrate> To 10 g of the reaction solution obtained in Synthesis Example S3, 0.80 g of CELOXIDE 2021P and 11.8 g of PGMEA were added, and stirred at 23° C. for 24 hours to prepare a composition for forming a resin substrate物F4. [0087] <Preparation Example 5 Composition F5 for Forming Resin Substrate> To 10 g of the reaction solution obtained in Synthesis Example S3, 0.60 g of VESTAGON B 1530 and 11.8 g of PGMEA were added, and stirred at 23° C. for 24 hours to prepare resin substrate formation Composition F5. [0088] <Preparation Example 6 Composition F6 for forming a resin substrate> In an eggplant-shaped flask containing 100 g of carbon tetrachloride, Zeonor (registered trademark) 1020R (Nippon Zeon Co., Ltd. product, cycloolefin polymer resin) was added. 10g and GT-401 3g. This solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare composition F6 for forming a resin substrate. [0089] <Preparation Example 7 Composition F7 for Forming Resin Substrate> In an eggplant flask containing 100 g of carbon tetrachloride, Zeonor (registered trademark) 1060R (manufactured by Zeon Co., Ltd., cycloolefin polymer resin) was added. 10g. This solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare composition F7 for forming a resin substrate. [5] Preparation of a composition for forming a peeling layer [Example 1-1] To the reaction solution obtained in Synthesis Example L1, BCS and NMP were added so that the polymer concentration was 5% by mass and BCS was 20. It is diluted by mass% to obtain a composition for forming a peeling layer. [Example 1-2] The reaction solution obtained in Synthesis Example L2 was directly used as a composition for forming a release layer. [Example 1-3] In the reaction solution obtained in Synthesis Example L3, BCS and NMP were added to dilute so that the polymer concentration became 5% by mass and BCS became 20% by mass, thereby obtaining peeling Composition for layer formation. [Example 1-4] The reaction solution obtained in Synthesis Example L4 was directly used as a composition for forming a peeling layer. [Comparative Example 1-1] In the reaction solution obtained in Comparative Synthesis Example HL1, BCS and NMP were added to dilute the polymer concentration to 5 mass% and BCS to 20 mass% to obtain A composition for forming a release layer. [Comparative Example 1-2] In the reaction solution obtained in Comparative Synthesis Example HL2, BCS and NMP were added to dilute the polymer concentration to 5 mass% and BCS to 20 mass% to obtain A composition for forming a release layer. [6] Preparation of peeling layer and resin substrate [Example 2-1] Using a spin coater (condition: at a rotation speed of 3,000 rpm for about 30 seconds), the peeling layer obtained in Example 1-1 The composition L1 for formation was coated on a glass substrate of 100 mm×100 mm (the same applies hereinafter) as a glass substrate. Then, the obtained coating film was heated at 80°C for 10 minutes using a hot plate, and then heated at 300°C for 30 minutes in an oven, and the heating temperature was increased to 400°C (10°C/min, followed by heating at 400°C for 30 minutes). Minutes, a peeling layer with a thickness of about 0.1 μm is formed on the glass substrate, and a glass substrate with a peeling layer is obtained. Still, during the temperature rise, the substrate with the film is not taken out from the oven, but is heated in the oven. [0097] Using a bar coater (gap: 250 μm), the composition F1 for forming a resin substrate was coated on the release layer (resin film) on the glass substrate obtained above. Then, a hot plate was used at 80°C. The obtained coating film was heated for 30 minutes, and then heated at 140°C for 30 minutes in an oven, the heating temperature was increased to 210°C (2°C/min, the same below), and then heated at 210°C for 30 minutes, and the heating temperature Raise the temperature to 300°C, then heat at 300°C for 30 minutes, raise the heating temperature to 400°C, and heat at 400°C for 60 minutes to form a resin substrate with a thickness of about 20μm on the peeling layer to obtain a resin substrate with peeling Layer glass substrate. During the temperature rise, the substrate with the film is not taken out of the oven, but heated in the oven. [0098] [Example 2-2] Except for using the resin substrate forming composition F2 instead of implementation Except for the composition F1 for forming a resin substrate used in Example 2-1, a peeling layer and a resin substrate were produced in the same manner as in Example 2-1 to obtain a glass substrate with a peeling layer, and a resin substrate with a peeling layer. [0099] [Example 2-3] Except for using the release layer forming composition L2 obtained in Example 1-2 instead of the release layer forming composition L1 obtained in Example 1-1, The peeling layer and the resin substrate were produced in the same manner as in Example 2-1, and a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer were obtained. [0100] [Example 2-4] As As the composition for forming a release layer, the composition L2 for forming a release layer obtained in Example 1-2 was used, and as the composition for forming a resin substrate, the composition F2 for forming a resin substrate used in Example 2-2 was used. The peeling layer and the resin substrate were produced in the same manner as in Example 2-1, and a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer were obtained. [0101] [Example 2-5] As the release layer forming composition, the release layer forming composition L1 obtained in Example 1-1 was used, and the resin substrate forming composition F4 was used as the resin substrate forming composition. The peeling layer and the resin substrate were produced in the same way, and a glass substrate with a peeling layer and a glass plate with a resin substrate and a peeling layer were obtained. [0102] [Example 2-6] As a composition system for forming a peeling layer Use Example 1- 1. The obtained composition L1 for forming a peeling layer, using composition F5 for forming a resin substrate as a composition for forming a resin substrate, and producing a peeling layer and a resin substrate in the same manner as in Example 2-1. A glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained. [Example 2-7] The composition L2 for forming a peeling layer obtained in Example 1-2 was used as the composition for forming a peeling layer, and the composition for forming a resin substrate was used as the composition for forming a resin substrate F5, the peeling layer and the resin substrate were produced by the same method as in Example 2-1 to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer. [Example 2-8] Using the composition L1 for forming a peeling layer obtained in Example 1-1, a peeling layer was formed in the same manner as in Example 2-1 to obtain a peeling layer-attached Glass base board. Immediately after that, using a spin coater (condition: about 15 seconds at a rotation speed of 200 rpm), the resin substrate forming composition F6 was applied on the release layer (resin film) on the glass substrate. Use a hot plate to heat the resulting coating film at 80°C for 2 minutes, and then use a hot plate to heat at 230°C for 30 minutes to form a resin substrate with a thickness of about 3 μm on the release layer, and obtain a resin substrate with a release layer Glass base board. After that, using an ultraviolet visible spectrophotometer (Shimadzu Corporation UV-2600) to measure the light transmittance, the resin substrate showed a transmittance of 80% or more at 400 nm. [Example 2-9] Except that the composition L2 for forming a peeling layer obtained in Example 1-2 was used instead of the composition L1 for forming a peeling layer obtained in Example 1-1, the same as the example The peeling layer and the resin substrate are produced in the same way as 2-8, and the glass substrate with the peeling layer and the glass substrate with the resin substrate and the peeling layer are obtained. [Example 2-10] Using the composition L1 for forming a peeling layer obtained in Example 1-1, a peeling layer was formed in the same manner as in Example 2-1 to obtain a glass with a peeling layer Substrate. Immediately after that, using a spin coater (condition: about 15 seconds at a rotation speed of 200 rpm), the resin substrate forming composition F7 was applied on the release layer (resin film) on the glass substrate. Use a hot plate to heat the resulting coating film at 80°C for 2 minutes, and then use a hot plate to heat at 230°C for 30 minutes to form a resin substrate with a thickness of about 3 μm on the release layer, and obtain a resin substrate with a release layer Glass base board. After that, using an ultraviolet visible spectrophotometer (Shimadzu Corporation UV-2600) to measure the light transmittance, the resin substrate showed a transmittance of 80% or more at 400 nm. [Example 2-11] Except that the composition L2 for forming a peeling layer obtained in Example 1-2 was used instead of the composition L1 for forming a peeling layer obtained in Example 1-1, the same as the example 2-10 The same method is used to produce the peeling layer and the resin substrate to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer. [Comparative Examples 2-1 to 2-4] Except that the composition for forming a peeling layer obtained in Comparative Examples 1-1 to 1-2 was used instead of the composition for forming a peeling layer obtained in Example 1-1 Other than that, the peeling layer and the resin substrate were produced by the same method as the above-mentioned Example, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained. The combination of the release layer and the resin substrate is as shown in Table 1. [Example 2-12] Using a spin coater (condition: about 30 seconds at a rotation speed of 3,000 rpm), the release layer forming composition L3 obtained in Example 1-3 was applied to glass as On the base 100mm×100mm glass substrate (the same below). Then, the obtained coating film was heated at 80°C for 10 minutes using a hot plate, and then heated at 300°C for 30 minutes in an oven, and the heating temperature was increased to 400°C (10°C/min, followed by heating at 400°C for 30 minutes). Minutes, a peeling layer with a thickness of about 0.1 μm is formed on the glass substrate, and a glass substrate with a peeling layer is obtained. Still, during the temperature rise, the substrate with the film is not taken out from the oven, but is heated in the oven. [0110] Using a spin coater (condition: about 10 seconds at a rotation speed of 800 rpm), the resin substrate forming composition F3 was applied on the release layer (resin film) on the glass substrate obtained above. , Use a hot plate to heat the resulting coating film at 80°C for 30 minutes, and then use an oven to heat it at 230°C for 30 minutes to form an acrylic substrate with a thickness of about 3μm on the release layer. Do not take it out of the oven during the temperature rise The substrate with the film is heated in an oven. [0111] [Example 2-13] Except that the composition F4 for forming a resin substrate was used instead of the composition F3 for forming a resin substrate used in Example 2-12 The peeling layer and the resin substrate were produced in the same manner as in Example 2-12, and a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer were obtained. [0112] [Example 2-14] Except that the resin substrate forming composition F5 was used instead of the resin substrate forming composition F3 used in Example 2-12, the release layer and the resin substrate were produced in the same manner as in Example 2-12 to obtain A glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer. [0113] [Example 2-15] Except that the composition L4 for forming a peeling layer obtained in Example 1-4 was used instead of Example 1- 3 Except for the obtained composition L3 for forming a peeling layer, a peeling layer and a resin substrate were produced in the same manner as in Example 2-12 to obtain a glass substrate with a peeling layer and a glass with a resin substrate and a peeling layer Substrate. [0114] [Example 2-16] The composition L4 for forming a peeling layer obtained in Example 1-4 was used as the composition for forming a peeling layer, and Example 2 was used as the composition for forming a resin substrate. 14. Using the composition F5 for forming a resin substrate, a peeling layer and a resin substrate were produced in the same manner as in Example 2-12 to obtain a glass substrate with a peeling layer and a glass with a resin substrate and a peeling layer [0115] [Example 2-17] Using the composition L3 for forming a peeling layer obtained in Example 1-3, a peeling layer was formed in the same manner as in Example 2-12 to obtain a peeling layer attached After that, immediately use a spin coater (condition: about 15 seconds at a rotation speed of 200 rpm) to coat the resin substrate forming composition F6 on the release layer (resin film) on the glass substrate. superior. Use a hot plate to heat the resulting coating film at 80°C for 2 minutes, and then use a hot plate to heat at 230°C for 30 minutes to form a resin substrate with a thickness of about 3 μm on the release layer, and obtain a resin substrate with a release layer Glass base board. After that, using an ultraviolet visible spectrophotometer (Shimadzu Corporation UV-2600) to measure the light transmittance, the resin substrate showed a transmittance of 80% or more at 400 nm. [Example 2-18] Except that the release layer forming composition L4 obtained in Example 1-4 was used instead of the release layer forming composition L3 obtained in Example 1-3, the same as the example 2-17 The peeling layer and the resin substrate are produced in the same way, and the glass substrate with the peeling layer and the glass substrate with the resin substrate and the peeling layer are obtained. [Example 2-19] Using the composition L3 for forming a peeling layer obtained in Example 1-3, a peeling layer was formed in the same manner as in Example 2-12 to obtain a glass with a peeling layer Substrate. Immediately after that, using a spin coater (condition: about 15 seconds at a rotation speed of 200 rpm), the resin substrate forming composition F7 was applied on the release layer (resin film) on the glass substrate. Use a hot plate to heat the resulting coating film at 80°C for 2 minutes, and then use a hot plate to heat at 230°C for 30 minutes to form a resin substrate with a thickness of about 3 μm on the release layer, and obtain a resin substrate with a release layer Glass base board. After that, using an ultraviolet visible spectrophotometer (Shimadzu Corporation UV-2600) to measure the light transmittance, the resin substrate showed a transmittance of 80% or more at 400 nm. [Example 2-20] Except that the release layer forming composition L4 obtained in Example 1-4 was used instead of the release layer forming composition L3 obtained in Example 1-3, the same as the example 2-19 The peeling layer and the resin substrate are produced in the same way, and the glass substrate with the peeling layer and the glass substrate with the resin substrate and the peeling layer are obtained. [Comparative Example 2-5] Except that the release layer forming composition HL1 obtained in Comparative Example 1-1 was used instead of the release layer forming composition L3 obtained in Example 1-3, the same as the example 2-12 The same method is used to produce the peeling layer and the resin substrate to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer. The combination of the release layer and the resin substrate is shown in Table 2. [Comparative Example 2-6] As the release layer forming composition system, the release layer forming composition HL2 obtained in Comparative Example 1-2 was used, and as the resin substrate forming composition system, the same as in Example 2-13 was used. The resin substrate forming composition F4 used was used to produce a peeling layer and a resin substrate in the same manner as in Example 2-12 to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer. [7] Evaluation of the solvent resistance of the peeling layer. Use a straw to drop NMP and PGME into the obtained Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6. On the peeling layer of the glass substrate with the peeling layer. After 1 minute, after washing the peeling layer with pure water, the state of the peeling layer in the portion where the solvent was dropped was visually observed to evaluate the solvent resistance of the peeling layer. The criterion system is as follows. The results are shown in Table 1 and Table 2. <Criteria for Judgment> ○: No traces of droplets are particularly observed, and no dissolution is observed. △: Traces of droplets are found, but residual film is found. ×: It appears to be dissolved. The so-called release layer is not dissolved in the dropped solvent means that when the resin substrate is formed on the release layer, the organic solvent contained in the resin substrate forming composition is not dissolved, and the glass substrate will not damage the resin substrate. It means peelable. [8] Evaluation of peelability For the glass substrates with resin substrates and peeling layers obtained in Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6, the following methods were used To confirm the peelability of the peeling layer and the glass substrate. However, the following tests were performed on the same glass substrate. [0123] <Releasability evaluation of peeling layer and glass substrate> The peeling layer on the glass substrate with the peeling layer obtained in Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6 was cross-cut (1mm interval in vertical and horizontal, the same below), and cut 100 blocks. That is, by this cross cutting, 100 square meshes of 1 mm square are formed. Then, attach the adhesive tape to the cut part of the 100 blocks, and peel off the tape to evaluate the degree of peeling based on the following benchmarks (5B~0B, B, A, AA). Furthermore, among all the peeled substrates, the glass substrates with resin substrates and peeling layers produced in Examples 2-5 to 2-20 were used to perform a peeling force evaluation test. The test method is to use a blade to cut through the back of the resin substrate to make the resin substrate of the glass substrate with the resin substrate and the peeling layer into a rectangle with a width of 25 mm × 50 mm to form a long strip. Furthermore, after pasting Nichiban CT-24 on the manufactured strip, using Autograph AG-500N (manufactured by Shimadzu Corporation), it was peeled off at 90 degrees with respect to the surface of the substrate, that is, in the vertical direction. The peeling force is measured, and 100% peeling (full peeling), and the peeling force is less than 0.1N/25mm as AAA. The above results are shown in Table 1 and Table 2. <Judgment criteria> 5B: 0% peeling (no peeling) 4B: less than 5% peeling 3B: 5 to less than 15% peeling 2B: 15 to less than 35% peeling 1B: 35 to less than 65% Peeling 0B: 65% to less than 80% peeling B: 80% to less than 95% peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling) AAA: 100% peeling and peeling The force is less than 0.1N/25mm [0124] <Evaluation of peelability between peeling layer and resin substrate> For the resin substrates obtained in Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6• The peelability of the glass substrate of the peeling layer was evaluated according to the same procedure as the peelability evaluation described above. The results are shown in Table 1 and Table 2. [0125]
Figure 02_image033
[0126]
Figure 02_image035
[0127] As shown in Table 1 and Table 2, it was confirmed that the peeling layer system of Examples 2-1 to 2-20 had excellent adhesion to the glass substrate and easily peeled off from the resin film. In addition, it was also confirmed from the results of the solubility test that it was not dissolved in the organic solvent contained in the composition for forming a resin substrate. On the other hand, it can be confirmed that the peeling layer of Comparative Examples 2-1 to 2-6 has excellent adhesion to the glass substrate, but poor peelability to the resin substrate.

Claims (10)

一種剝離層形成用組成物，其特徵係包含下述式(1)所表示之聚醯胺酸，與有機溶劑，
Figure 106126261-A0305-02-0047-11
 (式中，X係表示下述式(2a)或(2b)所表示之芳香族基，Y係表示具有氟原子的2價的芳香族基，當X為式(2a)所表示之芳香族基時，Z係相互獨立表示下述式(3a)或(4a)所表示之芳香族基，當X為式(2b)所表示之芳香族基時，Z係相互獨立表示下述式(3b)或(4b)所表示之芳香族基，m係表示自然數)
Figure 106126261-A0305-02-0047-12
 A composition for forming a peeling layer, characterized by comprising polyamide acid represented by the following formula (1), and an organic solvent,
Figure 106126261-A0305-02-0047-11
 (In the formula, X represents an aromatic group represented by the following formula (2a) or (2b), Y represents a divalent aromatic group having a fluorine atom, when X is an aromatic group represented by formula (2a) In the case of a group, Z systems independently represent an aromatic group represented by the following formula (3a) or (4a), and when X is an aromatic group represented by a formula (2b), Z systems independently represent the following formula (3b) ) Or (4b) represents the aromatic group, m is a natural number)
Figure 106126261-A0305-02-0047-12
 如請求項1之剝離層形成用組成物，其中，上述Y為下述式(5)所表示之芳香族基，
Figure 106126261-A0305-02-0048-13
 The composition for forming a release layer according to claim 1, wherein the Y is an aromatic group represented by the following formula (5),
Figure 106126261-A0305-02-0048-13
 如請求項2之剝離層形成用組成物，其中，上述Y為下述式(6)所表示之芳香族基，
Figure 106126261-A0305-02-0048-14
 The composition for forming a release layer according to claim 2, wherein the Y is an aromatic group represented by the following formula (6),
Figure 106126261-A0305-02-0048-14
 如請求項1~3中任一項之剝離層形成用組成物，其中，上述X中，上述式(2a)所表示之芳香族基為下述式(7a)或(8a)所表示之芳香族基，上述Z係相互獨立為下述式(9a)或式(10a)所表示之芳香族基，
Figure 106126261-A0305-02-0048-15
 The composition for forming a release layer according to any one of claims 1 to 3, wherein, in the above X, the aromatic group represented by the above formula (2a) is an aromatic group represented by the following formula (7a) or (8a) Group group, the above-mentioned Z system is independently an aromatic group represented by the following formula (9a) or formula (10a),
Figure 106126261-A0305-02-0048-15
 如請求項1~3中任一項之剝離層形成用組成物，其中，上述X中，上述式(2b)所表示之芳香族基為下述式(7b)或(8b)所表示之芳香族基，上述Z係相互獨立為下述式(9b)或式(10b)所表示之芳香族基，
Figure 106126261-A0305-02-0048-16
Figure 106126261-A0305-02-0049-17
 The composition for forming a release layer according to any one of claims 1 to 3, wherein, in the above X, the aromatic group represented by the above formula (2b) is an aromatic group represented by the following formula (7b) or (8b) Group group, the above-mentioned Z system is independently an aromatic group represented by the following formula (9b) or formula (10b),
Figure 106126261-A0305-02-0048-16
Figure 106126261-A0305-02-0049-17
 如請求項1~3中任一項之剝離層形成用組成物，其中，上述有機溶劑為選自具有下述式(S1)~(S7)所表示之構造之有機溶劑之至少1種，
Figure 106126261-A0305-02-0049-18
 (式中，R1~R8係相互獨立表示氫原子、或碳數1~10的烷基，R9及R10係相互獨立表示氫原子、碳數1~10的烷基、或碳數1~10的醯基，b及n係表示自然數)。 The composition for forming a release layer according to any one of claims 1 to 3, wherein the organic solvent is at least one selected from organic solvents having a structure represented by the following formulas (S1) to (S7),
Figure 106126261-A0305-02-0049-18
 (In the formula, R 1 to R 8 independently represent a hydrogen atom, or an alkyl group with 1 to 10 carbons, and R 9 and R 10 independently represent a hydrogen atom, an alkyl group with 1 to 10 carbons, or a carbon number. The base of 1~10, b and n represent natural numbers). 如請求項6之剝離層形成用組成物，其中，上述有機溶劑為丙二醇單甲基醚或丙二醇單甲基醚乙酸酯。 The composition for forming a peeling layer according to claim 6, wherein the organic solvent is propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate. 一種剝離層，其係使用請求項1~7中任一項之剝離層形成用組成物而形成。 A peeling layer formed using the composition for forming a peeling layer according to any one of claims 1 to 7. 一種樹脂基板之製造方法，其係使用請求項8之剝離層。 A method for manufacturing a resin substrate, which uses the peeling layer of claim 8. 如請求項9之製造方法，其中，上述樹脂基板為聚醯亞胺樹脂基板或波長400nm的光穿透率為80%以上的樹脂基板。The manufacturing method of claim 9, wherein the resin substrate is a polyimide resin substrate or a resin substrate with a light transmittance of 80% or more at a wavelength of 400 nm.
TW106126261A 2016-08-03 2017-08-03 Composition for forming peeling layer and peeling layer TWI737781B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016-152507 2016-08-03
JP2016-152549 2016-08-03
JP2016152507 2016-08-03
JP2016152549 2016-08-03

Publications (2)

Publication Number Publication Date
TW201817775A TW201817775A (en) 2018-05-16
TWI737781B true TWI737781B (en) 2021-09-01

Family

ID=61073040

Family Applications (1)

Application Number Title Priority Date Filing Date
TW106126261A TWI737781B (en) 2016-08-03 2017-08-03 Composition for forming peeling layer and peeling layer

Country Status (5)

Country Link
JP (1) JP7063266B2 (en)
KR (2) KR20230020011A (en)
CN (1) CN109476951B (en)
TW (1) TWI737781B (en)
WO (1) WO2018025953A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021132383A1 (en) * 2019-12-25 2021-07-01 日産化学株式会社 Composition for forming release layer, and release layer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012040836A (en) * 2010-08-23 2012-03-01 Kaneka Corp Laminate, and utilization thereof
TW201610021A (en) * 2014-07-17 2016-03-16 Asahi Kasei E Materials Corp Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same
JP2016086158A (en) * 2014-10-22 2016-05-19 セントラル硝子株式会社 Laminate for wafer processing, temporary adhesive material for wafer processing and method of manufacturing thin wafer

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3809681B2 (en) 1996-08-27 2006-08-16 セイコーエプソン株式会社 Peeling method
JP4619462B2 (en) 1996-08-27 2011-01-26 セイコーエプソン株式会社 Thin film element transfer method
JP4619461B2 (en) 1996-08-27 2011-01-26 セイコーエプソン株式会社 Thin film device transfer method and device manufacturing method
GB0327093D0 (en) 2003-11-21 2003-12-24 Koninkl Philips Electronics Nv Active matrix displays and other electronic devices having plastic substrates
JP2008070480A (en) 2006-09-12 2008-03-27 Az Electronic Materials Kk Photoresist solvent and photoresist composition for slit coating using it
TWI354854B (en) 2008-09-15 2011-12-21 Ind Tech Res Inst Substrate structures applied in flexible electrica
KR101227280B1 (en) 2009-09-10 2013-01-28 도레이 카부시키가이샤 Photosensitive resin composition and method for producing photosensitive resin film
JP5725017B2 (en) * 2010-03-31 2015-05-27 Jsr株式会社 Substrate manufacturing method and composition used therefor
JP6204478B2 (en) * 2012-09-24 2017-09-27 アクロン ポリマー システムズ，インク． Polyamide solution, display element, optical element, or lighting element manufacturing method, and polyamide solution manufacturing method
KR20150107765A (en) * 2013-01-16 2015-09-23 닛산 가가쿠 고교 가부시키 가이샤 Method for producing resin thin film for display substrates and composition for forming resin thin film for display substrates
KR20140122677A (en) * 2013-04-09 2014-10-20 주식회사 엘지화학 Polyimide-based film and mehtod for preparing same
JP6094353B2 (en) * 2013-04-17 2017-03-15 Jsr株式会社 Protective film forming composition, protective film forming method, protective film and protective film removing method
JP6185283B2 (en) * 2013-05-10 2017-08-23 ユニチカ株式会社 Laminated body for flexible devices
JP2015078254A (en) * 2013-10-15 2015-04-23 東レ株式会社 Resin composition, polyimide resin film using the same, color filter, tft substrate and display device including the same, and their production method
JP2016120630A (en) * 2014-12-24 2016-07-07 株式会社カネカ Method for producing peeling layer and polyimide laminate
CN111234217A (en) * 2015-02-10 2020-06-05 日产化学工业株式会社 Composition for forming release layer
KR20230023831A (en) * 2015-03-31 2023-02-17 닛산 가가쿠 가부시키가이샤 Composition for forming release layer, and release layer
KR102358122B1 (en) * 2016-03-31 2022-02-04 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 Manufacturing method of flexible substrate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012040836A (en) * 2010-08-23 2012-03-01 Kaneka Corp Laminate, and utilization thereof
TW201610021A (en) * 2014-07-17 2016-03-16 Asahi Kasei E Materials Corp Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same
JP2016086158A (en) * 2014-10-22 2016-05-19 セントラル硝子株式会社 Laminate for wafer processing, temporary adhesive material for wafer processing and method of manufacturing thin wafer

Also Published As

Publication number Publication date
JPWO2018025953A1 (en) 2019-06-06
CN109476951B (en) 2022-07-29
KR20190037265A (en) 2019-04-05
CN109476951A (en) 2019-03-15
WO2018025953A1 (en) 2018-02-08
JP7063266B2 (en) 2022-05-09
TW201817775A (en) 2018-05-16
KR20230020011A (en) 2023-02-09

Similar Documents

Publication Publication Date Title
JP6743807B2 (en) Release layer forming composition and release layer
TWI817931B (en) laminated body
TWI746611B (en) Composition for forming peeling layer, and laminate containing the same
WO2021125308A1 (en) Release layer forming composition
TWI737781B (en) Composition for forming peeling layer and peeling layer
TWI757319B (en) Composition for forming peeling layer
KR102500563B1 (en) Composition for Forming a Substrate Protection Layer
KR102439472B1 (en) Method for producing a release layer
JP6927204B2 (en) A composition for forming a release layer and a release layer
JP6933209B2 (en) A composition for forming a release layer and a release layer