KR102310011B1 - Composition for forming release layer - Google Patents

Composition for forming release layer Download PDF

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KR102310011B1
KR102310011B1 KR1020167029656A KR20167029656A KR102310011B1 KR 102310011 B1 KR102310011 B1 KR 102310011B1 KR 1020167029656 A KR1020167029656 A KR 1020167029656A KR 20167029656 A KR20167029656 A KR 20167029656A KR 102310011 B1 KR102310011 B1 KR 102310011B1
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composition
release layer
bis
skeleton
component
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KR1020167029656A
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Korean (ko)
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KR20160141768A (en
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가즈야 에바라
가즈야 신도
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닛산 가가쿠 가부시키가이샤
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
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    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
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    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C09J2477/005—Presence of polyamide in the release coating
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    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/085—Presence of polyamine or polyimide polyimide in the release coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
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Abstract

본 발명은, 박리층이 형성되는 유리 기판과의 밀착성이 유지되고 유리 기판과의 계면에서의 박리가 발생하지 않는 한편, 박리층보다 상부에 형성되는 층 또는 층군을 박리층으로부터 간이하게 박리할 수 있는, 그 박리층을 형성하기 위한 조성물을 제공한다. 본 발명은, 유리 기판 바로 위에 형성하는 박리층을 형성하기 위한 조성물로서, 그 조성물이 (A) 방향족 폴리이미드 및/또는 방향족 폴리이미드 전구체；및 (B) 아미드계 용매；를 갖고, 상기 (A) 유래의 방향족 폴리이미드는, 하기 (1) ∼ (4) 를 만족하는 조성물을 제공한다：
(1) 가열시의 중량 변화에 있어서의 1 ％ 중량 감소의 온도가 500 ℃ 이상；
(2) 파장 1000 ㎚ 에서 굴절률이 1.7 이상；
(3) 파장 1000 ㎚ 에서 굴절률과 복굴절의 차가 0.15 이상；및
(4) 표면 에너지가 40 dyne/㎝ 이상.In the present invention, the adhesiveness with the glass substrate on which the release layer is formed is maintained and peeling does not occur at the interface with the glass substrate, while the layer or group of layers formed above the release layer can be easily peeled from the release layer. A composition for forming the release layer is provided. The present invention is a composition for forming a release layer formed directly on a glass substrate, wherein the composition comprises (A) an aromatic polyimide and/or an aromatic polyimide precursor; and (B) an amide solvent; ) derived aromatic polyimide provides a composition satisfying the following (1) to (4):
(1) a temperature of 1% weight loss in a weight change during heating is 500° C. or higher;
(2) a refractive index of 1.7 or more at a wavelength of 1000 nm;
(3) the difference between the refractive index and the birefringence at a wavelength of 1000 nm is 0.15 or more; and
(4) The surface energy is 40 dyne/cm or more.

Description

박리층 형성용 조성물{COMPOSITION FOR FORMING RELEASE LAYER}Composition for forming a release layer

본 발명은 유리 기판 바로 위에 형성하는 박리층을 형성하기 위한 조성물에 관한 것이다.The present invention relates to a composition for forming a release layer to be formed directly on a glass substrate.

최근, 전자 디바이스에는 구부린다는 기능 부여나 박형화 및 경량화와 같은 성능이 요구되고 있다. 이로부터, 종래의 무겁고 취약하고 구부릴 수 없는 유리 기판 대신에, 경량인 플렉시블 플라스틱 기판을 사용하는 것이 요구된다. 또, 신세대 디스플레이에서는, 경량인 플렉시블 플라스틱 기판을 사용하는, 액티브 풀 컬러 (active full-color) TFT 디스플레이 패널의 개발이 요구되고 있다. In recent years, performance, such as provision of a bending function, and thickness reduction and weight reduction, is calculated|required by an electronic device. From this, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, brittle and inflexible glass substrate. Moreover, in a new-generation display, development of the active full-color TFT display panel using a lightweight flexible plastic substrate is calculated|required.

그래서, 수지 필름을 기판으로 한 전자 디바이스의 제조 방법이 각종 검토되기 시작하였으며, 신세대 디스플레이에서는, 기존의 TFT 설비를 전용 (轉用) 가능한 프로세스로 제조 검토가 진행되고 있다.Then, various examinations of the manufacturing method of the electronic device which used the resin film as a board|substrate were begun, and in a new-generation display, manufacturing examination is advancing in the process which can divert existing TFT equipment.

특허문헌 1, 2 및 3 은, 유리 기판 상에 아모르퍼스 실리콘 박막층을 형성하고, 그 박막층 상에 플라스틱 기판을 형성한 후에, 유리면측으로부터 레이저를 조사하여, 아모르퍼스 실리콘의 결정화에 수반하여 발생하는 수소 가스에 의해 플라스틱 기판을 유리 기판으로부터 박리하는 방법을 개시한다.Patent Documents 1, 2, and 3 disclose that an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side, resulting in crystallization of amorphous silicon. A method of peeling a plastic substrate from a glass substrate by hydrogen gas is disclosed.

또, 특허문헌 4 는, 특허문헌 1 ∼ 3 개시의 기술을 이용하여 피박리층 (특허문헌 4 에 있어서 「피전사층」 이라고 기재된다) 을 플라스틱 필름에 첩부 (貼付) 하여 액정 표시 장치를 완성시키는 방법을 개시한다.Moreover, patent document 4 affixes a to-be-released layer (it describes as a "transfer target layer" in patent document 4) to a plastic film using the technique of patent documents 1 - 3 indication, and completes a liquid crystal display device. disclose how to do it.

그러나, 특허문헌 1 ∼ 4 개시의 방법, 특히 특허문헌 4 개시의 방법은, 투광성이 높은 기판을 사용하는 것이 필수이며, 기판을 통과시키고, 또한 비정질 실리콘에 포함되는 수소를 방출시키는 데 충분한 에너지를 주기 때문에, 비교적 큰 레이저 광의 조사가 필요해지고, 피박리층에 손상을 주어 버린다는 문제가 있다. 또, 레이저 처리에 장시간을 필요로 하고, 큰 면적을 갖는 피박리층을 박리하는 것은 곤란하기 때문에, 디바이스 제조의 생산성을 올리는 것은 어렵다는 문제도 있다.However, in the method disclosed in Patent Documents 1 to 4, particularly, the method disclosed in Patent Document 4, it is essential to use a substrate with high light transmittance, and sufficient energy to pass through the substrate and release hydrogen contained in amorphous silicon Therefore, there is a problem that relatively large laser light irradiation is required and damage to the layer to be peeled is caused. Moreover, since a long time is required for laser processing, and since it is difficult to peel the to-be-released layer which has a large area, there also exists a problem that it is difficult to raise the productivity of device manufacture.

일본 공개특허공보 평10-125929호.Japanese Patent Laid-Open No. 10-125929. 일본 공개특허공보 평10-125931호.Japanese Patent Application Laid-Open No. 10-125931. WO2005/050754호 팸플릿.WO2005/050754 pamphlet. 일본 공개특허공보 평10-125930호.Japanese Patent Application Laid-Open No. 10-125930.

그래서, 본 발명의 목적은 상기 과제를 해결하는 것에 있다.Then, the objective of this invention is to solve the said subject.

구체적으로는, 본 발명의 목적은, 플렉시블 전자 디바이스에 적용되는 기판에 손상을 주는 일 없이 박리시키기 위한 박리층을 형성하기 위한 조성물을 제공하는 것에 있다.Specifically, an object of the present invention is to provide a composition for forming a release layer for peeling without damaging a substrate applied to a flexible electronic device.

또, 본 발명의 목적은, 상기 목적에 더하여, 또는 상기 목적 이외에, 박리층이 형성되는 유리 기판과의 밀착성이 유지되고 유리 기판과의 계면에서의 박리가 발생하지 않는 한편, 박리층보다 상부에 형성되는 층 또는 층군을 박리층으로부터 간이하게 박리할 수 있는, 그 박리층을 형성하기 위한 조성물을 제공하는 것에 있다.Further, an object of the present invention is, in addition to or in addition to the above object, adhesion to the glass substrate on which the release layer is formed is maintained and peeling does not occur at the interface with the glass substrate, while the upper portion of the release layer is not It is to provide the composition for forming the peeling layer which can peel easily from the peeling layer the layer or layer group to be formed.

본 발명자는 이하의 발명을 알아내었다.MEANS TO SOLVE THE PROBLEM This inventor discovered the following invention.

＜1＞ 유리 기판 바로 위에 형성하는 박리층을 형성하기 위한 조성물로서, <1> A composition for forming a release layer formed directly on a glass substrate,

그 조성물이that composition

(A) 방향족 폴리이미드 및/또는 방향족 폴리이미드 전구체；및(A) an aromatic polyimide and/or an aromatic polyimide precursor; and

(B) 아미드계 용매；(B) an amide solvent;

를 갖고,have,

(A) 유래의 방향족 폴리이미드는 하기 (1) ∼ (4) 를 만족하는, 상기 조성물.The said composition in which the aromatic polyimide derived from (A) satisfy|fills following (1)-(4).

(1) 가열시의 중량 변화에 있어서의 1 ％ 중량 감소의 온도가 500 ℃ 이상；(1) a temperature of 1% weight loss in a weight change during heating is 500° C. or higher;

(2) 파장 1000 ㎚ 에서 굴절률이 1.7 이상；(2) a refractive index of 1.7 or more at a wavelength of 1000 nm;

(3) 파장 1000 ㎚ 에서 굴절률과 복굴절의 차가 0.15 이상；및(3) the difference between the refractive index and the birefringence at a wavelength of 1000 nm is 0.15 or more; and

(4) 표면 에너지가 40 dyne/㎝ 이상.(4) The surface energy is 40 dyne/cm or more.

＜2＞ 상기 ＜1＞ 에 있어서, (A) 성분이, p-페닐렌디아민 및 터페닐디아민으로 이루어지는 군에서 선택되는 적어도 1 종의 디아민 성분을 사용하여 제조되는 것이 좋다.<2> In <1>, it is preferable that the component (A) is produced using at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine.

＜3＞ 상기 ＜2＞ 에 있어서, p-페닐렌디아민 및/또는 터페닐디아민의 양이, 전체 디아민 성분 100 몰％ 중, 70 몰％ 이상인 것이 좋다.In <3> said <2>, it is good that the quantity of p-phenylenediamine and/or terphenyldiamine is 70 mol% or more in 100 mol% of all the diamine components.

＜4＞ 상기 ＜1＞ ∼ ＜3＞ 중 어느 하나에 있어서, (A) 성분이, 비페닐 골격, 이미다졸 골격 및 옥사졸 골격으로 이루어지는 군에서 선택되는 적어도 1 종의 제 1 골격을 갖는 방향족 디아민을 사용하여 제조되는 것이 좋다.<4> The aromatic component according to any one of <1> to <3>, wherein the component (A) has at least one first skeleton selected from the group consisting of a biphenyl skeleton, an imidazole skeleton and an oxazole skeleton. It is preferably prepared using a diamine.

＜5＞ 상기 ＜1＞ ∼ ＜4＞ 중 어느 하나에 있어서, (A) 성분이, 벤젠 골격, 나프탈렌 골격 및 비페닐 골격으로 이루어지는 군에서 선택되는 적어도 1 종의 제 2 골격을 갖는 산 2무수물을 사용하여 제조되는 것이 좋다.<5> acid dianhydride according to any one of <1> to <4>, wherein the component (A) has at least one second skeleton selected from the group consisting of a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton It is recommended to be manufactured using

＜6＞ 상기 ＜1＞ ∼ ＜3＞ 중 어느 하나에 있어서, (B) 성분이, 하기 식 (I) 로 나타내는 용매, 및/또는 (II) (식 중, R1 및 R2 는 각각 독립적으로, 탄소 원자수 1 ∼ 4 의 알킬기를 나타내고, h 는 자연수를 나타낸다) 로 나타내는 용매인 것이 좋다.<6> In any one of said <1>-<3>, (B) component is a solvent represented by following formula (I), and/or (II) (in formula, R<1> and R<2> are each independent , where an alkyl group having 1 to 4 carbon atoms is represented, and h is a natural number).

[화학식 1][Formula 1]

Figure 112016103265558-pct00001
Figure 112016103265558-pct00001

＜7＞ 상기 ＜1＞ ∼ ＜6＞ 중 어느 하나에 기재되는 조성물을 사용하여 형성되는, 유리 기판 바로 위에 형성되는 박리층.<7> A release layer formed directly on a glass substrate, formed using the composition according to any one of <1> to <6>.

＜8＞ 피박리체의 제조 방법으로서,<8> A method for producing an object to be removed, comprising:

a) 상기 ＜1＞ ∼ ＜6＞ 중 어느 하나에 기재되는 조성물을 유리 기판 상에 도포한 후, 박리층을 형성하는 공정；a) After apply|coating the composition in any one of said <1>-<6> on a glass substrate, the process of forming a peeling layer;

b) 그 박리층 상에, 피박리체를 형성하는 공정；및b) a step of forming an object to be removed on the release layer; and

c) 박리층과 피박리체의 계면에 있어서, 피박리체를 박리하는 공정；c) at the interface between the release layer and the object to be peeled, a step of peeling the object to be peeled;

을 가짐으로써, 피박리체를 얻는 상기 방법.The said method of obtaining a to-be-removed body by having.

본 발명에 의해 상기 과제를 해결할 수 있다.The present invention can solve the above problems.

구체적으로는, 본 발명에 의해, 플렉시블 전자 디바이스에 적용되는 기판에 손상을 주는 일 없이 박리시키기 위한 박리층을 형성하기 위한 조성물을 제공할 수 있다.Specifically, according to the present invention, it is possible to provide a composition for forming a release layer for peeling without damaging a substrate applied to a flexible electronic device.

또, 본 발명에 의해, 상기 효과에 더하여, 또는 상기 효과 이외에, 박리층이 형성되는 유리 기판과의 밀착성이 유지되고 유리 기판과의 계면에서의 박리가 발생하지 않는 한편, 박리층보다 상부에 형성되는 층 또는 층군을 박리층으로부터 간이하게 박리할 수 있는, 그 박리층을 형성하기 위한 조성물을 제공할 수 있다.Further, according to the present invention, in addition to or in addition to the above effects, adhesiveness with the glass substrate on which the release layer is formed is maintained and peeling does not occur at the interface with the glass substrate, while forming above the release layer It is possible to provide a composition for forming the release layer that can easily peel the layer or group of layers to be used from the release layer.

본원은, 유리 기판 바로 위에 형성하는 박리층을 형성하기 위한 조성물을 제공한다.The present application provides a composition for forming a release layer to be formed directly on a glass substrate.

이하, 그 조성물에 대하여 상세히 서술한다.Hereinafter, the composition will be described in detail.

＜조성물＞<Composition>

본 발명의 조성물은, (A) 방향족 폴리이미드 및/또는 방향족 폴리이미드 전구체；및 (B) 아미드계 용매；를 갖는다.The composition of the present invention has (A) an aromatic polyimide and/or an aromatic polyimide precursor; and (B) an amide-based solvent.

＜＜(A) 성분＞＞ <<(A) component>>

(A) 성분은, 방향족 폴리이미드 및/또는 방향족 폴리이미드 전구체이다.(A) A component is an aromatic polyimide and/or an aromatic polyimide precursor.

여기서, 「방향족 폴리이미드」 란, 폴리이미드를 구성하는 디아민 성분 및 산 2무수물 성분 중 쌍방이 방향족기를 갖고, 그러므로 그것에 의해 얻어진 폴리이미드가, 오로지 방향족기를 주사슬에 갖는 것을 의미한다.Here, "aromatic polyimide" means that both of the diamine component and the acid dianhydride component constituting the polyimide have an aromatic group, and therefore the polyimide obtained thereby has only an aromatic group in the main chain.

또, 「방향족 폴리이미드 전구체」 란, 상기 방향족 폴리이미드의 전구체를 말하며, 전형적으로는, 폴리아믹산, 폴리아믹산에스테르, 폴리이소이미드를 들 수 있으며, 바람직하게는 폴리아믹산인 것이 좋다.Moreover, "aromatic polyimide precursor" means the precursor of the said aromatic polyimide, and a polyamic acid, polyamic acid ester, and polyisoimide are mentioned typically, It is preferable that it is a polyamic acid.

구체적으로는, 방향족 폴리이미드로서, 그 폴리이미드를 구성하는 디아민 성분 및 산 2무수물 성분으로 나누어, 다음의 것을 들 수 있지만, 이들에 한정되지 않는다.It is divided into the diamine component and acid dianhydride component which comprise this polyimide as an aromatic polyimide specifically, and although the following is mentioned, it is not limited to these specifically,.

＜디아민 성분＞ <Diamine component>

방향족기를 갖는 디아민 성분으로서, 1,4-디아미노벤젠(p-페닐렌디아민), 1,3-디아미노벤젠(m-페닐렌디아민), 1,2-디아미노벤젠(o-페닐렌디아민), 2,4-디아미노톨루엔, 2,5-디아미노톨루엔, 2,6-디아미노톨루엔, 4,6-디메틸-m-페닐렌디아민, 2,5-디메틸-p-페닐렌디아민2,6-디메틸-p-페닐렌디아민2,4-비스(아미노-t-부틸)톨루엔2,4,6-트리메틸-1,3-페닐렌디아민, 2,3,5,6-테트라메틸-p-페닐렌디아민, m-자일릴렌디아민, p-자일릴렌디아민, 5-트리플루오로메틸벤젠-1,3-디아민, 5-트리플루오로메틸벤젠-1,2-디아민, 3,5-비스(트리플루오로메틸)벤젠-1,2-디아민 등의 벤젠 핵 1 개의 디아민, 4,4'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 4,4'-디아미노디페닐메탄, 3,3'-디메틸-4,4'-디아미노비페닐, 2,2'-디메틸-4,4'-디아미노비페닐, 2,2'-비스(트리플루오로메틸)-4,4'-디아미노비페닐, 3,3'-디메틸-4,4'-디아미노디페닐메탄, 3,3'-디카르복시-4,4'-디아미노디페닐메탄, 3,3',5,5'-테트라메틸-4,4'-디아미노디페닐메탄, 비스(4-아미노페닐)술파이드, 4,4'-디아미노벤즈아닐리드, 3,3'-디클로로벤지딘, 3,3'-디메틸벤지딘, 2,2'-디메틸벤지딘, 3,3'-디메톡시벤지딘, 2,2'-디메톡시벤지딘, 3,3'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 4,4'-디아미노디페닐에테르, 3,3'-디아미노디페닐술파이드, 3,4'-디아미노디페닐술파이드, 4,4'-디아미노디페닐술파이드, 3,3'-디아미노디페닐술폰, 3,4'-디아미노디페닐술폰, 4,4'-디아미노디페닐술폰, 3,3'-디아미노벤조페논, 3,3'-디아미노-4,4'-디클로로벤조페논, 3,3'-디아미노-4,4'-디메톡시벤조페논, 3,3'-디아미노디페닐메탄, 3,4'-디아미노디페닐메탄, 4,4'-디아미노디페닐메탄, 2,2-비스(3-아미노페닐)프로판, 2,2-비스(4-아미노페닐)프로판, 2,2-비스(3-아미노페닐)-1,1,1,3,3,3-헥사플루오로프로판, 2,2-비스(4-아미노페닐)-1,1,1,3,3,3-헥사플루오로프로판, 3,3'-디아미노디페닐술폭시드, 3,4'-디아미노디페닐술폭시드, 4,4'-디아미노디페닐술폭시드, 2,2'-비스(트리플루오로메틸)비페닐-4,4'-디아민, 3,3'-비스(트리플루오로메틸)비페닐-4,4'-디아민, 3,3',5,5'-테트라플루오로비페닐-4,4'-디아민, 4,4'-디아미노옥타플루오로비페닐 등의 벤젠 핵 2 개의 디아민, 1,3-비스(3-아미노페닐)벤젠, 1,3-비스(4-아미노페닐)벤젠, 1,4-비스(3-아미노페닐)벤젠, 1,4-비스(4-아미노페닐)벤젠, 1,3-비스(4-아미노페녹시)벤젠, 1,4-비스(3-아미노페녹시)벤젠, 1,4-비스(4-아미노페녹시)벤젠, 1,3-비스(3-아미노페녹시)-4-트리플루오로메틸벤젠, 3,3'-디아미노-4-(4-페닐)페녹시벤조페논, 3,3'-디아미노-4,4'-디(4-페닐페녹시)벤조페논, 1,3-비스(3-아미노페닐술파이드)벤젠, 1,3-비스(4-아미노페닐술파이드)벤젠, 1,4-비스(4-아미노페닐술파이드)벤젠, 1,3-비스(3-아미노페닐술폰)벤젠, 1,3-비스(4-아미노페닐술폰)벤젠, 1,4-비스(4-아미노페닐술폰)벤젠, 1,3-비스[2-(4-아미노페닐)이소프로필]벤젠, 1,4-비스[2-(3-아미노페닐)이소프로필]벤젠, 1,4-비스[2-(4-아미노페닐)이소프로필]벤젠 등의 벤젠 핵 3 개의 디아민, 3,3'-비스(3-아미노페녹시)비페닐, 3,3'-비스(4-아미노페녹시)비페닐, 4,4'-비스(3-아미노페녹시)비페닐, 4,'-비스(4-아미노페녹시)비페닐, 비스[3-(3-아미노페녹시)페닐]에테르, 비스[3-(4-아미노페녹시)페닐]에테르, 비스[4-(3-아미노페녹시)페닐]에테르, 비스[4-(4-아미노페녹시)페닐]에테르, 비스[3-(3-아미노페녹시)페닐]케톤, 비스[3-(4-아미노페녹시)페닐]케톤, 비스[4-(3-아미노페녹시)페닐]케톤, 비스[4-(4-아미노페녹시)페닐]케톤 (비스(4-아미노페녹시)벤조페논), 비스[3-(3-아미노페녹시)페닐]술파이드, 비스[3-(4-아미노페녹시)페닐]술파이드, 비스[4-(3-아미노페녹시)페닐]술파이드, 비스[4-(4-아미노페녹시)페닐]술파이드, 비스[3-(3-아미노페녹시)페닐]술폰, 비스[3-(4-아미노페녹시)페닐]술폰, 비스[4-(3-아미노페녹시)페닐]술폰, 비스[4-(4-아미노페녹시)페닐]술폰, 비스[3-(3-아미노페녹시)페닐]메탄, 비스[3-(4-아미노페녹시)페닐]메탄, 비스[4-(3-아미노페녹시)페닐]메탄, 비스[4-(4-아미노페녹시)페닐]메탄, 2,2-비스[3-(3-아미노페녹시)페닐]프로판, 2,2-비스[3-(4-아미노페녹시)페닐]프로판, 2,2-비스[4-(3-아미노페녹시)페닐]프로판, 2,2-비스[4-(4-아미노페녹시)페닐]프로판, 2,2-비스[3-(3-아미노페녹시)페닐]-1,1,1,3,3,3-헥사플루오로프로판, 2,2-비스[3-(4-아미노페녹시)페닐]-1,1,1,3,3,3-헥사플루오로프로판, 2,2-비스[4-(3-아미노페녹시)페닐]-1,1,1,3,3,3-헥사플루오로프로판, 2,2-비스[4-(4-아미노페녹시)페닐]-1,1,1,3,3,3-헥사플루오로프로판, 9,9-비스(4-아미노페닐)플루오렌, 9,9-비스(4-아미노페닐)플루오렌, 9,9'-비스(4-아미노페녹시페닐)플루오렌 등의 벤젠 핵 4 개 이상의 디아민, 5-아미노-2-(p-아미노페닐)벤조옥사졸, 5-아미노-2-(m-아미노페닐)벤조옥사졸, 6-아미노-2-(p-아미노페닐)벤조옥사졸, 6-아미노-2-(m-아미노페닐)벤조옥사졸, 2,2'-p-페닐렌비스(5-아미노벤조옥사졸), 2,2'-p-페닐렌비스(6-아미노벤조옥사졸), 1-(5-아미노벤조옥사졸로)-4-(6-아미노벤조옥사졸로)벤젠, 2,6-(4,4'-디아미노디페닐)벤조[1,2-d：5,4-d']비스옥사졸, 2,6-(4,4'-디아미노디페닐)벤조[1,2-d：4,5-d']비스옥사졸, 2,6-(3,4'-디아미노디페닐)벤조[1,2-d：5,4-d']비스옥사졸, 2,6-(3,4'-디아미노디페닐)벤조[1,2-d：4,5-d']비스옥사졸, 2,6-(3,3'-디아미노디페닐)벤조[1,2-d：5,4-d']비스옥사졸, 2,6-(3,3'-디아미노디페닐)벤조[1,2-d：4,5-d']비스옥사졸, 2,4-디아미노피리딘, 2,6-디아미노피리딘, 2,5-디아미노피리딘 등의 벤조옥사졸 구조를 갖는 디아민 등을 들 수 있지만, 이들에 한정되지 않는다. 이들은 단독으로도, 2 종 이상을 혼합하여 사용할 수도 있다.As the diamine component having an aromatic group, 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine) ), 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine 2 ,6-Dimethyl-p-phenylenediamine 2,4-bis(amino-t-butyl)toluene 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl- p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5- Diamine with one benzene nucleus, such as bis(trifluoromethyl)benzene-1,2-diamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-dia minodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl ) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3 ,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl)sulfide, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine , 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodi Phenyl sulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3 '-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diamino Diphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-amino phenyl)-1,1,1,3,3,3- Hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylsulfoxide, 3,4' -diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 2,2'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 3,3'-bis(tri Benzene such as fluoromethyl)biphenyl-4,4'-diamine, 3,3',5,5'-tetrafluorobiphenyl-4,4'-diamine, and 4,4'-diaminooctafluorobiphenyl 2 nuclei diamine, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis( 4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1 , 3-bis (3-aminophenoxy) -4-trifluoromethylbenzene, 3,3'-diamino-4- (4-phenyl) phenoxybenzophenone, 3,3'-diamino-4, 4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis( 4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)benzene , 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4- Diamine with three benzene nuclei, such as aminophenyl) isopropyl] benzene, 3,3'-bis (3-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 4,4 '-Bis(3-aminophenoxy)biphenyl, 4,'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4- Aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl ]ketone, bis[3-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone (bis( 4-aminophenoxy)benzophenone), bis[3-(3-aminophenoxy)phenyl]sulfide , bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis [3-(3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4) -Aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy) Phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-amino) Phenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis [3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1, 1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane; 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9 Diamine with 4 or more benzene nuclei, such as 9-bis(4-aminophenyl)fluorene, 9,9'-bis(4-aminophenoxyphenyl)fluorene, 5-amino-2-(p-aminophenyl) Benzoxazole, 5-amino-2-(m-aminophenyl)benzoxazole, 6-amino-2-(p-aminophenyl)benzoxazole, 6-amino-2-(m-aminophenyl)benzoxazole Sol, 2,2'-p-phenylenebis(5-aminobenzoxazole), 2,2'-p-phenylenebis(6-aminobenzoxazole), 1-(5-aminobenzoxazolo) -4-(6-aminobenzoxazolo)benzene, 2,6-(4,4'-diaminodiphenyl)benzo[1,2-d:5,4-d']bisoxazole, 2,6 -(4,4'-diaminodiphenyl)benzo[1,2-d:4,5-d']bisoxazole, 2,6-(3,4'-diaminodiphenyl)benzo[1, 2-d: 5,4-d'] bisoxazole, 2,6- (3,4'-diaminodiphenyl) benzo [1,2-d: 4,5-d'] bisoxazole, 2 ,6- (3,3'-diaminodiphenyl) benzo [1,2 -d: 5,4-d'] bisoxazole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2-d: 4,5-d'] bisoxazole, 2, Diamines having a benzoxazole structure, such as 4-diaminopyridine, 2,6-diaminopyridine, and 2,5-diaminopyridine, may be mentioned, but are not limited thereto. These may be used individually or in mixture of 2 or more types.

디아민 성분은, 어느 면에 있어서, p-페닐렌디아민 및 터페닐디아민으로 이루어지는 군에서 선택되는 적어도 1 종의 디아민 성분을 사용하는 것이 좋다.As the diamine component, in any aspect, it is preferable to use at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine.

이 경우, p-페닐렌디아민 및/또는 터페닐디아민의 양이, 전체 디아민 성분 100 몰％ 중, 70 몰％ 이상, 바람직하게는 80 몰％ 이상, 보다 바람직하게는 90 몰％ 이상인 것이 좋다.In this case, it is good that the amount of p-phenylenediamine and/or terphenyldiamine is 70 mol% or more, Preferably it is 80 mol% or more, More preferably, it is 90 mol% or more in 100 mol% of all the diamine components.

디아민 성분은, 다른 면에 있어서, 비페닐 골격, 이미다졸 골격 및 옥사졸 골격으로 이루어지는 군에서 선택되는 적어도 1 종의 제 1 골격을 갖는 방향족 디아민인 것이 좋다.In another aspect, the diamine component is preferably an aromatic diamine having at least one first skeleton selected from the group consisting of a biphenyl skeleton, an imidazole skeleton and an oxazole skeleton.

＜산 2무수물 성분＞ <Acid dianhydride component>

방향족기를 갖는 산 2무수물 성분으로서, 벤젠 골격을 갖는 산 2무수물, 나프탈렌 골격을 갖는 산 2무수물, 비페닐 골격을 갖는 산 2무수물 등을 들 수 있지만, 이들에 한정되지 않는다.Examples of the acid dianhydride component having an aromatic group include, but are not limited to, acid dianhydride having a benzene skeleton, acid dianhydride having a naphthalene skeleton, and acid dianhydride having a biphenyl skeleton.

구체적으로는, 피로멜리트산 2무수물, 3,3',4,4'-비페닐테트라카르복실산 2무수물, 2,2',3,3'-비페닐테트라카르복실산 2무수물, 2,3,3',4'-비페닐테트라카르복실산 2무수물 옥시디프탈산 2무수물, 디페닐술폰-3,4,3',4'-테트라카르복실산 2무수물, 비스(3,4-디카르복시페닐)술파이드 2무수물, 2,2-비스(3,4-디카르복시페닐)-1,1,1,3,3,3-헥사플루오로프로판 2무수물, 2,3,3',4'-벤조페논테트라카르복실산 2무수물, 3,3',4,4'-벤조페논테트라카르복실산 2무수물, 비스(3,4-디카르복시페닐)메탄 2무수물, 2,2-비스(3,4-디카르복시페닐)프로판 2무수물, p-페닐렌비스(트리멜리트산모노에스테르산 무수물), p-메틸페닐렌비스(트리멜리트산모노에스테르산 무수물), p-(2,3-디메틸페닐렌)비스(트리멜리트산모노에스테르산 무수물), 4,4'-비페닐렌비스(트리멜리트산모노에스테르산 무수물), 1,4-나프탈렌비스(트리멜리트산모노에스테르산 무수물), 2,6-나프탈렌비스(트리멜리트산모노에스테르산 무수물) 2,2-비스(4-하이드록시페닐)프로판디벤조에이트-3,3',4,4'-테트라카르복실산 2무수물, m-터페닐-3,4,3',4'-테트라카르복실산 2무수물, p-터페닐-3,4,3',4'-테트라카르복실산 2무수물, 1,3-비스(3,4-디카르복시페녹시)벤젠 2무수물, 1,4-비스(3,4-디카르복시페녹시)벤젠 2무수물, 1,4-비스(3,4-디카르복시페녹시)비페닐 2무수물, 2,2-비스[(3,4-디카르복시페녹시)페닐]프로판 2무수물, 2,3,6,7-나프탈렌테트라카르복실산 2무수물, 1,4,5,8-나프탈렌테트라카르복실산 2무수물, 4,4'-(2,2-헥사플루오로이소프로필리덴)디프탈산 2무수물, N,N'-(2,2'-비스{트리플루오로메틸}-[1,1'-비페닐]-4,4'-디일)비스(1,3-디옥소-1,3-디하이드록시벤조푸란-5-카르복시아미드) 등을 들 수 있지만, 이들에 한정되지 않는다. 이들은 단독으로도, 2 종 이상을 혼합하여 사용할 수도 있다.Specifically, pyromellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2, 3,3',4'-biphenyltetracarboxylic dianhydride Oxydiphthalic dianhydride, diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride, bis(3,4-dihydride) Carboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4 '-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis( 3,4-dicarboxyphenyl)propane dianhydride, p-phenylenebis(trimellitic acid monoesteric anhydride), p-methylphenylenebis(trimellitic acid monoesteric anhydride), p-(2,3-dimethyl Phenylene)bis(trimellitic acid monoesteric anhydride), 4,4'-biphenylenebis(trimellitic acid monoesteric anhydride), 1,4-naphthalenebis(trimellitic acid monoesteric anhydride), 2 ,6-naphthalenebis(trimellitic acid monoesteric anhydride) 2,2-bis(4-hydroxyphenyl)propanedibenzoate-3,3',4,4'-tetracarboxylic dianhydride, m- Terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3, 4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxyl Acid dianhydride, 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride, N,N'-(2,2'-bis{trifluoromethyl}-[1,1' -biphenyl]-4,4'-diyl)bis(1,3-dioxo-1,3-dihydroxybenzofuran-5-carboxyamide) etc. are mentioned, However, It is not limited to these. These may be used individually or in mixture of 2 or more types.

＜(A) 유래의 방향족 폴리이미드의 특성＞ <Characteristics of aromatic polyimide derived from (A)>

본원의 조성물의 (A) 에서 유래하는 방향족 폴리이미드는, 다음의 (1) ∼ (4) 의 특성을 갖는다.The aromatic polyimide derived from (A) of the composition of the present application has the following characteristics (1) to (4).

＜＜(1) ∼ (4) 의 특성＞＞ << Characteristics of (1) to (4)>>

(1) 가열시의 중량 변화에 있어서의 1 ％ 중량 감소의 온도가 500 ℃ 이상, 바람직하게는 520 ℃ 이상, 보다 바람직하게는 550 ℃ 이상；(1) a temperature of 1% weight loss in a weight change during heating is 500°C or higher, preferably 520°C or higher, more preferably 550°C or higher;

(2) 파장 1000 ㎚ 에서 굴절률이 1.7 이상；(2) a refractive index of 1.7 or more at a wavelength of 1000 nm;

(3) 파장 1000 ㎚ 에서 굴절률과 복굴절의 차가 0.15 이상, 바람직하게는 0.16 이상；및(3) the difference between the refractive index and the birefringence at a wavelength of 1000 nm is 0.15 or more, preferably 0.16 or more; and

(4) 표면 에너지가 40 dyne/㎝ 이상, 바람직하게는 45 ∼ 70 dyne/㎝, 보다 바람직하게는 45 ∼ 60 dyne/㎝.(4) A surface energy of 40 dyne/cm or more, preferably 45 to 70 dyne/cm, more preferably 45 to 60 dyne/cm.

또한, 「(A) 에서 유래하는 방향족 폴리이미드」 또는 「(A) 유래의 방향족 폴리이미드」 란, (A) 성분이 「방향족 폴리이미드」 만으로 이루어지는 경우에는, 그 「방향족 폴리이미드」 를 말한다. 또, (A) 성분이 「방향족 폴리이미드 전구체」 만으로 이루어지는 경우, 그 전구체가 모두 「방향족 폴리이미드」 가 되었을 경우의 그 「방향족 폴리이미드」 를 말한다. (A) 성분이 「방향족 폴리이미드 A」 및 「방향족 폴리이미드 전구체 B」 를 갖는 경우, 「방향족 폴리이미드 전구체 B」 로부터 형성되는 「방향족 폴리이미드 B'」 와「방향족 폴리이미드 A」 의 전체를 말한다.In addition, "aromatic polyimide derived from (A)" or "aromatic polyimide derived from (A)" means the "aromatic polyimide" when (A) component consists only of "aromatic polyimide". Moreover, when (A) component consists only of "aromatic polyimide precursor", the "aromatic polyimide" when all the precursors become "aromatic polyimide" is said. (A) When the component has "aromatic polyimide A" and "aromatic polyimide precursor B", the whole of "aromatic polyimide B'" and "aromatic polyimide A" formed from "aromatic polyimide precursor B" say

이들 특성을 가짐으로써, 조성물로부터 박리층을 형성한 경우, 그 박리층은 유리 기판과의 밀착성이 양호해지는 한편, 박리층 상에 피박리체를 형성한 경우, 그 피박리체는 커터 등으로 절입을 넣음으로써 용이하게 박리할 수 있다.By having these characteristics, when a release layer is formed from the composition, the release layer has good adhesion to a glass substrate, while when an object to be peeled is formed on the release layer, the object to be peeled is cut with a cutter or the like. Thus, it can be easily peeled off.

＜(B) 성분＞ <(B) component>

본원의 조성물은, (B) 성분으로서, 아미드계 용매를 갖는다.The composition of this application has an amide type solvent as (B) component.

아미드계 용매란, 아미드기, 알킬아미드기를 갖는 액체를 의미한다.The amide solvent means a liquid having an amide group and an alkylamide group.

아미드계 용매로서, 예를 들어 N메틸피롤리돈, N에틸피롤리돈, DMAc, DMF, 에크아미드 M, 에크아미드 B (이데미츠 흥산 (주) 제조) 등을 들 수 있지만, 이들에 한정되지 않는다.Examples of the amide solvent include, but are not limited to, Nmethylpyrrolidone, Nethylpyrrolidone, DMAc, DMF, Ecamide M, Ecamide B (manufactured by Idemitsu Kogsan Co., Ltd.) .

아미드계 용매로서, 하기 식 (I) 로 나타내는 용매, 및/또는 (II) (식 중, R1 및 R2 는 각각 독립적으로, 탄소 원자수 1 ∼ 4 의 알킬기를 나타내고, h 는 자연수를 나타낸다) 로 나타내는 용매인 것이 좋다.As the amide solvent, a solvent represented by the following formula (I), and/or (II) (wherein, R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, and h represents a natural number. ) is preferably a solvent represented by

[화학식 2][Formula 2]

Figure 112016103265558-pct00002
Figure 112016103265558-pct00002

본원의 조성물은, 상기 (A) 성분 및 (B) 성분 외에, 여러 가지 성분을 가져도 된다. 예를 들어, 가교제 (이하, 가교성 화합물이라고도 한다.) 를 들 수 있지만, 이들에 한정되지 않는다.The composition of this application may have various components other than the said (A) component and (B) component. For example, although a crosslinking agent (henceforth a crosslinking compound is also mentioned.) is mentioned, It is not limited to these.

그 가교성 화합물로서, 예를 들어 에폭시기를 2 개 이상 함유하는 화합물, 아미노기의 수소 원자가 메틸올기, 알콕시메틸기 또는 그 양방으로 치환된 기를 갖는, 멜라민 유도체, 벤조구아나민 유도체 또는 글리콜우릴 등을 들 수 있지만, 이들에 한정되지 않는다.Examples of the crosslinkable compound include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both. However, it is not limited to these.

이하에, 가교성 화합물의 구체예를 들지만, 이것에 한정되지 않는다.Although the specific example of a crosslinkable compound is given below, it is not limited to this.

에폭시기를 2 개 이상 함유하는 화합물로서, 에폴리드 GT-401, 에폴리드 GT-403, 에폴리드 GT-301, 에폴리드 GT-302, 셀록사이드 2021, 셀록사이드 3000 (이상, (주) 다이 셀 제조) 등의 시클로헥센 구조를 갖는 에폭시 화합물；에피코트 1001, 에피코트 1002, 에피코트 1003, 에피코트 1004, 에피코트 1007, 에피코트 1009, 에피코트 1010, 에피코트 828 (이상, 재팬 에폭시 레진 (주) 제조 (현：미츠비시 화학 (주) 제조, jER (등록상표) 시리즈)) 등의 비스페놀 A 형 에폭시 화합물；에피코트 807 (재팬 에폭시 레진 (주) 제조) 등의 비스페놀 F 형 에폭시 화합물；에피코트 152, 에피코트 154 (이상, 재팬 에폭시 레진 (주) 제조 (현：미츠비시 화학 (주) 제조, jER (등록상표) 시리즈)), EPPN201, EPPN202 (이상, 닛폰 화약 (주) 제조) 등의 페놀 노볼락형 에폭시 화합물；ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (이상, 닛폰 화약 (주) 제조), 에피코트 180S75 (재팬 에폭시 레진 (주) (현：미츠비시 화학 (주) 제조, jER (등록상표) 시리즈) 제조) 등의 크레졸 노볼락형 에폭시 화합물；V8000-C7 (DIC (주) 제조) 등의 나프탈렌형 에폭시 화합물；데나콜 EX-252 (나가세 켐텍스 (주) 제조), CY175, CY177, CY179, 아랄다이트 CY-182, 아랄다이트 CY-192, 아랄다이트 CY-184 (이상, BASF 사 제조), 에피클론 200, 에피클론 400 (이상, DIC (주) 제조), 에피코트 871, 에피코트 872 (이상, 재팬 에폭시 레진 (주) 제조 (현：미츠비시 화학 (주) 제조, jER (등록상표) 시리즈)), ED-5661, ED-5662 (이상, 셀라니즈 코팅 (주) 제조) 등의 지환식 에폭시 화합물；데나콜 EX-611, 데나콜 EX-612, 데나콜 EX-614, 데나콜 EX-622, 데나콜 EX-411, 데나콜 EX-512, 데나콜 EX-522, 데나콜 EX-421, 데나콜 EX-313, 데나콜 EX-314, 데나콜 EX-312 (이상, 나가세 켐텍스 (주) 제조) 등의 지방족 폴리글리시딜에테르 화합물 등을 들 수 있다.As a compound containing two or more epoxy groups, EPOLID GT-401, EPOLID GT-403, EPOLID GT-301, EPOLID GT-302, Celoxide 2021, Celoxide 3000 ( ) Epoxy compound having a cyclohexene structure (manufactured by Daicel); Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, Japan) Bisphenol A-type epoxy compounds such as Epoxy Resin Co., Ltd. (current: Mitsubishi Chemical Corporation, jER (registered trademark) series)); Bisphenol F-type epoxy such as Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.) Compound; Epicoat 152, Epicoat 154 (above, manufactured by Japan Epoxy Resin Co., Ltd. (currently: manufactured by Mitsubishi Chemical Co., Ltd., jER (registered trademark) series)), EPPN201, EPPN202 (above, manufactured by Nippon Kayaku Co., Ltd.) ) phenol novolac-type epoxy compounds; ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy) Cresol novolac-type epoxy compounds such as Resin Co., Ltd. (current: manufactured by Mitsubishi Chemical Co., Ltd., jER (registered trademark) series)); Naphthalene-type epoxy compounds such as V8000-C7 (manufactured by DIC Corporation); Cole EX-252 (manufactured by Nagase Chemtex Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, manufactured by BASF), Epiclone 200, Epiclone 400 (above, manufactured by DIC Corporation), Epicoat 871, Epicoat 872 (above, manufactured by Japan Epoxy Resin Co., Ltd. (current: manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series)) , ED-5661, ED-5662 (above, manufactured by Celanese Coating Co., Ltd.) and other alicyclic epoxy compounds; Denacol EX-611, Denacol EX-612, and Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX- Aliphatic polyglycidyl ether compounds, such as 312 (above, Nagase Chemtex Co., Ltd. product), etc. are mentioned.

아미노기의 수소 원자가 메틸올기, 알콕시메틸기 또는 그 양방으로 치환된 기를 갖는, 멜라민 유도체, 벤조구아나민 유도체 또는 글리콜우릴로서, 트리아진 고리 1 개당 메톡시메틸기가 평균 3.7 개 치환되어 있는 MX-750, 트리아진 고리 1 개당 메톡시메틸기가 평균 5.8 개 치환되어 있는 MW-30 (이상, (주) 산와 케미컬 제조)；사이멜 300, 사이멜 301, 사이멜 303, 사이멜 350, 사이멜 370, 사이멜 771, 사이멜 325, 사이멜 327, 사이멜 703, 사이멜 712 등의 메톡시메틸화 멜라민；사이멜 235, 사이멜 236, 사이멜 238, 사이멜 212, 사이멜 253, 사이멜 254 등의 메톡시메틸화부톡시메틸화 멜라민；사이멜 506, 사이멜 508 등의 부톡시메틸화 멜라민；사이멜 1141 과 같은 카르복실기 함유 메톡시메틸화이소부톡시메틸화 멜라민；사이멜 1123 과 같은 메톡시메틸화에톡시메틸화벤조구아나민；사이멜 1123-10 과 같은 메톡시메틸화부톡시메틸화벤조구아나민；사이멜 1128 과 같은 부톡시메틸화벤조구아나민；사이멜 1125-80 과 같은 카르복실기 함유 메톡시메틸화에톡시메틸화벤조구아나민；사이멜 1170 과 같은 부톡시메틸화글리콜우릴；사이멜 1172 와 같은 메틸올화글리콜우릴 (이상, 미츠이 사이아나미드 (주) 제조 (현：닛폰 사이텍 인더스트리즈 (주)) 등을 들 수 있다.A melamine derivative, a benzoguanamine derivative, or a glycoluril in which the hydrogen atom of the amino group has a methylol group, an alkoxymethyl group, or a group substituted with both of them, MX-750, in which an average of 3.7 methoxymethyl groups are substituted per triazine ring MW-30 in which an average of 5.8 methoxymethyl groups are substituted per azine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel Methoxymethylated melamines, such as 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254, etc. Toxymethylated butoxymethylated melamine; Butoxymethylated melamine such as Cymel 506 and Cymel 508; Carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141; Methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123 ; Methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10; Butoxymethylated benzoguanamine such as Cymel 1128; Carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80; Butoxymethylation glycoluril like Mel 1170; Methylolation glycoluril like Cymel 1172 (above, Mitsui Cyanamide Co., Ltd. product (current: Nippon Cytec Industries Co., Ltd.) etc. are mentioned.

본원의 조성물에 의해, 유리 기판 바로 위에 형성되는 박리층을 형성할 수 있다.With the composition of this application, the peeling layer formed directly on a glass substrate can be formed.

예를 들어, 유리 기판에 본원의 조성물을 종래 공지된 수법에 의해 도포하고, 얻어진 도포막을 소정의 온도에서 가열함으로써 박리층을 형성할 수 있다.For example, a peeling layer can be formed by apply|coating the composition of this application to a glass substrate by a conventionally well-known method, and heating the obtained coating film at predetermined temperature.

또, 피박리체층은, 박리층 상에 형성할 수 있다. 피박리체층은, 1 층이어도 되고 복수 층이어도 된다. 여러 가지 디바이스를 제조하려면, 복수 층인 것이 현실적이다.Moreover, the to-be-released body layer can be formed on a peeling layer. The number of layers to be removed may be one or multiple layers may be sufficient as them. In order to manufacture various devices, it is realistic that there are multiple layers.

피박리체층 중 박리층 바로 위의 층은, 사용하는 박리층에 의존하지만, 그 박리층과의 박리성이 좋은 것, 바꾸어 말하면, 사용하는 박리층과의 밀착성이 좋지 않은 것을 사용하는 것이 좋다.Among the layers to be removed, the layer immediately above the release layer depends on the release layer to be used, but it is preferable to use one having good releasability with the release layer, in other words, those having poor adhesion with the release layer to be used.

본원의 다른 면으로서, 피박리체의 제조 방법을 제공한다.As another aspect of the present application, there is provided a method for producing an object to be removed.

그 방법은,That way,

a) 본원의 조성물을 유리 기판 상에 도포한 후, 박리층을 형성하는 공정；a) after applying the composition of the present application on a glass substrate, the step of forming a release layer;

b) 그 박리층 상에, 피박리체를 형성하는 공정；및b) a step of forming an object to be removed on the release layer; and

c) 박리층과 피박리체의 계면에 있어서, 피박리체를 박리하는 공정；c) at the interface between the release layer and the object to be peeled, a step of peeling the object to be peeled;

을 가짐으로써, 피박리체를 얻을 수 있다.By having it, a to-be-released body can be obtained.

b) 공정에 있어서, 「피박리체」 는 1 층이어도 되고 복수 층이어도 된다. 또한, 「피박리체」 중 박리층 바로 위의 층은, 사용하는 박리층에 의존하지만, 그 박리층과의 박리성이 좋은 것, 바꾸어 말하면, 사용하는 박리층과의 밀착성이 좋지 않은 것인 것이 좋다.b) Step WHEREIN: One layer or multiple layers may be sufficient as "the to-be-released body". In addition, although the layer immediately above the release layer in the "subject to be peeled" depends on the release layer to be used, it is necessary to have good releasability with the release layer, in other words, those with poor adhesion to the release layer to be used. good.

이하, 본 발명을 실시예를 따라 설명하는데, 본 발명은 그 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

실시예Example

본 실시예에 사용하는 약어에 대해, 이하에 열거하고, 설명한다.Abbreviations used in the present Examples are listed and described below.

＜용매＞ <solvent>

NMP：N-메틸피롤리돈.NMP: N-methylpyrrolidone.

＜아민류＞<Amines>

PDA：p-페닐렌디아민.PDA: p-phenylenediamine.

APAB：2-(3-아미노페닐)-5-아미노벤즈이미다졸.APAB: 2-(3-aminophenyl)-5-aminobenzimidazole.

DATP：4,4＂-디아미노-p-터페닐.DATP: 4,4"-diamino-p-terphenyl.

6FAP：2,2-비스(3-아미노-4-하이드록시페닐)헥사플루오로프로판.6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

＜산 2무수물＞ <Acid dianhydride>

BPDA：3,3',4,4'-비페닐테트라카르복실산 2무수물.BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride.

BA-TME：4,4'-비페닐렌비스(트리멜리트산모노에스테르산 무수물).BA-TME: 4,4'-biphenylenebis(trimellitic acid monoesteric anhydride).

PMDA:피로멜리트산 2무수물.PMDA: Pyromellitic dianhydride.

＜알데히드＞ <aldehyde>

IPHA：이소프탈알데히드.IPHA: isophthalaldehyde.

[수 평균 분자량 및 중량 평균 분자량의 측정][Measurement of number average molecular weight and weight average molecular weight]

폴리머의 중량 평균 분자량 (이하, 「Mw」 라고 약기한다) 과 분자량 분포는, 닛폰 분광 주식회사 GPC 장치 (Shodex (등록상표) 칼럼 KF803L 및 KF805L) 를 사용하고 용출 용매로서 디메틸포름아미드를 유량 1 ㎖/분, 칼럼 온도 50 ℃ 의 조건으로 측정하였다. 또한, Mw 는 폴리스티렌 환산값으로 하였다.The weight average molecular weight (hereinafter, abbreviated as "Mw") and molecular weight distribution of the polymer were measured using Nippon Spectroscopy Co., Ltd. GPC apparatus (Shodex (registered trademark) columns KF803L and KF805L) and dimethylformamide as the elution solvent at a flow rate of 1 ml/ It measured on the conditions of minute and a column temperature of 50 degreeC. In addition, Mw was made into polystyrene conversion value.

＜합성예＞ <Synthesis example>

＜합성예 1 폴리이미드 전구체 P1 의 합성＞ <Synthesis example 1 synthesis|combination of polyimide precursor P1>

PDA 17.8 g (0.164 몰), DATP 2.38 g (0.009 몰), 및 APABI 2.05 g (0.009 몰) 을 NMP 425 g 에 용해시키고, BPDA 52.8 g (0.179 몰) 을 동시에 첨가한 후, 재차 NMP 7.4 g 을 첨가하고, 질소 분위기하 23 ℃, 24 시간 반응시켰다. 얻어진 폴리이미드 전구체 P1 의 Mw 는 63000, 분자량 분포 9.9 였다.17.8 g (0.164 mol) of PDA, 2.38 g (0.009 mol) of DATP, and 2.05 g (0.009 mol) of APABI were dissolved in 425 g of NMP, and 52.8 g (0.179 mol) of BPDA were simultaneously added thereto, followed by 7.4 g of NMP again. It was added, and it was made to react in nitrogen atmosphere at 23 degreeC for 24 hours. Mw of the obtained polyimide precursor P1 was 63000 and molecular weight distribution 9.9.

＜합성예 2 폴리이미드 전구체 P2 의 합성＞ <Synthesis example 2 synthesis|combination of polyimide precursor P2>

DATP 30.8 g (0.118 몰) 을 NMP 425 g 에 용해시키고, BPDA 34.1 g (0.116 몰) 을 동시에 첨가한 후, 재차 NMP 10 g 을 첨가하고, 질소 분위기하 23 ℃, 24 시간 반응시켰다. 얻어진 폴리이미드 전구체 P2 의 Mw 는 70700, 분자량 분포 9.7 이었다.After dissolving 30.8 g (0.118 mol) of DATP in 425 g of NMP and simultaneously adding 34.1 g (0.116 mol) of BPDA, 10 g of NMP was added again, and reaction was performed at 23° C. under a nitrogen atmosphere for 24 hours. Mw of the obtained polyimide precursor P2 was 70700, and molecular weight distribution 9.7.

＜합성예 3 폴리이미드 전구체 P3 의 합성＞ <Synthesis example 3 synthesis|combination of polyimide precursor P3>

PDA 20.261 g (0.1875 몰) 과 TPDA 12.206 g (0.0469 몰) 을 NMP 617.4 g 에 용해하고, 15 ℃ 로 냉각 후, PMDA 50.112 g (0.2298 몰) 을 첨가하고, 질소 분위기하, 50 ℃ 에서 48 시간 반응시켰다. 얻어진 폴리이미드 전구체 P3 의 Mw 는 82,100, 분자량 분포는 2.7 이었다.20.261 g (0.1875 mol) of PDA and 12.206 g (0.0469 mol) of TPDA were dissolved in NMP 617.4 g, cooled to 15°C, 50.112 g (0.2298 mol) of PMDA was added, and reaction was performed at 50°C in a nitrogen atmosphere for 48 hours. did it Mw of the obtained polyimide precursor P3 was 82,100, and molecular weight distribution was 2.7.

＜합성예 4 폴리이미드 전구체 P4 의 합성＞ <Synthesis example 4 synthesis|combination of polyimide precursor P4>

PDA 9.66 g (0.089 몰) 과 APAB 1.05 g (0.005 몰) 을 NMP 440 g 에 용해하고, BP-TME 49.2 g (0.092 몰) 을 첨가하고, 질소 분위기하, 실온에서 24 시간 반응시켰다. 얻어진 폴리이미드 전구체 P4 의 Mw 는 57000, 분자량 분포는 9.3 이었다.9.66 g (0.089 mol) of PDA and 1.05 g (0.005 mol) of APAB were dissolved in 440 g of NMP, 49.2 g (0.092 mol) of BP-TME was added thereto, and the reaction was carried out at room temperature in a nitrogen atmosphere for 24 hours. Mw of the obtained polyimide precursor P4 was 57000, and molecular weight distribution was 9.3.

＜합성예 5 폴리이미드 전구체 P5 의 합성＞ <Synthesis example 5 synthesis|combination of polyimide precursor P5>

PDA 3.176 g (0.02937 몰) 을 NMP 88.2 g 에 용해하고, BPDA 8.624 g (0.02931 몰) 을 첨가한 후, 질소 분위기하, 23 ℃ 에서 24 시간 반응시켰다. 얻어진 폴리이미드 전구체 P5 의 Mw 는 107,300, 분자량 분포 4.6 이었다.After dissolving 3.176 g (0.02937 mol) of PDA in 88.2 g of NMP and adding 8.624 g (0.02931 mol) of BPDA, it was made to react at 23°C in a nitrogen atmosphere for 24 hours. Mw of the obtained polyimide precursor P5 was 107,300 and molecular weight distribution 4.6.

＜합성예 6 폴리벤조옥사졸 전구체 (P6) 의 합성＞ <Synthesis Example 6 Synthesis of polybenzoxazole precursor (P6)>

6FAP 3.18 g (0.059 몰) 을 NMP 70 g 에 용해하고, IPHA 7.92 g (0.060 몰) 을 첨가한 후, 질소 분위기하, 23 ℃ 에서 24 시간 반응시켰다. 얻어진 폴리머의 Mw 는 107,300, 분자량 분포 4.6 이었다.After dissolving 3.18 g (0.059 mol) of 6FAP in 70 g of NMP and adding 7.92 g (0.060 mol) of IPHA, it was reacted at 23° C. under a nitrogen atmosphere for 24 hours. The obtained polymer had a Mw of 107,300 and a molecular weight distribution of 4.6.

＜합성예 7 폴리이미드 전구체 P7 의 합성＞ <Synthesis example 7 synthesis|combination of polyimide precursor P7>

PMDA (98)//p-PDA (100)PMDA (98) //p-PDA (100)

p-PDA 10.078 g (93 m㏖) 을 NMP 220.0 g 에 용해시켰다. 얻어진 용액에, PMDA 19.922 g (91 m㏖) 을 첨가하고, 질소 분위기하, 23 ℃ 에서 24 시간 반응시켰다. 얻어진 폴리머의 Mw 는 55,900, 분자량 분포 3.1 이었다.10.078 g (93 mmol) of p-PDA was dissolved in 220.0 g of NMP. 19.922 g (91 mmol) of PMDA was added to the obtained solution, and it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours. The obtained polymer had a Mw of 55,900 and a molecular weight distribution of 3.1.

＜박리층 기판 제조＞ <Preparation of release layer substrate>

상기 합성예 1 ∼ 7 에서 얻은 P1 ∼ P7 을 NMP 로 4 wt％ 로 희석하고, 100 ㎜ ×100 ㎜ 유리 기판 (OA-10G 무알칼리 유리) 또는 실리콘 웨이퍼 상에 스핀 코터를 사용하여 도포한 후, 큐어 조건 A ∼ C 중 어느 것으로, 오븐으로 소성하여 박리층을 제조하였다.After diluting P1 to P7 obtained in Synthesis Examples 1 to 7 to 4 wt% with NMP, and applying on a 100 mm × 100 mm glass substrate (OA-10G alkali-free glass) or a silicon wafer using a spin coater, Under any of the curing conditions A to C, it was baked in an oven to prepare a release layer.

큐어 조건 A：120 ℃ 에서 30 분 유지 → 승온 → 300 ℃ 에서 60 분 유지 → 승온 → 400 ℃ 에서 60 분 유지. 또한, 승온 속도는 10 ℃/분이었다. Cure condition A : Hold at 120 °C for 30 minutes → Increase in temperature → Hold at 300 °C for 60 minutes → Increase in temperature → Hold at 400 °C for 60 minutes. In addition, the rate of temperature increase was 10°C/min.

큐어 조건 B：120 ℃ 에서 30 분 유지 → 승온 → 180 ℃ 에서 20 분 유지 → 승온 → 240 ℃ 에서 20 분 유지 → 승온 → 300 ℃ 에서 20 분 유지 → 승온 → 400 ℃ 에서 20 분 유지 → 승온 → 450 ℃ 에서 60 분 유지. 또한, 승온 속도는 10 ℃/분이었다. Cure condition B : Hold at 120 °C for 30 minutes → Increase temperature → Hold at 180 °C for 20 minutes → Increase temperature → Hold at 240 °C for 20 minutes → Increase temperature → Hold at 300 °C for 20 minutes → Increase temperature → Hold at 400 °C for 20 minutes → Increase temperature → 450 Hold for 60 minutes at °C. In addition, the rate of temperature increase was 10°C/min.

큐어 조건 C：80 ℃ 에서 10 분 유지 → 승온 → 300 ℃ 에서 30 분 유지 → 승온 → 400 ℃ 에서 30 분 유지. 또한, 승온 속도는 10 ℃/분이었다. Cure condition C : Hold at 80 °C for 10 minutes → temperature rise → hold at 300 °C for 30 minutes → temperature rise → hold at 400 °C for 30 minutes. In addition, the rate of temperature increase was 10°C/min.

얻어진 도포막의 막두께는, 접촉식 막두께 측정기 (주식회사 ULVAC 제조 Dektak 3ST) 를 사용하고, 측정하였다.The film thickness of the obtained coating film was measured using the contact-type film thickness meter (Dektak 3ST by ULVAC Corporation).

표 1 에, 사용한 P1 ∼ P7 의 전구체, 도포 기판, 큐어 조건, 및 제조한 박리층의 막두께를 나타낸다.In Table 1, the precursors of P1 to P7 used, the application substrate, the curing conditions, and the film thickness of the produced release layer are shown.

Figure 112016103265558-pct00003
Figure 112016103265558-pct00003

＜크로스컷 시험 I＞ <Cross Cut Test I>

표 1 에서 나타내는 실시예 1 ∼ 5 및 비교예 1 ∼ 3 의, 박리층을 구비한 기판에 대해, 크로스컷 시험 I 로, 기판 (유리 또는 실리콘 웨이퍼)/박리층의 밀착력을 확인하였다.About the board|substrate with a peeling layer of Examples 1-5 and Comparative Examples 1-3 shown in Table 1, the adhesive force of the board|substrate (glass or silicon wafer) / peeling layer was confirmed by the crosscut test I.

크로스컷 시험 I 은, 다음과 같이 실시하였다.The crosscut test I was implemented as follows.

(1) 박리층 상에, 가로세로 1 ㎜ 의 정방형을 100 개 제조하였다.(1) On the release layer, 100 squares of 1 mm in width were produced.

(2) 그 후, 점착 테이프 (셀로테이프 (등록상표)) 로 상기 정방형을 첩부하고, 박리 공정을 실시하였다.(2) Then, the said square was affixed with the adhesive tape (Cellotape (trademark)), and the peeling process was implemented.

(3) 박리 공정 후, 기판에 잔존하는, 상기 정방형을 세었다.(3) After the peeling step, the square remaining on the substrate was counted.

＜크로스컷 시험 I 의 결과의 지표＞ <Indices of results of cross-cut test I>

크로스컷 시험의 결과, 박리의 정도를 이하의 지표로 나타낸다.As a result of the cross-cut test, the degree of peeling is shown with the following index|index.

5B：박리되지 않음.5B: It does not peel.

4B：5 ％ 이하의 박리.4B: Peeling of 5% or less.

3B：5 ∼ 15 ％ 의 박리.3B: 5 to 15% of peeling.

2B：15 ∼ 35 ％ 의 박리.2B: 15 to 35% of peeling.

1B：35 ∼ 65 ％ 의 박리.1B: 35 to 65% of peeling.

0B：65 ％ ∼ 80 ％ 의 박리.0B: 65% to 80% of peeling.

B：80 ％ ∼ 95 ％ 의 박리.B: 80% to 95% of peeling.

A：95 ％ ∼ 100 ％ 미만의 박리.A: 95% to less than 100% peeling.

AA：100 ％ 의 박리.AA: 100% peeling.

상기 크로스컷 시험 I 과는 별도로, 표 1 에서 나타내는 실시예 1 ∼ 5 및 비교예 1 ∼ 3 의, 박리층을 구비한 기판에 대해, 그 박리층을 구성하는 성분의 특성, 즉 (1) 가열시의 중량 변화에 있어서의 1 ％ 중량 감소를 나타내는 온도, (2) 파장 1000 ㎚ 에서의 굴절률, (3) 파장 1000 ㎚ 에서의 복굴절, 및 (4) 표면 에너지를 측정하였다. 또한, 각 특성의 측정 조건 등을 이하에 나타낸다.Separately from the crosscut test I, for the substrates with a release layer in Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the properties of the components constituting the release layer, that is, (1) heating The temperature at which a 1% weight loss with respect to the change in weight at time, (2) refractive index at a wavelength of 1000 nm, (3) birefringence at a wavelength of 1000 nm, and (4) surface energy was measured was measured. In addition, the measurement conditions of each characteristic, etc. are shown below.

＜(1) 가열시의 중량 변화에 있어서의 1 ％ 중량 감소를 나타내는 온도＞ <(1) Temperature at which 1% weight loss in weight change during heating>

브루커 (주) 제조 TD-DTA2000ST 를 사용하여, 질소 분위기하에서 열 중량 (TG) 측정을 실시하고, 중량이 1 ％ 감소하는 온도를 구하였다.Thermogravimetric (TG) measurement was performed in nitrogen atmosphere using Bruker Co., Ltd. product TD-DTA2000ST, and the temperature at which weight decreases 1% was calculated|required.

＜(2) 파장 1000 ㎚ 에서의 굴절률 및 (3) 복굴절률＞ <(2) refractive index at a wavelength of 1000 nm and (3) birefringence>

고속 분광 엘립소미터 M-2000 (제이·에이·울람·재팬 (주) 제조) 을 사용하여, 굴절률 및 복굴절률을 측정하였다. 또한, 굴절률은, 1000 ㎚ 값의 면내 굴절률로 하고, 복굴절률은, 면내 굴절률과 면외 굴절률의 차로 하였다.The refractive index and the birefringence were measured using high-speed spectroscopic ellipsometer M-2000 (manufactured by J.A. Ulam Japan Co., Ltd.). In addition, the refractive index was made into the in-plane refractive index of 1000 nm value, and the birefringence was made into the difference between the in-plane refractive index and the out-of-plane refractive index.

＜(4) 표면 에너지＞ <(4) surface energy>

전자동 접촉각계 DM-701 (쿄와 계면 과학 (주) 제조) 을 사용하여, 상기 합성예 1 ∼ 7 에서 얻은 P1 ∼ P7 로부터 얻어진 박리층의 표면 에너지를 측정하였다. 또한, 측정에 사용한 용매는, 물과 요오드화메틸렌이며, 이들 용매의 접촉각으로부터 산출하였다.Using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.), the surface energy of the release layer obtained from P1 to P7 obtained in Synthesis Examples 1 to 7 was measured. In addition, the solvent used for the measurement was water and methylene iodide, Computing from the contact angle of these solvents.

＜피박리체의 형성과 그 박리 시험 (크로스컷 시험 II)＞ <Formation of object to be removed and its peel test (Crosscut Test II)>

실시예 1 ∼ 5 및 비교예 1 ∼ 3 의, 박리층을 구비한 기판 상에 피박리체를 형성하고, 그 박리의 정도를 크로스컷 시험 II 로 확인하였다.The body to be peeled was formed on the board|substrate with a peeling layer of Examples 1-5 and Comparative Examples 1-3, and the degree of the peeling was confirmed by the crosscut test II.

＜＜피박리체층의 제조＞＞ <<Preparation of layer to be removed>>

박리층을 구비한 기판의 그 박리층 상에, 피박리체로서 폴리이미드 층을 형성하였다.On the release layer of the substrate provided with the release layer, a polyimide layer was formed as an object to be released.

구체적으로는, 표 1 에 나타내는, 실시예 1 ∼ 5 및 비교예 1 ∼ 3 의, 박리층을 구비하는 기판의, 박리층 상에, 상기 합성예 5 또는 합성예 1 에서 얻어진 전구체 P5 또는 P1 을 바 코터로 도포하였다. 그 후, 오븐으로 120 ℃ 에서 30 분 유지 → 승온 → 180 ℃ 에서 20 분 유지 → 승온 → 240 ℃/20 분 유지 → 승온 → 300 ℃ 에서 20 분 유지 → 승온 → 400 ℃ 에서 20 분 유지 → 승온 → 450 ℃ 에서 60 분 유지 (어느 승온에 있어서도 그 속도는 10 ℃/분이었다) 로 큐어를 실시하고, 폴리이미드로 이루어지는 막두께 15 ㎛ 의 피박리체층을 제조하였다.Specifically, the precursor P5 or P1 obtained in Synthesis Example 5 or Synthesis Example 1 above on the release layer of the substrate provided with the release layer of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1 was added. It was applied with a bar coater. After that, in an oven, keep at 120 ℃ for 30 minutes → raise the temperature → maintain at 180 ℃ for 20 minutes → increase the temperature → keep at 240 ℃/20 min → increase the temperature → keep at 300 ℃ for 20 minutes → increase the temperature → keep at 400 ℃ for 20 minutes → increase the temperature → Curing was performed at 450 degreeC for 60 minutes (in any temperature increase, the rate was 10 degreeC/min), the to-be-released body layer with a film thickness of 15 micrometers which consists of polyimide was manufactured.

＜＜크로스컷 시험 II＞＞ <<Cross Cut Test II>>

상기에서 얻어진, 피박리체층 및 박리층을 구비하는 기판에 대해, 피박리체층/박리층간의 밀착력을 크로스컷 시험 II 로 확인하였다.About the board|substrate provided with the to-be-released body layer and peeling layer obtained above, the adhesive force between the to-be-released body layer / peeling layer was confirmed by crosscut test II.

크로스컷 시험 II 는, 크로스컷 시험 I 과 동일하게 실시하였다.Crosscut test II was implemented similarly to crosscut test I.

표 2 에, (1) 가열시의 중량 변화에 있어서의 1 ％ 중량 감소를 나타내는 온도 (표 2 중, 「(1)」 로 표기한다), (2) 파장 1000 ㎚ 에서의 굴절률 (표 2 중, 「(2)」 로 표기한다), (3) 그 (2) 의 굴절률과 복굴절의 차 (표 2 중, 「(3)」 으로 표기한다), (4) 표면 에너지 (표 2 중, 「(4)」 로 표기한다. 단, 단위는 dyne/㎝ 이다), 피박리체층에서 사용한 폴리이미드 전구체, 그리고 크로스컷 시험 I 및 II 의 결과를 나타낸다.In Table 2, (1) a temperature at which a weight loss of 1% in a weight change upon heating (in Table 2, it is denoted as "(1)"), (2) a refractive index at a wavelength of 1000 nm (in Table 2) , "(2)"), (3) the difference between the refractive index and birefringence (in Table 2, "(3)"), (4) surface energy (in Table 2, " (4)". However, the unit is dyne/cm), the polyimide precursor used in the layer to be removed, and the results of the crosscut tests I and II are shown.

Figure 112016103265558-pct00004
Figure 112016103265558-pct00004

표 2 로부터 다음의 것을 알 수 있다. 실시예 1 ∼ 5 의 박리층은, 시험 I 의 결과가 5B 인 것으로부터, 기판으로부터 박리층이 벗겨지는 경우가 없는 한편, 시험 II 의 결과가 AA 인 것으로부터, 박리층으로부터 피박리체층만이 박리되는 것을 알 수 있다. 요컨대, 본 발명의 박리층용 조성물로부터 형성된 박리층은, 원하는 박리 결과를 가져오는 것을 알 수 있다.Table 2 shows the following. As for the release layer of Examples 1 to 5, since the result of Test I was 5B, the release layer did not peel off from the substrate, while the result of Test II was AA, so only the release layer peeled from the release layer. it can be seen that That is, it turns out that the peeling layer formed from the composition for peeling layers of this invention brings a desired peeling result.

한편, 비교예 1 및 비교예 3 은, 시험 I 의 결과가 AA 이기 때문에, 박리층이 기판으로부터 박리되는 것을 알 수 있다. 요컨대, 비교예 1 및 비교예 3 은, 원하는 박리 결과를 얻을 수 없는 것을 알 수 있다. 또, 비교예 2 는, 시험 I 및 시험 II 가 함께 5B 인 것으로부터, 박리층과 기판의 계면에 있어서도, 박리층과 피박리체층의 계면에 있어서도 박리되지 않아, 원하는 박리 결과를 얻을 수 없는 것을 알 수 있다.On the other hand, in Comparative Example 1 and Comparative Example 3, since the result of Test I is AA, it turns out that the peeling layer peels from a board|substrate. That is, it turns out that the comparative example 1 and the comparative example 3 cannot obtain the desired peeling result. Further, in Comparative Example 2, since Test I and Test II were both 5B, there was no peeling either at the interface between the release layer and the substrate or at the interface between the release layer and the layer to be peeled, so that the desired peeling result could not be obtained. Able to know.

Claims (6)

유리 기판 바로 위에 설치하는 박리층을 형성하기 위한 조성물로서, 그 조성물이
(A) 방향족 폴리이미드 및/또는 방향족 폴리이미드 전구체；및
(B) 아미드계 용매；
를 갖고,
상기 (A) 유래의 방향족 폴리이미드는, 하기 (1) ∼ (4) 를 만족하는 상기 조성물：
(1) 가열시의 중량 변화에 있어서의 1 ％ 중량 감소의 온도가 500 ℃ 이상；
(2) 파장 1000 ㎚ 에서 굴절률이 1.7 이상；
(3) 파장 1000 ㎚ 에서 굴절률과 복굴절의 차가 0.15 이상；및
(4) 표면 에너지가 40 dyne/㎝ 이상.A composition for forming a release layer provided directly on a glass substrate, the composition comprising:
(A) an aromatic polyimide and/or an aromatic polyimide precursor; and
(B) an amide solvent;
have,
The said composition which the aromatic polyimide derived from said (A) satisfy|fills following (1)-(4):
(1) a temperature of 1% weight loss in a weight change during heating is 500° C. or higher;
(2) a refractive index of 1.7 or more at a wavelength of 1000 nm;
(3) the difference between the refractive index and the birefringence at a wavelength of 1000 nm is 0.15 or more; and
(4) The surface energy is 40 dyne/cm or more. 제 1 항에 있어서,
상기 (A) 성분이, p-페닐렌디아민 및 터페닐디아민으로 이루어지는 군에서 선택되는 적어도 1 종의 디아민 성분을 사용하여 제조되는 조성물.The method of claim 1,
A composition in which the component (A) is produced using at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine. 제 2 항에 있어서,
p-페닐렌디아민 및/또는 터페닐디아민의 양이, 전체 디아민 성분 100 몰％ 중, 70 몰％ 이상인 조성물.3. The method of claim 2,
The composition in which the quantity of p-phenylenediamine and/or terphenyldiamine is 70 mol% or more in 100 mol% of all the diamine components. 제 1 항에 있어서,
상기 (A) 성분이, 비페닐 골격, 이미다졸 골격 및 옥사졸 골격으로 이루어지는 군에서 선택되는 적어도 1 종의 제 1 골격을 갖는 방향족 디아민을 사용하여 제조되는 조성물.The method of claim 1,
A composition in which the component (A) is produced using an aromatic diamine having at least one first skeleton selected from the group consisting of a biphenyl skeleton, an imidazole skeleton and an oxazole skeleton. 제 1 항에 있어서,
상기 (A) 성분이, 벤젠 골격, 나프탈렌 골격 및 비페닐 골격으로 이루어지는 군에서 선택되는 적어도 1 종의 제 2 골격을 갖는 산 2무수물을 사용하여 제조되는 조성물.The method of claim 1,
A composition in which the component (A) is produced using an acid dianhydride having at least one second skeleton selected from the group consisting of a benzene skeleton, a naphthalene skeleton and a biphenyl skeleton. 제 1 항 내지 제 5 항 중 어느 한 항에 있어서,
상기 (B) 성분이, 하기 식 (I) 로 나타내는 용매, 및/또는 (II) (식 중, R1 및 R2 는 각각 독립적으로, 탄소 원자수 1 ∼ 4 의 알킬기를 나타내고, h 는 자연수를 나타낸다) 로 나타내는 용매인 조성물.
[화학식 1]
Figure 112016103265558-pct00005
6. The method according to any one of claims 1 to 5,
The component (B) is a solvent represented by the following formula (I), and/or (II) (wherein, R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, and h is a natural number is a solvent represented by ).
[Formula 1]
Figure 112016103265558-pct00005
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