JP6996764B2 - Laminates, their manufacturing methods and usage methods, and polyimide precursor solutions for laminating glass substrates - Google Patents

Laminates, their manufacturing methods and usage methods, and polyimide precursor solutions for laminating glass substrates Download PDF

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JP6996764B2
JP6996764B2 JP2019167246A JP2019167246A JP6996764B2 JP 6996764 B2 JP6996764 B2 JP 6996764B2 JP 2019167246 A JP2019167246 A JP 2019167246A JP 2019167246 A JP2019167246 A JP 2019167246A JP 6996764 B2 JP6996764 B2 JP 6996764B2
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朗 繁田
猛 吉田
祐己 山田
達弥 森北
宗紀 山田
良彰 越後
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/28—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
    • B32B27/281—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 comprising polyimides
    • 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
    • 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
    • G02F1/00—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
    • 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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • 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
    • B32B2457/00—Electrical equipment

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  • Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • General Physics & Mathematics (AREA)
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  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Surface Treatment Of Glass (AREA)

Description

本発明は、積層体、特に、優れた耐熱性と寸法安定性とを有するポリイミド層（被膜）とガラス基板とからなる積層体、およびその製造方法および使用方法ならびにガラス基板積層用ポリイミド前駆体溶液（ポリイミド被膜形成用ポリイミド前駆体溶液）に関する。 The present invention relates to a laminate, particularly a laminate composed of a polyimide layer (coating) having excellent heat resistance and dimensional stability and a glass substrate, a method for producing and using the laminate, and a polyimide precursor solution for laminating a glass substrate. (Polyimide precursor solution for forming a polyimide film).

従来、液晶ディスプレイ（ＬＣＤ）、プラズマディスプレイパネル（ＰＤＰ）、有機ＥＬディスプレイ（ＯＬＥＤ）等のフラットパネルディスプレイ（ＦＰＤ）、および電子ペーパー等の電子デバイスの分野では、主としてガラス基板上に電子素子を形成したものが用いられているが、ガラス基板は剛直であり、しなやかさに欠けるため、フレキシブルになりにくいという問題がある。 Conventionally, in the field of flat panel displays (FPD) such as liquid crystal displays (LCD), plasma display panels (PDP), organic EL displays (OLED), and electronic devices such as electronic paper, electronic elements are mainly formed on a glass substrate. However, since the glass substrate is rigid and lacks flexibility, there is a problem that it is difficult to be flexible.

そこで、フレキシブル性を有しかつ良好な耐熱性と寸法安定性とを有するポリイミド等の有機高分子材料をガラス基板に積層一体化した積層体を基板として用いる方法が提案されている。 Therefore, a method has been proposed in which a laminate obtained by laminating and integrating an organic polymer material such as polyimide, which has flexibility and good heat resistance and dimensional stability, on a glass substrate is used as the substrate.

特許文献１～３には、低い熱膨張係数（ＣＴＥ）を有するポリイミド被膜をガラス基板上に形成して積層一体化し、これを電子素子形成のための基板として利用することが提案されている。ここで、ポリイミドのＣＴＥは、ポリイミドの寸法安定性を示す指標の１つであり、低いＣＴＥを有するガラス基板（例えば、特許文献３に記載されているようなＣＴＥが４ｐｐｍ／℃以下の無アルカリガラス基板）のＣＴＥに近いほど、電子素子形成工程における高温処理過程で、積層体界面で生じるポリイミドの歪が小さくなり、ポリイミド被膜の寸法安定性が向上する。 Patent Documents 1 to 3 propose that a polyimide film having a low coefficient of thermal expansion (CTE) is formed on a glass substrate, laminated and integrated, and used as a substrate for forming an electronic element. Here, the CTE of polyimide is one of the indexes showing the dimensional stability of the polyimide, and is a glass substrate having a low CTE (for example, a non-alkali with a CTE of 4 ppm / ° C. or less as described in Patent Document 3). The closer it is to the CTE of the glass substrate), the smaller the strain of the polyimide generated at the interface of the laminate in the high temperature treatment process in the electronic element forming step, and the more the dimensional stability of the polyimide film is improved.

前記低熱膨張係数（ＣＴＥ）のポリイミドとしては、３，３’，４，４’―ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）等の芳香族テトラカルボン酸類とｐ－フェニレンジアミン（ＰＤＡ）等の芳香族ジアミンとから得られるポリイミドが、ＣＴＥが比較的低く、かつ優れた耐熱性を有することが知られている。 The polyimide having a low thermal expansion coefficient (CTE) includes aromatic tetracarboxylic acids such as 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and aromatics such as p-phenylenediamine (PDA). It is known that the polyimide obtained from the group diamine has a relatively low CTE and excellent heat resistance.

このようなポリイミド被膜が積層されたガラス基板においては、ガラス基板をキャリア用の基板として利用する場合、ポリイミド被膜の表面に電子素子を形成後、最後にポリイミド被膜をガラス基板から剥離することにより、フレキシブル基板とすることができる。 In a glass substrate on which such a polyimide film is laminated, when the glass substrate is used as a substrate for a carrier, an electronic element is formed on the surface of the polyimide film, and then the polyimide film is finally peeled off from the glass substrate. It can be a flexible substrate.

特開２００２－２９７０５４号公報Japanese Unexamined Patent Publication No. 2002-297054 特開２０１２－３５５８３号公報Japanese Unexamined Patent Publication No. 2012-35583 特開２０１４－２０５３２７号公報Japanese Unexamined Patent Publication No. 2014-205327

しかしながら、従来開示されたポリイミド被膜では、ＣＴＥを充分に小さくすることが難しく、その寸法安定性は充分なものではなかった。従い、例えば、ガラス基板から剥離されたポリイミド被膜がカールしやすいという問題があった。カールの曲率半径が小さいほど、ポリイミド被膜の取り扱いが煩雑となり、作業性に問題が生じた。また、ポリイミド被膜のガラス基板からの剥離特性も充分なものではなかった。 However, with the polyimide film disclosed conventionally, it is difficult to make the CTE sufficiently small, and its dimensional stability is not sufficient. Therefore, for example, there is a problem that the polyimide film peeled off from the glass substrate is easily curled. The smaller the radius of curvature of the curl, the more complicated the handling of the polyimide film, which causes a problem in workability. In addition, the peeling characteristics of the polyimide film from the glass substrate were not sufficient.

そこで、本発明は前記課題を解決するものであって、ポリイミド被膜と、ガラス基板とからなる積層体において、ポリイミド被膜を、ガラス基板から剥離する際、良好な剥離特性を有し、かつ剥離されたポリイミド被膜がカールしにくい積層体とその製造方法および使用方法、ならびにこのようなポリイミド被膜を形成させることができるガラス基板積層用ポリイミド前駆体溶液の提供を目的とする。 Therefore, the present invention solves the above-mentioned problems, and in a laminate composed of a polyimide film and a glass substrate, when the polyimide film is peeled from the glass substrate, it has good peeling characteristics and is peeled off. It is an object of the present invention to provide a laminate in which the polyimide film is hard to curl, a method for producing and using the laminate, and a polyimide precursor solution for laminating a glass substrate capable of forming such a polyimide film.

本発明者らは、前記課題を解決するために鋭意研究した結果、前記積層体にておいて、ガラス基板とポリイミド被膜とからなる積層体において、ポリイミド被膜の構成を特定のものとすることにより前記課題が解決されることを見出し、本発明の完成に至った。 As a result of diligent research to solve the above problems, the present inventors have made the structure of the polyimide film specific in the laminate composed of the glass substrate and the polyimide film in the laminate. It was found that the above-mentioned problems could be solved, and the present invention was completed.

すなわち、本発明は下記を趣旨とするものである。
（１）ガラス基板と、このガラス基板上に形成されたフィラ含有ポリイミド層を含むポリイミド被膜とからなる積層体であって、前記フィラの熱膨張係数が１０ｐｐｍ／℃以下であることを特徴とする積層体。
（２）前記ポリイミド被膜が、前記フィラ含有ポリイミド層、および当該フィラ含有ポリイミド層上に形成されたフィラ非含有ポリイミド層を含む、（１）に記載の積層体。
（３）前記フィラが、カーボン粒子、セラミック粒子およびシリコン粒子からなる群から選択される１種以上のフィラである、（１）または（２）に記載の積層体。
（４）フィラ含有ポリイミド前駆体溶液をガラス基板上に塗布、乾燥し、熱処理することにより、フィラ含有ポリイミド層を形成することを特徴とする（１）～（３）のいずれかに記載の積層体の製造方法。
（５）（１）～（３）のいずれかに記載の積層体を電子デバイスの製造に用いることを特徴とする積層体の使用方法。
（６）熱膨張係数が１０ｐｐｍ／℃以下のフィラを含有することを特徴とするガラス基板積層用ポリイミド前駆体溶液。 That is, the present invention has the following object.
(1) A laminate composed of a glass substrate and a polyimide coating containing a filler-containing polyimide layer formed on the glass substrate, wherein the coefficient of thermal expansion of the filler is 10 ppm / ° C. or less. Laminated body.
(2) The laminate according to (1), wherein the polyimide film includes the filler-containing polyimide layer and the filler-free polyimide layer formed on the filler-containing polyimide layer.
(3) The laminate according to (1) or (2), wherein the filler is one or more fillers selected from the group consisting of carbon particles, ceramic particles and silicon particles.
(4) The laminate according to any one of (1) to (3), wherein a filler-containing polyimide layer is formed by applying a filler-containing polyimide precursor solution on a glass substrate, drying the glass substrate, and heat-treating the solution. How to make a body.
(5) A method for using a laminate according to any one of (1) to (3), wherein the laminate is used for manufacturing an electronic device.
(6) A polyimide precursor solution for laminating a glass substrate, which contains a filler having a coefficient of thermal expansion of 10 ppm / ° C. or less.

本発明の積層体のポリイミド被膜は、ガラス基板に接しているポリイミド被膜のＣＴＥが充分に低く、カールしにくい。カールしたとしても、カールの曲率半径が充分に大きい。また本発明の積層体は、ポリイミド被膜が良好な剥離性を有しているので、フラットパネルディスプレイおよびフレキシブルデバイス等の電子デバイスを製造する際の積層体として好適に用いることができる。 The polyimide film of the laminate of the present invention has a sufficiently low CTE of the polyimide film in contact with the glass substrate and is difficult to curl. Even if curled, the radius of curvature of the curl is large enough. Further, since the polyimide film has good peelability, the laminate of the present invention can be suitably used as a laminate when manufacturing electronic devices such as flat panel displays and flexible devices.

以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.

［積層体］
本発明の積層体は、ガラス基板と、ポリイミド被膜とからなるものである。ガラス基板としては、例えば、ソーダライムガラス、ホウ珪酸ガラス、または無アルカリガラス等からなる基板を用いることができ、これらのなかで、無アルカリガラス基板を好ましく用いることができる。これらのガラス基板は、シランカップリング剤処理等公知の表面処理がなされていてもよい。 [Laminate]
The laminate of the present invention comprises a glass substrate and a polyimide coating. As the glass substrate, for example, a substrate made of soda lime glass, borosilicate glass, non-alkali glass, or the like can be used, and among these, a non-alkali glass substrate can be preferably used. These glass substrates may be subjected to a known surface treatment such as a silane coupling agent treatment.

前記ガラス基板の厚みとしては、０．３～５．０ｍｍが好ましい。厚みが０．３ｍｍより薄いと基板のハンドリング性が低下することがある。また、厚みが５．０ｍｍより厚いと生産性が低下することがある。 The thickness of the glass substrate is preferably 0.3 to 5.0 mm. If the thickness is thinner than 0.3 mm, the handleability of the substrate may deteriorate. Further, if the thickness is thicker than 5.0 mm, the productivity may decrease.

本発明の積層体は、ガラス基板と、このガラス基板上に形成されたフィラ含有ポリイミド層を含むポリイミド被膜とからなる。ここで、フィラ含有ポリイミド層とは、ポリイミド層の全質量に対し、フィラ含有量が５質量％以上であるポリイミド層をいう。フィラ非含有ポリイミド層とは、フィラ含有量が５質量％未満であるポリイミド層をいう。本発明の積層体においては、ポリイミド層に含有されるフィラは、後で詳述するＣＴＥが１０ｐｐｍ／℃以下のフィラ（以下、「特定フィラ」と略記することがある）である。これにより、良好な剥離性を確保することができる。しかも、当該ポリイミド被膜のＣＴＥを充分に低減化できるため、剥離時のカールの発生を充分に防止できる。カールが発生したとしても、カールの曲率半径を充分に大きくすることができる。ポリイミド被膜が特定フィラを含有しないと、当該ポリイミド被膜のＣＴＥを充分に低減化できないため、剥離時にカールの発生を充分に防止できない。また剥離性を確保できないことがある。 The laminate of the present invention comprises a glass substrate and a polyimide film containing a filler-containing polyimide layer formed on the glass substrate. Here, the filler-containing polyimide layer means a polyimide layer having a filler content of 5% by mass or more with respect to the total mass of the polyimide layer. The filler-free polyimide layer means a polyimide layer having a filler content of less than 5% by mass. In the laminated body of the present invention, the filler contained in the polyimide layer is a filler having a CTE of 10 ppm / ° C or less, which will be described in detail later (hereinafter, may be abbreviated as “specific filler”). Thereby, good peelability can be ensured. Moreover, since the CTE of the polyimide film can be sufficiently reduced, the occurrence of curl at the time of peeling can be sufficiently prevented. Even if curl occurs, the radius of curvature of the curl can be sufficiently increased. If the polyimide film does not contain a specific filler, the CTE of the polyimide film cannot be sufficiently reduced, so that the generation of curl cannot be sufficiently prevented at the time of peeling. In addition, peelability may not be ensured.

ポリイミド被膜は、単層の特定フィラ含有ポリイミド層（以下、「層－１」と略記することがある）のみからなってもよいが、当該層－１とフィラ非含有ポリイミド層（以下、「層－２」と略記することがある）とからなる多層構造とし、層－１がガラス基板に直接的に接したものであってもよい。ポリイミド層（層－１または層－２）には、通常ポリイミドフィルム製造の際に用いられる公知の添加剤（例えば、二酸化珪素、酸化アルミニウム等の滑剤等）等が含有されていてもよい。 The polyimide film may consist of only a single layer of a specific filler-containing polyimide layer (hereinafter, may be abbreviated as "layer-1"), but the layer-1 and a filler-free polyimide layer (hereinafter, "layer") may be formed. -2" may be abbreviated), and layer-1 may be in direct contact with the glass substrate. The polyimide layer (layer-1 or layer-2) may contain a known additive (for example, a lubricant such as silicon dioxide or aluminum oxide) usually used in the production of a polyimide film.

ポリイミド被膜（ポリイミド層）とは、原料となるテトラカルボン酸類とジアミンの略等モルを、溶媒中で反応させて得られるポリイミド前駆体であるポリアミック酸（以下、「ＰＡＡ」と略記することがある）溶液をガラス基板上に塗布して、乾燥、熱硬化（イミド化）してポリイミド被膜（ポリイミド層）としたものをいう。ここで、このＰＡＡから得られるポリイミドは、非熱可塑性ポリイミドであることが好ましく、そのガラス転移温度は２５０℃以上であることが好ましい。 The polyimide film (polyimide layer) may be abbreviated as polyamic acid (hereinafter, abbreviated as "PAA"), which is a polyimide precursor obtained by reacting a tetracarboxylic acid as a raw material with an abbreviated molar of diamine in a solvent. ) A solution is applied on a glass substrate, dried and heat-cured (imidized) to form a polyimide film (polyimide layer). Here, the polyimide obtained from this PAA is preferably a non-thermoplastic polyimide, and its glass transition temperature is preferably 250 ° C. or higher.

本発明の積層体においては、ポリイミド被膜が、単層であっても、多層であっても、テトラカルボン酸類として芳香族テトラカルボン酸類を用いたポリイミドから得られる被膜を用いることが好ましい。ここで、芳香族環を有するテトラカルボン酸類（テトラカルボン酸、その二無水物またはエステル化物等）としては、例えば、ピロメリット酸類、３，３’，４，４’－ビフェニルテトラカルボン酸類、２，３，３’，４’－ビフェニルテトラカルボン酸類、２，２’，３，３’－ビフェニルテトラカルボン酸類、４，４’－オキシジフタル酸類、３，３’，４，４’－ベンゾフェノンテトラカルボン酸類、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸類、ｐ－ターフェニルテトラカルボン酸類、ｍ－ターフェニルテトラカルボン酸類等、およびそれらの混合物を挙げることができる。 In the laminate of the present invention, regardless of whether the polyimide coating is a single layer or a multilayer, it is preferable to use a coating obtained from polyimide using aromatic tetracarboxylic acids as tetracarboxylic acids. Here, examples of the tetracarboxylic acids having an aromatic ring (tetracarboxylic acids, dianhydrides thereof, esterified products, etc.) include pyromellitic acids, 3,3', 4,4'-biphenyltetracarboxylic acids, 2 , 3,3', 4'-biphenyltetracarboxylic acids, 2,2', 3,3'-biphenyltetracarboxylic acids, 4,4'-oxydiphthalic acids, 3,3', 4,4'-benzophenone tetracarboxylic acids Examples thereof include acids, 3,3', 4,4'-diphenylsulfonetetracarboxylic acids, p-terphenyltetracarboxylic acids, m-terphenyltetracarboxylic acids and the like, and mixtures thereof.

これらの中で、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、ピロメリット酸二無水物（ＰＭＤＡ）、およびそれらの混合物が好ましい。 Of these, 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and mixtures thereof are preferred.

ポリイミド被膜が多層構造の場合、芳香族テトラカルボン酸類の種類は、層－１および層－２のポリイミドにおいて、同一であっても、異なっていてもよく、好ましくは同一である。 When the polyimide film has a multilayer structure, the types of aromatic tetracarboxylic acids may be the same or different in the polyimides of layer-1 and layer-2, and are preferably the same.

本発明の積層体においては、ポリイミド被膜が、単層であっても、多層であっても、ジアミンとして芳香族ジアミンを用いたポリイミドから得られる被膜を用いることが好ましい。芳香族ジアミンとしては、例えば、ｐ－フェニレンジアミン（ＰＤＡ）、ｍ－フェニレンジアミン、４，４’－オキシジアニリン（ＯＤＡ）、３，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルエーテル（ＤＡＤＥ）、４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－４，４’－ジアミノジフェニルメタン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、１，２－ビス（アニリノ）エタン、ジアミノジフェニルスルホン、ジアミノベンズアニリド、ジアミノベンゾエート、ジアミノジフェニルスルフィド、２，２－ビス（ｐ－アミノフェニル）プロパン、２，２－ビス（ｐ－アミノフェニル）ヘキサフルオロプロパン、１，５－ジアミノナフタレン、ジアミノトルエン、ジアミノベンゾトリフルオライド、１，４－ビス（ｐ－アミノフェノキシ）ベンゼン、４，４’－ビス（ｐ－アミノフェノキシ）ビフェニル、ジアミノアントラキノン、４，４’－ビス（３－アミノフェノキシフェニル）ジフェニルスルホン等、およびそれらの混合物を挙げることができる。これらの芳香族ジアミンは、単体または混合物として使用することができる。 In the laminate of the present invention, regardless of whether the polyimide coating is a single layer or a multilayer, it is preferable to use a coating obtained from polyimide using an aromatic diamine as a diamine. Examples of the aromatic diamine include p-phenylenediamine (PDA), m-phenylenediamine, 4,4'-oxydianiline (ODA), 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether (DADE). ), 4,4'-Diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis (aniline) ) Etan, diaminodiphenylsulfone, diaminobenzaniline, diaminobenzoate, diaminodiphenylsulfide, 2,2-bis (p-aminophenyl) propane, 2,2-bis (p-aminophenyl) hexafluoropropane, 1,5- Diaminonaphthalene, diaminotoluene, diaminobenzotrifluoride, 1,4-bis (p-aminophenoxy) benzene, 4,4'-bis (p-aminophenoxy) biphenyl, diaminoanthraquinone, 4,4'-bis (3-) Aminophenoxyphenyl) diphenylsulfone and the like, and mixtures thereof can be mentioned. These aromatic diamines can be used alone or as a mixture.

これらの中で、ＰＤＡ、ＤＡＤＥ、ＯＤＡおよびそれらの混合物が好ましい。 Of these, PDA, DADE, ODA and mixtures thereof are preferred.

ポリイミド被膜が多層構造の場合、ジアミンの種類は、層－１および層－２のポリイミドにおいて、同一であっても、異なっていてもよく、好ましくは同一である。 When the polyimide film has a multi-layer structure, the type of diamine may be the same or different in the polyimides of layer-1 and layer-2, and is preferably the same.

本発明の積層体においては、ＣＴＥが１０ｐｐｍ／℃以下のフィラを含有したポリイミド被膜を用いる。このようなフィラとしては、ＣＴＥが所定範囲内のフィラであれば特に限定されず、例えば、カーボン粒子（黒鉛、カーボンブラック、カーボンナノチューブ、カーボンナノシート、グラフェン等）、セラミック粒子（窒化珪素、炭化珪素等）、シリコン粒子（同４．７ｐｐｍ／℃）等が挙げられる。ポリイミド被膜における剥離性のさらなる向上およびカールのさらなる防止の観点から、カーボン粒子、シリコン粒子、またはそれらの混合物が好ましい。これらの各フィラは、ＣＴＥが１０ｐｐｍ／℃以下であれば、不純物として他の原子を含むことを妨げるものではない。本発明で用いられるフィラのＣＴＥの下限に特段の制限はない。 In the laminate of the present invention, a polyimide film containing a filler having a CTE of 10 ppm / ° C. or less is used. Such a filler is not particularly limited as long as the CTE is within a predetermined range, and for example, carbon particles (graphite, carbon black, carbon nanotubes, carbon nanosheets, graphene, etc.) and ceramic particles (silicon nitride, silicon carbide). Etc.), silicon particles (4.7 ppm / ° C.) and the like. Carbon particles, silicon particles, or a mixture thereof are preferable from the viewpoint of further improving the peelability of the polyimide film and further preventing curling. Each of these fillers does not prevent the inclusion of other atoms as impurities as long as the CTE is 10 ppm / ° C. or less. There is no particular limitation on the lower limit of the CTE of the filler used in the present invention.

フィラのＣＴＥ値については、 Ｒ．Ｅ． Ｔａｙｌｏｒ， ＣＩＮＤＡＳ Ｄａｔａ Ｓｅｒｉｅｓ ｏｎ Ｍａｔｅｒｉａｌｓ Ｐｒｏｐｅｒｔｉｅｓ， Ｔｈｅｒｍａｌ Ｅｘｐａｎｓｉｏｎ ｏｆ Ｓｏｌｉｄｓ， Ｖｏｌ １-４， ＡＳＭ Ｉｎｔｅｒｎａｔｉｏｎａｌ， １９９８、Ｗｅｌｄｉｎｇ， Ｂｒａｚｉｎｇ， ａｎｄ Ｓｏｌｄｅｒｉｎｇ， Ｖｏｌ ６， ＡＳＭ Ｈａｎｄｂｏｏｋ， ＡＳＭ Ｉｎｔｅｒｎａｔｉｏｎａｌ， １９９３等の文献値を参照することができるが、フィラのＣＴＥが１０ｐｐｍ／℃以下かどうかは、以下のような方法によって判定することもできる。すなわち、ＣＴＥが１０～２０ｐｐｍ／℃のフィラ非含有のポリイミド被膜と、このポリイミド被膜に、被膜質量に対し３０質量％のフィラを含有したポリイミド被膜とのＣＴＥを比較し、フィラ含有ポリイミド被膜のＣＴＥが、フィラ非含有ポリイミド被膜のＣＴＥ以下であれば、そのフィラはＣＴＥが１０ｐｐｍ／℃以下と判定される。逆に、フィラ含有ポリイミド被膜のＣＴＥが、フィラ非含有ポリイミド被膜のＣＴＥを上回れば、そのフィラはＣＴＥが１０ｐｐｍ／℃超と判定される。例えば、銅、銀等の金属粒子はＣＴＥが１０ｐｐｍ／℃を超えており、本発明の積層体のフィラとして用いることはできない。 For the CTE value of Phila, refer to R. E. Taylor, CINDAS Data Series on Materials Properties, Thermal Expansion of Solids, Vol 1-4, ASM International, 1998, Welding, Brazing, and Soldering, However, whether or not the CTE of the filler is 10 ppm / ° C. or less can be determined by the following method. That is, the CTE of the filler-free polyimide film having a CTE of 10 to 20 ppm / ° C. and the polyimide film containing 30% by mass of filler with respect to the film mass is compared, and the CTE of the filler-containing polyimide film is compared. However, if it is CTE or less of the polyimide film containing no filler, the filler is determined to have a CTE of 10 ppm / ° C. or less. On the contrary, if the CTE of the polyimide film containing filler exceeds the CTE of the polyimide film containing no filler, the filler is determined to have a CTE of more than 10 ppm / ° C. For example, metal particles such as copper and silver have a CTE of more than 10 ppm / ° C. and cannot be used as a filler in the laminate of the present invention.

特定フィラの平均粒径範囲は、０．０１～２μｍ程度とすることが好ましい。ここで平均粒径はレーザー回折法で測定した体積基準の測定値をいう。特定フィラの粒子形状は、不定形状、球状、角状、線状等制限はないが、不定形状が好ましい。特定フィラの含有量は、ポリイミド被膜の全質量に対し、５～５０質量％とすることが好ましく、１０～４０質量％とすることがより好ましく、２０～３０質量％とすることが更に好ましい。このようにすることにより、ポリイミド被膜のＣＴＥをさらに充分に低減化できるとともに、さらに良好な剥離性を確保することができる。特定フィラの含有量の基準「ポリイミド被膜の全質量」とは、ポリイミド被膜が単層構造の場合は「当該単層構造のポリイミド被膜を構成するフィラ含有ポリイミド層（層－１）の全質量」のことであり、ポリイミド被膜が多層構造の場合は「当該多層構造のポリイミド被膜を構成するフィラ含有ポリイミド層（層－１）の全質量」のことである。 The average particle size range of the specific filler is preferably about 0.01 to 2 μm. Here, the average particle size refers to a volume-based measured value measured by a laser diffraction method. The particle shape of the specific filler is not limited to an indefinite shape, a spherical shape, a square shape, a linear shape, or the like, but an indefinite shape is preferable. The content of the specific filler is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 20 to 30% by mass with respect to the total mass of the polyimide film. By doing so, the CTE of the polyimide film can be further sufficiently reduced, and further good peelability can be ensured. The standard "total mass of the polyimide film" for the content of the specific filler is "the total mass of the filler-containing polyimide layer (layer-1) constituting the polyimide film having the single-layer structure" when the polyimide film has a single-layer structure. When the polyimide film has a multi-layer structure, it means "the total mass of the filler-containing polyimide layer (layer-1) constituting the polyimide film having the multi-layer structure".

ポリイミド被膜の厚みとしては、ポリイミド被膜が単層構造の場合は、１～５０μｍとすることが好ましい。また、ポリイミド被膜が層－１と層－２とからなる多層構造の場合は、層－１の厚みとしては、０．１～５μｍとすることが好ましく、０．５～４μｍとすることがより好ましい。層－２の厚みとしては５～５０μｍ程度とすることが好ましい。 When the polyimide film has a single-layer structure, the thickness of the polyimide film is preferably 1 to 50 μm. When the polyimide film has a multilayer structure composed of layer-1 and layer-2, the thickness of layer-1 is preferably 0.1 to 5 μm, more preferably 0.5 to 4 μm. preferable. The thickness of the layer-2 is preferably about 5 to 50 μm.

［積層体の製造方法］
本発明の積層体の製造方法は、フィラ含有ポリイミド前駆体溶液をガラス基板上に塗布、乾燥し、熱処理することにより、フィラ含有ポリイミド層（層－１）を形成することを特徴とする。フィラ含有ポリイミド前駆体溶液は、特定フィラを含有するガラス基板積層用ポリイミド前駆体溶液のことである。 [Manufacturing method of laminated body]
The method for producing a laminate of the present invention is characterized in that a filler-containing polyimide layer (layer-1) is formed by applying a filler-containing polyimide precursor solution on a glass substrate, drying the mixture, and heat-treating the mixture. The filler-containing polyimide precursor solution is a polyimide precursor solution for laminating a glass substrate containing a specific filler.

詳しくは、例えばポリイミド被膜が層－１のみからなる単層構造を有する場合、当該ポリイミド被膜は、例えば、特定フィラ未配合のＰＡＡ溶液（以下、「ＰＡＡ－Ｓ」と略記することがある）に、特定フィラを均一に配合したＰＡＡ溶液（以下、「ＰＡＡ－Ｆ」と略記することがある）を、ガラス基板上に、塗布、乾燥したのち、ＰＡＡを熱硬化することにより得られる。この溶液ＰＡＡ－Ｆが前記フィラ含有ポリイミド前駆体溶液に相当するものである。塗布後の乾燥温度としては、８０～１５０℃とすることが好ましい。熱硬化温度としては、３５０～４５０℃とすることが好ましく、３８０～４２０℃とすることがより好ましい。なお、熱硬化温度が高いほど、ポリイミド被膜のＣＴＥは低下するが、ポリイミド被膜とガラス基板との層間の接着強度が増加し、剥離特性は低下する傾向にある。熱硬化温度が４５０℃を超えると、ポリイミド被膜の一部が熱分解する虞がある。 Specifically, for example, when the polyimide film has a single-layer structure consisting of only layer-1, the polyimide film may be added to, for example, a PAA solution containing no specific filler (hereinafter, may be abbreviated as "PAA-S"). , A PAA solution (hereinafter, may be abbreviated as "PAA-F") in which a specific filler is uniformly blended is applied onto a glass substrate, dried, and then thermosetting the PAA. This solution PAA-F corresponds to the filler-containing polyimide precursor solution. The drying temperature after coating is preferably 80 to 150 ° C. The thermosetting temperature is preferably 350 to 450 ° C, more preferably 380 to 420 ° C. The higher the thermosetting temperature, the lower the CTE of the polyimide film, but the adhesive strength between the polyimide film and the glass substrate tends to increase, and the peeling characteristics tend to decrease. If the thermosetting temperature exceeds 450 ° C., a part of the polyimide film may be thermally decomposed.

特定フィラを均一に配合したＰＡＡ溶液には、ステアリン酸、パルミチン酸等の高級脂肪酸、およびそのアミドおよび金属塩等の離形剤を配合することができる。これらの中で、ステアリン酸が好ましい。離形剤の配合量としては、ポリイミド被膜の全質量に対して０．０１～２質量％添加することが好ましく、０．１～１質量％がより好ましい。 A higher fatty acid such as stearic acid and palmitic acid, and a release agent such as an amide and a metal salt thereof can be added to the PAA solution in which the specific filler is uniformly blended. Of these, stearic acid is preferred. The amount of the release agent to be blended is preferably 0.01 to 2% by mass, more preferably 0.1 to 1% by mass, based on the total mass of the polyimide film.

特定フィラを、ＰＡＡ－Ｓに均一に配合するには、プラネタリーミキサー、サンドミル、ボールミル、ジェットミル、三本ロール、撹拌プロペラ等公知の方法を用いて、均一に混合すればよい。これらのＰＡＡ溶液には、必要に応じて、各種界面活性剤および有機シランカップリング剤のような公知の添加物を、本発明の効果を損なわない範囲で添加してもよい。また、必要に応じて、ＰＡＡ以外の他のポリマーを、本発明の効果を損なわない範囲で添加してもよい。 In order to uniformly blend the specific filler into PAA-S, it may be uniformly mixed using a known method such as a planetary mixer, a sand mill, a ball mill, a jet mill, a triple roll, and a stirring propeller. If necessary, known additives such as various surfactants and organic silane coupling agents may be added to these PAA solutions as long as the effects of the present invention are not impaired. Further, if necessary, a polymer other than PAA may be added as long as the effect of the present invention is not impaired.

ＰＡＡ－Ｓは、例えば、前記した芳香族テトラカルボン酸二無水物と、芳香族ジアミンとの略等モルを溶媒中で重合反応させることにより得られる。前記溶媒としては、ＰＡＡを溶解する溶媒であれば、制限はないが、例えば、アミド系溶媒、尿素系溶媒、エーテル系溶媒等を用いることができる。 PAA-S can be obtained, for example, by polymerizing the above-mentioned aromatic tetracarboxylic dianhydride and abbreviated molars of aromatic diamine in a solvent. The solvent is not limited as long as it is a solvent that dissolves PAA, but for example, an amide-based solvent, a urea-based solvent, an ether-based solvent, or the like can be used.

アミド系溶媒の具体例としては、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）等が挙げられる。また、尿素系溶媒の具体例としては、テトラメチル尿素、テトラエチル尿素、ジメチルエチレン尿素、ジメチルプロピレン尿素等が挙げられる。また、エーテル系溶媒の具体例としては、２－メトキシエタノール、２－エトキシエタノール、２－（メトキシメトキシ）エトキシエタノール、２－イソプロポキシエタノール、２－ブトキシエタノール、テトラヒドロフルフリルアルコール、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコール、トリエチレングリコールモノエチルエーテル、テトラエチレングリコール、１－メトキシ－２－プロパノール、１－エトキシ－２－プロパノール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル、ポリエチレングリコール、ポリプロピレングリコール、テトラヒドロフラン、ジオキサン、１，２－ジメトキシエタン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル等が挙げられる。これらの溶媒は、単独または混合物として用いることができる。これらの中で、ＮＭＰ、ＤＭＡｃ、およびそれらの混合物が好ましい。 Specific examples of the amide-based solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc) and the like. Specific examples of the urea-based solvent include tetramethylurea, tetraethylurea, dimethylethyleneurea, and dimethylpropyleneurea. Specific examples of the ether solvent include 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, tetrahydrofurfuryl alcohol, diethylene glycol, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monoethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl Examples thereof include ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, polyethylene glycol, polypropylene glycol, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and the like. These solvents can be used alone or as a mixture. Of these, NMP, DMAc, and mixtures thereof are preferred.

ＰＡＡ溶液を製造する際の反応温度としては、－３０～７０℃が好ましく、－１５～６０℃がより好ましい。またこの反応において、モノマーおよび溶媒の添加順序は特に制限はなく、いかなる順序でもよい。ポリイミド前駆体の固形分濃度としては１～５０質量％が好ましく、５～３０質量％がより好ましい。このＰＡＡは部分的にイミド化されていてもよい。なお、これらのＰＡＡ溶液は市販品も用いることができる。 The reaction temperature for producing the PAA solution is preferably −30 to 70 ° C., more preferably −15 to 60 ° C. Further, in this reaction, the order of adding the monomer and the solvent is not particularly limited, and may be any order. The solid content concentration of the polyimide precursor is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. This PAA may be partially imidized. Commercially available products can also be used as these PAA solutions.

また例えば、ポリイミド被膜が層－１および層－２からなる多層構造を有する場合、当該ポリイミド被膜をガラス基板上に形成するには、先ず、ＰＡＡ－Ｆをガラス板上に塗布、乾燥する。次に、この被膜（層－１）上に、ＰＡＡ－Ｓを塗布、乾燥して層－２を形成後、一括して熱硬化する。塗布後の乾燥温度としては、層－１、層－２共に、８０～１５０℃とすることが好ましい。また、熱硬化温度としては、３５０～４５０℃とすることが好ましく、３８０～４２０℃とすることがより好ましい。なお、層－１を塗布、乾燥した後は、熱硬化することなく、ＰＡＡ－Ｓを塗布することが好ましい。このようにすることにより、層－１と層－２の界面での接着強度が向上し、強固に一体化されたポリイミド被膜とすることができる。 Further, for example, when the polyimide film has a multilayer structure composed of layer-1 and layer-2, in order to form the polyimide film on a glass substrate, PAA-F is first applied on a glass plate and dried. Next, PAA-S is applied onto this film (layer-1), dried to form layer-2, and then heat-cured collectively. The drying temperature after coating is preferably 80 to 150 ° C. for both layer-1 and layer-2. The thermosetting temperature is preferably 350 to 450 ° C, more preferably 380 to 420 ° C. After the layer-1 is applied and dried, it is preferable to apply PAA-S without heat curing. By doing so, the adhesive strength at the interface between the layer-1 and the layer-2 is improved, and a strongly integrated polyimide film can be obtained.

ガラス基板へのＰＡＡ－Ｆの塗布およびＰＡＡ－Ｆ被膜へのＰＡＡ－Ｓの塗布の方法としては、テーブルコータ、ディップコータ、バーコータ、スピンコータ、ダイコータ、スプレーコータ等公知の方法を用い、連続式またはバッチ式で塗布することができる。 As a method of applying PAA-F to a glass substrate and PAA-S to a PAA-F coating, a known method such as a table coater, a dip coater, a bar coater, a spin coater, a die coater, or a spray coater is used, and a continuous method or a continuous method is used. It can be applied in batch form.

本発明においては、ポリイミド被膜が単層構造を有する場合には層－１の上に、多層構造を有する場合には層－２の上に、さらに他のポリマー層を形成してもよい。 In the present invention, another polymer layer may be formed on the layer-1 when the polyimide film has a single-layer structure, and on the layer-2 when the polyimide film has a multi-layer structure.

［用途］
前記のようにして得られた本発明の積層体は、ポリイミド被膜の表面に電子素子を形成後、当該ポリイミド被膜をガラス基板から容易に剥離することができるので、電子デバイスの製造に有用である。ポリイミド被膜には、フィラが含有されているので、その分、ガラス界面との接着強度が弱まり、剥離を容易に行うことができる。また剥離後において、電子素子が形成されたポリイミド被膜はカールが充分に防止されている。 [Use]
The laminate of the present invention obtained as described above is useful for manufacturing electronic devices because the polyimide film can be easily peeled off from the glass substrate after forming an electronic element on the surface of the polyimide film. .. Since the polyimide film contains a filler, the adhesive strength with the glass interface is weakened by that amount, and peeling can be easily performed. Further, after peeling, the polyimide film on which the electronic element is formed is sufficiently prevented from curling.

電子素子としては、従来より電子デバイスの分野で用いられているあらゆる電子素子が使用可能である。電子素子の形成方法は、ポリイミド被膜（フィルム）をフレキシブル基板として用いる電子デバイスの分野で公知の方法を採用することができる。 As the electronic element, any electronic element conventionally used in the field of electronic devices can be used. As a method for forming an electronic element, a method known in the field of electronic devices using a polyimide film (film) as a flexible substrate can be adopted.

電子デバイスとしては、例えば、液晶ディスプレイ（ＬＣＤ）、プラズマディスプレイパネル（ＰＤＰ）、有機ＥＬディスプレイ（ＯＬＥＤ）等のフラットパネルディスプレイ（ＦＰＤ）；および電子ペーパー等のフレキシブルデバイスが挙げられる。 Examples of the electronic device include a flat panel display (FPD) such as a liquid crystal display (LCD), a plasma display panel (PDP), and an organic EL display (OLED); and a flexible device such as an electronic paper.

以下、本発明を実施例に基づいて具体的に説明するが、これらの実施例によって限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

＜フィラ非含有ポリイミド前駆体溶液ＰＡＡ－Ｓ１～ＰＡＡ－Ｓ２の調製＞
（ＰＡＡ－Ｓ１）
ガラス製反応容器に、窒素雰囲気下、ＰＤＡ（０．６モル）と脱水したＤＭＡｃ（重合溶媒）を投入して攪拌し、ＰＤＡを溶解した。この溶液をジャケットで３０℃以下に冷却しながら、ＢＰＤＡ（０．６モル）を徐々に加えた後、５０℃で１００分重合反応させることにより、ポリイミド前駆体溶液 ＰＡＡ－Ｓ１を得た。ＰＡＡ－Ｓ１の固形分濃度は１５質量％であり、ＧＰＣによるポリスチレン換算の重量平均分子量（Ｍｗ）は６２０００であった。 <Preparation of filler-free polyimide precursor solutions PAA-S1 to PAA-S2>
(PAA-S1)
PDA (0.6 mol) and dehydrated DMAc (polymerization solvent) were put into a glass reaction vessel under a nitrogen atmosphere and stirred to dissolve the PDA. While cooling this solution to 30 ° C. or lower with a jacket, BPDA (0.6 mol) was gradually added and then polymerized at 50 ° C. for 100 minutes to obtain a polyimide precursor solution PAA-S1. The solid content concentration of PAA-S1 was 15% by mass, and the polystyrene-equivalent weight average molecular weight (Mw) by GPC was 62000.

（ＰＡＡ－Ｓ２）
「ＰＤＡ（０．６モル）」を「ＰＤＡ（０．５モル）およびＯＤＡ（０．１モル）の混合物」としたこと以外は、ＰＡＡ－Ｓ１と同様にして、ポリイミド前駆体溶液ＰＡＡ－Ｓ２を得た。ＰＡＡ－Ｓ２の固形分濃度は１６質量％であり、ＧＰＣによるポリスチレン換算の重量平均分子量（Ｍｗ）は７２０００であった。 (PAA-S2)
Polyimide precursor solution PAA-S2 in the same manner as PAA-S1 except that "PDA (0.6 mol)" was changed to "a mixture of PDA (0.5 mol) and ODA (0.1 mol)". Got The solid content concentration of PAA-S2 was 16% by mass, and the polystyrene-equivalent weight average molecular weight (Mw) by GPC was 72000.

＜フィラ含有ポリイミド前駆体溶液ＰＡＡ－Ｆ２～ＰＡＡ－Ｆ６の調製＞
〔実施例１〕
（ＰＡＡ－Ｆ２）
ＰＡＡ－Ｓ１に、シリコン粒子（平均粒径：０．５μｍ、ＣＴＥ：４．７ｐｐｍ／℃）と脱水したＤＭＡｃ（希釈溶媒）を加え、プラネタリーミキサーを用いて６０分間混合処理を行い、固形分が１６質量％、シリコン粒子含有量が全固形分質量（シリコン粒子質量＋ポリイミド換算質量）に対し、３０質量％のフィラ含有ポリイミド前駆体溶液 ＰＡＡ－Ｆ２を得た。 <Preparation of filler-containing polyimide precursor solutions PAA-F2 to PAA-F6>
[Example 1]
(PAA-F2)
Silicon particles (average particle size: 0.5 μm, CTE: 4.7 ppm / ° C.) and dehydrated DMAc (diluted solvent) were added to PAA-S1 and mixed for 60 minutes using a planetary mixer to obtain a solid content. PAA-F2 was obtained as a filler-containing polyimide precursor solution having a mass of 16% by mass and a silicon particle content of 30% by mass with respect to the total solid content mass (silicon particle mass + polyimide equivalent mass).

（ＰＡＡ－Ｆ３）
シリコン粒子含有量を全固形分質量に対し、２０質量％としたこと以外は、ＰＡＡ－Ｆ２と同様にして、ＰＡＡ－Ｆ３を得た。 (PAA-F3)
PAA-F3 was obtained in the same manner as PAA-F2 except that the silicon particle content was 20% by mass with respect to the total solid content mass.

（ＰＡＡ－Ｆ４）
フィラとして黒鉛粒子（平均粒径：０．３μｍ、ＣＴＥ：０．５ｐｐｍ／℃）を用いたこと以外は、ＰＡＡ－Ｆ２と同様にして、ＰＡＡ－Ｆ４を得た。 (PAA-F4)
PAA-F4 was obtained in the same manner as PAA-F2 except that graphite particles (average particle size: 0.3 μm, CTE: 0.5 ppm / ° C.) were used as the filler.

（ＰＡＡ－Ｆ５）
フィラとしてカーボンブラック（平均粒径０．０３μｍのチャンネルブラック、ＣＴＥ：０．５ｐｐｍ／℃）を用い、カーボンブラック含有量を、全固形分質量に対し、２３質量％としたこと以外は、ＰＡＡ－Ｆ２と同様にして、ＰＡＡ－Ｆ５を得た。 (PAA-F5)
PAA- PAA-F5 was obtained in the same manner as F2.

（ＰＡＡ－Ｆ６）
ＰＡＡ－Ｓ２に、シリコン粒子（平均粒径：０．５μｍ、ＣＴＥ：４．７ｐｐｍ／℃）、ステアリン酸、脱水したＤＭＡｃ（希釈溶媒）を加え、プラネタリーミキサーを用いて６０分間混合処理を行い、全固形分質量（シリコン粒子質量＋ポリイミド換算質量＋ステアリン酸）に対し、シリコン粒子を３０質量％、ステアリン酸を０．５質量％含有したポリイミド前駆体溶液ＰＡＡ－Ｆ６を得た。 (PAA-F6)
Silicon particles (average particle size: 0.5 μm, CTE: 4.7 ppm / ° C.), stearic acid, and dehydrated DMAc (diluting solvent) were added to PAA-S2, and the mixture was mixed for 60 minutes using a planetary mixer. , A polyimide precursor solution PAA-F6 containing 30% by mass of silicon particles and 0.5% by mass of stearic acid with respect to the total solid content mass (silicon particle mass + polyimide reduced mass + stearic acid) was obtained.

〔比較例１〕
（ＰＡＡ－Ｆ７）
フィラとして銅粒子（平均粒径：０．６μｍ、ＣＴＥ：１７ｐｐｍ／℃）を用いたこと以外は、ＰＡＡ－Ｆ２と同様にして、ＰＡＡ－Ｆ７得た。 [Comparative Example 1]
(PAA-F7)
PAA-F7 was obtained in the same manner as PAA-F2 except that copper particles (average particle size: 0.6 μm, CTE: 17 ppm / ° C.) were used as the filler.

＜単層構造型積層体の製造＞
〔実施例２〕
厚み０．７ｍｍの無アルカリガラス基板（ＣＴＥ：３．２ｐｐｍ／℃）の表面上に、フィラ含有ポリイミド前駆体溶液ＰＡＡ－Ｆ２をテーブルコータにより塗布し、１３０℃で１０分間乾燥してＰＡＡ被膜を形成した。次いで、窒素ガス気流下で、１００℃から４００℃まで２時間かけて昇温した後、４００℃で２時間熱処理し、ＰＡＡを熱硬化させてイミド化した。これによって、ガラス基板と厚み約１５μｍのフィラ含有ポリイミド被膜とからなる積層体Ａ－２を得た。 <Manufacturing of single-layer structure type laminate>
[Example 2]
A filler-containing polyimide precursor solution PAA-F2 is applied on the surface of a 0.7 mm-thick non-alkali glass substrate (CTE: 3.2 ppm / ° C.) with a table coater, and dried at 130 ° C. for 10 minutes to form a PAA coating. Formed. Then, the temperature was raised from 100 ° C. to 400 ° C. for 2 hours under a nitrogen gas stream, and then heat-treated at 400 ° C. for 2 hours to thermoset the PAA and imidize it. As a result, a laminate A-2 composed of a glass substrate and a filler-containing polyimide film having a thickness of about 15 μm was obtained.

（被膜のＣＴＥ）
積層体Ａ－２からポリイミド被膜を剥離して、ＣＴＥを測定した結果、ＣＴＥは６．３ｐｐｍ／℃であった。なお、ＣＴＥの測定は、パーキンエルマー社製ＴＭＡ－７を用い、１３ｍｍ×３ｍｍの試料に対して長手方向に２０ｍＮの荷重を加え、１０℃／分の昇温速度で測定したときの１００℃～２５０℃における寸法変化量を測定することにより行った。Ａ－２のポリイミド被膜のＣＴＥ測定結果を表１に示す。 (CTE of coating)
As a result of peeling the polyimide film from the laminate A-2 and measuring the CTE, the CTE was 6.3 ppm / ° C. The CTE was measured using TMA-7 manufactured by PerkinElmer Co., Ltd., and a load of 20 mN was applied to a sample of 13 mm × 3 mm in the longitudinal direction, and the temperature was measured at a temperature rise rate of 10 ° C./min. This was done by measuring the amount of dimensional change at 250 ° C. Table 1 shows the CTE measurement results of the polyimide film of A-2.

（剥離特性）
積層体Ａ－２のポリイミド被膜とガラス基板界面との剥離特性を以下のようにして評価した。すなわち、ポリイミド被膜とガラス基板界面との接着強度をＪＩＳ Ｋ６８５４に基づいて１８０°剥離試験により測定し、接着強度が０．１Ｎ／ｃｍ未満の場合、界面での剥離特性が「良好」と判定した。逆に、接着強度が０．１Ｎ／ｃｍ以上の場合、剥離特性が「不良」と判定した。Ａ－２の剥離特性評価結果を表１に示す。 (Peeling characteristics)
The peeling characteristics between the polyimide film of the laminate A-2 and the interface of the glass substrate were evaluated as follows. That is, the adhesive strength between the polyimide film and the glass substrate interface was measured by a 180 ° peeling test based on JIS K6854, and when the adhesive strength was less than 0.1 N / cm, the peeling property at the interface was judged to be "good". .. On the contrary, when the adhesive strength was 0.1 N / cm or more, the peeling property was judged to be "poor". Table 1 shows the peeling characteristic evaluation results of A-2.

（カール特性）
次に、積層体から剥離されたポリイミド被膜のカール特性を以下のようにして評価した。すなわち、ガラス基板から剥離して、１０ｃｍ角に切り出したポリイミド被膜の曲率半径を測定した。その曲率半径が５０ｍｍ以上の場合、カール特性が「良好」と判定した。逆に、曲率半径が５０ｍｍ未満の場合、カール特性が「不良」と判定した。Ａ－２から得られたポリイミド被膜のカール特性評価結果を表１に示す。 (Curl characteristics)
Next, the curl characteristics of the polyimide film peeled from the laminate were evaluated as follows. That is, the radius of curvature of the polyimide film cut out into a 10 cm square by peeling from the glass substrate was measured. When the radius of curvature was 50 mm or more, the curl characteristic was judged to be "good". On the contrary, when the radius of curvature is less than 50 mm, the curl characteristic is determined to be "defective". Table 1 shows the curl characteristic evaluation results of the polyimide film obtained from A-2.

〔実施例３〕
フィラ含有ポリイミド前駆体溶液として、ＰＡＡ－Ｆ３を用いたこと以外は、実施例２と同様に行い、フィラ含有ポリイミド被膜からなる積層体Ａ－３を得た。Ａ－３の被膜ＣＴＥ、剥離特性、およびカール特性を実施例２と同様の方法により測定または評価し、表１に示す。 [Example 3]
The same procedure as in Example 2 was carried out except that PAA-F3 was used as the filler-containing polyimide precursor solution to obtain a laminate A-3 composed of a filler-containing polyimide coating. The coating CTE, peeling characteristics, and curling characteristics of A-3 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.

〔実施例４〕
フィラ含有ポリイミド前駆体溶液として、ＰＡＡ－Ｆ４を用いたこと以外は、実施例２と同様に行い、フィラ含有ポリイミド被膜からなる積層体Ａ－４を得た。Ａ－４の被膜ＣＴＥ、剥離特性、およびカール特性を実施例２と同様の方法により測定または評価し、表１に示す。 [Example 4]
The same procedure as in Example 2 was carried out except that PAA-F4 was used as the filler-containing polyimide precursor solution to obtain a laminate A-4 composed of a filler-containing polyimide coating. The coating CTE, peeling characteristics, and curling characteristics of A-4 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.

〔実施例５〕（参考例）
フィラ含有ポリイミド前駆体溶液として、ＰＡＡ－Ｆ５を用いたこと以外は、実施例２と同様に行い、フィラ含有ポリイミド被膜からなる積層体Ａ－５を得た。Ａ－５の被膜ＣＴＥ、剥離特性、およびカール特性を実施例２と同様の方法により測定または評価し、表１に示す。
[Example 5] (Reference example)
The same procedure as in Example 2 was carried out except that PAA-F5 was used as the filler-containing polyimide precursor solution to obtain a laminate A-5 composed of a filler-containing polyimide coating. The coating CTE, peeling characteristics, and curling characteristics of A-5 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.

〔実施例６〕
厚み０．７ｍｍの無アルカリガラス基板（ＣＴＥ：３．２ｐｐｍ／℃）の表面上に、ＰＡＡ－Ｆ６をテーブルコータにより塗布し、１３０℃で１０分間乾燥してＰＡＡ被膜を形成した。次いで、窒素ガス気流下で、１００℃から３８０℃まで２時間かけて昇温した後、３８０℃で２時間熱処理し、ＰＡＡを熱硬化させてイミド化した。これによって、ガラス基板と厚み約２０μｍのフィラ含有ポリイミド被膜とからなる積層体Ａ－６を得た。Ａ－６の被膜ＣＴＥ、剥離特性、およびカール特性を実施例２と同様の方法により測定または評価し、表１に示す。 [Example 6]
PAA-F6 was applied on the surface of a non-alkali glass substrate (CTE: 3.2 ppm / ° C.) having a thickness of 0.7 mm with a table coater and dried at 130 ° C. for 10 minutes to form a PAA film. Then, the temperature was raised from 100 ° C. to 380 ° C. over 2 hours under a nitrogen gas stream, and then heat-treated at 380 ° C. for 2 hours to thermoset the PAA and imidize it. As a result, a laminate A-6 composed of a glass substrate and a filler-containing polyimide film having a thickness of about 20 μm was obtained. The coating CTE, peeling characteristics, and curling characteristics of A-6 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.

〔比較例２〕
ポリイミド前駆体溶液として、ＰＡＡ－Ｓ１を用いたこと以外は、実施例２と同様に行い、フィラを含有しないポリイミド被膜からなる積層体ＡＲ－１を得た。ＡＲ－１の被膜ＣＴＥ、剥離特性、およびカール特性を実施例２と同様の方法により測定または評価し、表１に示す。 [Comparative Example 2]
The same procedure as in Example 2 was carried out except that PAA-S1 was used as the polyimide precursor solution to obtain a laminated body AR-1 composed of a polyimide coating containing no filler. The coating CTE, peeling characteristics, and curling characteristics of AR-1 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.

〔比較例３〕
フィラ含有ポリイミド前駆体溶液として、ＰＡＡ－Ｓ２を用いたこと以外は、実施例２と同様に行い、フィラ含有ポリイミド被膜からなる積層体ＡＲ－２を得た。ＡＲ－２の被膜ＣＴＥ、剥離特性、およびカール特性を実施例２と同様の方法により測定または評価し、表１に示す。 [Comparative Example 3]
The same procedure as in Example 2 was carried out except that PAA-S2 was used as the filler-containing polyimide precursor solution to obtain a laminated body AR-2 composed of a filler-containing polyimide coating. The coating CTE, peeling characteristics, and curling characteristics of AR-2 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.

〔比較例４〕
フィラ含有ポリイミド前駆体溶液として、ＰＡＡ－Ｆ７を用いたこと以外は、実施例２と同様に行い、フィラ含有ポリイミド被膜からなる積層体ＡＲ－７を得た。ＡＲ－７の被膜ＣＴＥ、剥離特性、およびカール特性を実施例２と同様の方法により測定または評価し、表１に示す。 [Comparative Example 4]
The same procedure as in Example 2 was carried out except that PAA-F7 was used as the filler-containing polyimide precursor solution to obtain a laminated body AR-7 composed of a filler-containing polyimide coating. The coating CTE, peeling properties, and curling properties of the AR-7 were measured or evaluated by the same method as in Example 2, and are shown in Table 1.

Figure 0006996764000001
Figure 0006996764000001

表１に示したように、本発明の積層体Ａ－２～Ａ－６は、ガラス基板に接している層に、所定のフィラが含有されている。このため、ポリイミド被膜の剥離特性が良好であり、かつＣＴＥが低く、カール特性も良好であることが判る。 As shown in Table 1, in the laminates A-2 to A-6 of the present invention, a predetermined filler is contained in the layer in contact with the glass substrate. Therefore, it can be seen that the peeling property of the polyimide film is good, the CTE is low, and the curl property is also good.

これに対し、比較例４で示したＡＲ－７のポリイミド被膜には、フィラが含有されているので、剥離特性は良好であっても、フィラである銅粒子のＣＴＥが高いために、カール特性が不良であることが判る。
また、比較例２，３で示したように、フィラ非含有のポリイミド被膜では、剥離特性およびカール特性が共に不良であることが判る。 On the other hand, since the polyimide film of AR-7 shown in Comparative Example 4 contains a filler, even if the peeling characteristic is good, the CTE of the copper particles as the filler is high, so that the curl characteristic is obtained. Turns out to be defective.
Further, as shown in Comparative Examples 2 and 3, it can be seen that both the peeling property and the curl property are poor in the polyimide film containing no filler.

＜複層構造型積層体の製造＞
〔実施例７〕
前記無アルカリガラス基板の表面上にＰＡＡ－Ｆ２をテーブルコータにより塗布し、１３０℃で１０分間乾燥してＰＡＡ被膜を形成した。次いで、室温（２５℃）に戻し、このＰＡＡ被膜上に、ＰＡＡ－Ｓ１をテーブルコータによって塗布し、１３０℃で１０分間乾燥して２層目のＰＡＡ被膜を形成した。次いで、窒素ガス気流下で、１００℃から４００℃まで２時間かけて昇温した後、４００℃で２時間熱処理し、ＰＡＡを熱硬化させてイミド化した。これによって、ガラス基板と、このガラス基板上に層－１（フィラ含有ポリイミド層：厚み３μｍ）および層－２（フィラ非含有ポリイミド層：厚み２０μｍ）がこの順に形成されたポリイミド被膜（厚み：２３μｍ）とからなる積層体Ｌ－２を得た。この剥離特性およびカール特性を実施例２と同様の方法により評価し、表２に示す。 <Manufacturing of multi-layer structure type laminate>
[Example 7]
PAA-F2 was applied on the surface of the non-alkali glass substrate with a table coater and dried at 130 ° C. for 10 minutes to form a PAA film. Then, the temperature was returned to room temperature (25 ° C.), PAA-S1 was applied onto the PAA coating with a table coater, and dried at 130 ° C. for 10 minutes to form a second PAA coating. Then, the temperature was raised from 100 ° C. to 400 ° C. for 2 hours under a nitrogen gas stream, and then heat-treated at 400 ° C. for 2 hours to thermoset the PAA and imidize it. As a result, a glass substrate and a polyimide film (thickness: 23 μm) in which layer-1 (fila-containing polyimide layer: thickness 3 μm) and layer-2 (filler-free polyimide layer: thickness 20 μm) are formed on the glass substrate in this order. ) Was obtained. The peeling characteristics and curling characteristics are evaluated by the same method as in Example 2 and are shown in Table 2.

〔実施例８〕
層－１形成用として、ＰＡＡ－Ｆ３を用いたこと以外は、実施例７と同様にして、ガラス基板と、このガラス基板上に、層－１（フィラ含有ポリイミド層：厚み３μｍ）および層－２（フィラ非含有ポリイミド層：厚み２１μｍ）がこの順に形成されたポリイミド被膜（厚み：２４μｍ）とからなる積層体Ｌ－３を得た。この剥離特性およびカール特性を実施例２と同様の方法により評価し、表２に示す。 [Example 8]
A glass substrate and a layer-1 (fila-containing polyimide layer: thickness 3 μm) and a layer-on the glass substrate in the same manner as in Example 7 except that PAA-F3 was used for forming the layer-1. A laminated body L-3 composed of a polyimide film (thickness: 24 μm) in which 2 (fila-free polyimide layer: thickness 21 μm) was formed in this order was obtained. The peeling characteristics and curling characteristics are evaluated by the same method as in Example 2 and are shown in Table 2.

〔実施例９〕
層－１形成用として、ＰＡＡ－Ｆ４を用いたこと以外は、実施例７と同様にして、ガラス基板と、このガラス基板上に、層－１（フィラ含有ポリイミド層：厚み２μｍ）および層－２（フィラ非含有ポリイミド層：厚み２０μｍ）がこの順に形成されたポリイミド被膜（厚み：２２μｍ）とからなる積層体Ｌ－４を得た。この剥離特性およびカール特性を実施例２と同様の方法により評価し、表２に示す。 [Example 9]
A glass substrate and a layer-1 (fila-containing polyimide layer: thickness 2 μm) and a layer-on the glass substrate in the same manner as in Example 7 except that PAA-F4 was used for forming the layer-1. A laminated body L-4 composed of a polyimide film (thickness: 22 μm) in which 2 (fila-free polyimide layer: thickness 20 μm) was formed in this order was obtained. The peeling characteristics and curling characteristics are evaluated by the same method as in Example 2 and are shown in Table 2.

〔実施例１０〕（参考例）
層－１形成用として、ＰＡＡ－Ｆ５を用いたこと以外は、実施例７と同様にして、ガラス基板と、このガラス基板上に、層－１（フィラ含有ポリイミド層：厚み２μｍ）および層－２（フィラ非含有ポリイミド層：厚み２１μｍ）がこの順に形成されたポリイミド被膜（厚み：２３μｍ）とからなる積層体Ｌ－５を得た。この剥離特性およびカール特性を実施例２と同様の方法により評価し、表２に示す。

[Example 10] (Reference example)
A glass substrate and a layer-1 (fila-containing polyimide layer: thickness 2 μm) and a layer-on the glass substrate in the same manner as in Example 7 except that PAA-F5 was used for forming the layer-1. A laminated body L-5 composed of a polyimide film (thickness: 23 μm) in which 2 (fila-free polyimide layer: thickness 21 μm) was formed in this order was obtained. The peeling characteristics and curling characteristics are evaluated by the same method as in Example 2 and are shown in Table 2.

〔実施例１１〕
層－１形成用として、ＰＡＡ－Ｆ６を用いたこと以外は、実施例７と同様にして、ガラス基板と、このガラス基板上に、層－１（フィラ含有ポリイミド層：厚み２μｍ）および層－２（フィラ非含有ポリイミド層：厚み２１μｍ）がこの順に形成されたポリイミド被膜（厚み：２３μｍ）とからなる積層体Ｌ－６を得た。この剥離特性およびカール特性を実施例２と同様の方法により評価し、表２に示す。 [Example 11]
A glass substrate and a layer-1 (fila-containing polyimide layer: thickness 2 μm) and a layer-on the glass substrate in the same manner as in Example 7 except that PAA-F6 was used for forming the layer-1. A laminated body L-6 composed of a polyimide film (thickness: 23 μm) in which 2 (fila-free polyimide layer: thickness 21 μm) was formed in this order was obtained. The peeling characteristics and curling characteristics are evaluated by the same method as in Example 2 and are shown in Table 2.

〔比較例５〕
層－１形成用として、フィラ非含有のＰＡＡ－Ｓ１を用いたこと以外は、実施例７と同様にして、ガラス基板と、このガラス基板上に、層－１（フィラ非含有ポリイミド層：厚み３μｍ）および層－２（フィラ非含有ポリイミド層：厚み２０μｍ）がこの順に形成されたポリイミド被膜（厚み：２３μｍ）とからなる積層体ＬＲ－１を得た。この剥離特性およびカール特性を実施例２と同様の方法により評価し、表２に示す。 [Comparative Example 5]
Layer-1 (fila-free polyimide layer: thickness) was placed on the glass substrate and the glass substrate in the same manner as in Example 7 except that PAA-S1 containing no filler was used for forming the layer-1. A laminated body LR-1 composed of a polyimide film (thickness: 23 μm) in which 3 μm) and layer-2 (fila-free polyimide layer: thickness 20 μm) were formed in this order was obtained. The peeling characteristics and curling characteristics are evaluated by the same method as in Example 2 and are shown in Table 2.

〔比較例６〕
層－１形成用として、ＰＡＡ－Ｆ７を用いたこと以外は、実施例７と同様にして、ガラス基板と、このガラス基板上に、層－１（フィラ含有ポリイミド層：厚み３μｍ）および層－２（フィラ非含有ポリイミド層：厚み２０μｍ）がこの順に形成されたポリイミド被膜（厚み：２３μｍ）とからなる積層体ＬＲ－７を得た後、この剥離特性およびカール特性を実施例２と同様の方法により評価し、表２に示す。 [Comparative Example 6]
A glass substrate and a layer-1 (fila-containing polyimide layer: thickness 3 μm) and a layer-on the glass substrate in the same manner as in Example 7 except that PAA-F7 was used for forming the layer-1. After obtaining a laminated body LR-7 composed of a polyimide film (thickness: 23 μm) in which 2 (fila-free polyimide layer: thickness 20 μm) was formed in this order, the peeling characteristics and curl characteristics were the same as in Example 2. Evaluated by the method and shown in Table 2.

Figure 0006996764000002
Figure 0006996764000002

表２に示したように、本発明の積層体Ｌ－２～Ｌ－６は、ガラス基板に接している層－１には、所定のフィラが含有されている。このため、剥離特性が良好であり、かつ層－１のＣＴＥが低く、カール特性も良好であることが判る。 As shown in Table 2, in the laminated bodies L-2 to L-6 of the present invention, the layer-1 in contact with the glass substrate contains a predetermined filler. Therefore, it can be seen that the peeling characteristics are good, the CTE of the layer-1 is low, and the curling characteristics are also good.

これに対し、比較例６で示したＬＲ－７の層－１には、フィラが含有されているので、剥離特性は良好であっても、フィラである銅粒子のＣＴＥが高いために、カール特性が不良であることが判る。
また、比較例５より、層－１としてフィラ非含有のポリイミド被膜を用いると、ポリイミド被膜が多層であっても、剥離特性およびカール特性が共に不良であることが判る。 On the other hand, since the layer-1 of LR-7 shown in Comparative Example 6 contains a filler, even if the peeling characteristics are good, the CTE of the copper particles which are the fillers is high, so that the curls are formed. It turns out that the characteristics are poor.
Further, from Comparative Example 5, it can be seen that when the polyimide film containing no filler is used as the layer-1, both the peeling property and the curl property are poor even if the polyimide film has a plurality of layers.

本発明の積層体は、良好な剥離性を有し、かつ剥離されたポリイミド被膜がカールしにくいので、当該積層体を構成するポリイミド被膜の表面に電子素子を形成することにより電子デバイスの製造に有用である。 Since the laminate of the present invention has good peelability and the peeled polyimide coating is difficult to curl, it is possible to manufacture an electronic device by forming an electronic element on the surface of the polyimide coating constituting the laminate. It is useful.

Claims (5)

ガラス基板と、このガラス基板上に形成されたフィラ含有ポリイミド層を含むポリイミド被膜とからなる積層体であって、前記フィラが黒鉛粒子および／またはシリコン粒子であり、前記フィラの含有量が、ポリイミド被膜の全質量に対し、１０～４０質量％（ただし、１０質量％を除く）であることを特徴とする積層体。 A laminate composed of a glass substrate and a polyimide film containing a filler-containing polyimide layer formed on the glass substrate, wherein the filler is graphite particles and / or silicon particles, and the content of the filler is polyimide. A laminate characterized in that it is 10 to 40% by mass (excluding 10% by mass) with respect to the total mass of the coating film. 前記ポリイミド被膜が、前記フィラ含有ポリイミド層、および当該フィラ含有ポリイミド層上に形成されたフィラ非含有ポリイミド層を含む、請求項１に記載の積層体。 The laminate according to claim 1, wherein the polyimide film includes the filler-containing polyimide layer and the filler-free polyimide layer formed on the filler-containing polyimide layer. フィラ含有ポリイミド前駆体溶液をガラス基板上に塗布、乾燥し、熱処理することにより、フィラ含有ポリイミド層を形成することを特徴とする請求項１または２に記載の積層体の製造方法。 The method for producing a laminate according to claim 1 or 2, wherein a filler-containing polyimide layer is formed by applying a filler-containing polyimide precursor solution on a glass substrate, drying the glass substrate, and heat-treating the mixture. 請求項１または２に記載の積層体を電子デバイスの製造に用いることを特徴とする積層体の使用方法。 A method for using a laminate according to claim 1 or 2, wherein the laminate is used for manufacturing an electronic device. 黒鉛粒子および／またはシリコン粒子をフィラとして含有し、前記フィラの含有量が、全固形分質量に対し、１０～４０質量％（ただし、１０質量％を除く）であることを特徴とするガラス基板積層用ポリイミド前駆体溶液。 A glass substrate containing graphite particles and / or silicon particles as a filler, and the content of the filler is 10 to 40% by mass (excluding 10% by mass) with respect to the total solid content mass. Polyimide precursor solution for lamination.
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