JP2020199766A - Laminated substrate, and package - Google Patents

Laminated substrate, and package Download PDF

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Publication number
JP2020199766A
JP2020199766A JP2020086614A JP2020086614A JP2020199766A JP 2020199766 A JP2020199766 A JP 2020199766A JP 2020086614 A JP2020086614 A JP 2020086614A JP 2020086614 A JP2020086614 A JP 2020086614A JP 2020199766 A JP2020199766 A JP 2020199766A
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Prior art keywords
resin layer
protective film
polyimide resin
base material
laminated substrate
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JP7115510B2 (en
Inventor
洋平 長尾
Yohei Nagao
洋平 長尾
周馬 川崎
Shuma Kawasaki
周馬 川崎
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AGC Inc
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Asahi Glass Co Ltd
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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
    • 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
    • B32B17/10009—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 number, the constitution or treatment of glass sheets
    • B32B17/10018—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 number, the constitution or treatment of glass sheets comprising only one glass sheet
    • 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
    • B32B27/28—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
    • 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
    • B32B27/283—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 polysiloxanes
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • 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
    • 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
    • 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
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D71/00—Bundles of articles held together by packaging elements for convenience of storage or transport, e.g. portable segregating carrier for plural receptacles such as beer cans or pop bottles; Bales of material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68377—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support with parts of the auxiliary support remaining in the finished device

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Buffer Packaging (AREA)
  • Packaging Frangible Articles (AREA)

Abstract

To provide a laminated substrate that suppresses flaw generation on the surface of a polyimide resin layer when laminated, damage of a support substrate when peeling a protective film, and foreign matter generation on the polyimide resin layer, and to provide a package on which a plurality of the laminated substrates are mounted.SOLUTION: A laminated substrate is formed by laminating a polyimide resin layer and a protective film covering the polyimide resin layer on a support substrate made of glass. Following expressions are satisfied, wherein F1 is a first adhesion force between the polyimide resin layer and the protective film and F2 is a second adhesion force between the support substrate and the protective film. 0.001 N/10 mm≤F1≤0.17 N/10 mm, 0.05 N/10 mm≤F2≤(F1(N/10 mm)+0.3 N/10 mm).SELECTED DRAWING: Figure 2

Description

本発明は、積層基板、および、梱包体に関する。 The present invention relates to a laminated substrate and a package.

太陽電池；液晶パネル（ＬＣＤ）；有機ＥＬパネル（ＯＬＥＤ）；電磁波、Ｘ線、紫外線、可視光線、赤外線等を感知する受信センサーパネル；等の電子デバイスを製造する際に、特許文献１に記載されるように、ポリイミド樹脂層を基板として用いる態様が開示されている。ポリイミド樹脂層は、ガラス基板上に設けられた積層基板の状態で用いられ、積層基板が電子デバイスの製造に提供されている。電子デバイスを形成した後、ポリイミド樹脂層とガラス基板とが分離される。 Described in Patent Document 1 when manufacturing electronic devices such as solar cells; liquid crystal panels (LCDs); organic EL panels (OLEDs); receiving sensor panels that detect electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, etc. As described above, an embodiment in which the polyimide resin layer is used as a substrate is disclosed. The polyimide resin layer is used in the state of a laminated substrate provided on a glass substrate, and the laminated substrate is provided for manufacturing an electronic device. After forming the electronic device, the polyimide resin layer and the glass substrate are separated.

一方で、複数のガラス基板を搬送する際、例えば、特許文献２に記載されるように、バージンパルプからなる合紙を介して複数のガラス板を積層してなるガラス板梱包体の形で搬送される。 On the other hand, when transporting a plurality of glass substrates, for example, as described in Patent Document 2, the plurality of glass plates are laminated in the form of a glass plate package formed by laminating a plurality of glass plates via an interleaving paper made of virgin pulp. Will be done.

日本国特開２０１５−１０４８４３号公報Japanese Patent Application Laid-Open No. 2015-104843 日本国内公開第２０１６／１０４４５０号Published in Japan 2016/10450

上述したように、積層基板中のポリイミド樹脂層上には、電子デバイスを構成する各種電子デバイス用部材が形成されるため、ポリイミド樹脂層の表面にはキズや異物がないことが望ましい。
一方で、本発明者らは、特許文献２に記載されるように、バージンパルプからなる合紙を介して、ガラス基板上にポリイミド樹脂層が形成されてなる積層基板を複数積層して得られる梱包体を用いて複数の積層基板の搬送を試みたところ、重ねられた積層基板中のポリイミド樹脂層の表面にキズが発生してしまうことを知見した。
また、本発明者らは、合紙の代わりに保護フィルムをポリイミド樹脂層に貼り合わせて上記キズの発生の防止を試みたところ、保護フィルムの種類によって、保護フィルムを剥離する際に支持基材が破損する場合や、保護フィルムの剥離後にポリイミド樹脂層表面上に異物が発生する場合や、ポリイミド樹脂層の外周部分に異物が発生する場合があることを知見した。
そこで、本発明は、積層された際にもポリイミド樹脂層の表面にキズの発生が抑制され、保護フィルムを剥離する際に支持基材の破損が抑制され、さらに、ポリイミド樹脂層上での異物の発生が抑制された積層基板、および複数の積層基板が積載された梱包体を提供することを目的とする。 As described above, since various electronic device members constituting the electronic device are formed on the polyimide resin layer in the laminated substrate, it is desirable that the surface of the polyimide resin layer is free from scratches and foreign substances.
On the other hand, as described in Patent Document 2, the present inventors can obtain a plurality of laminated substrates in which a polyimide resin layer is formed on a glass substrate via an interleaving paper made of virgin pulp. When we tried to transport a plurality of laminated substrates using a package, we found that the surface of the polyimide resin layer in the laminated substrates was scratched.
Further, the present inventors tried to prevent the above-mentioned scratches by attaching a protective film to the polyimide resin layer instead of the interleaving paper. Depending on the type of the protective film, the supporting base material was used when the protective film was peeled off. It was found that foreign matter may be generated on the surface of the polyimide resin layer after the protective film is peeled off, or foreign matter may be generated on the outer peripheral portion of the polyimide resin layer.
Therefore, in the present invention, the generation of scratches on the surface of the polyimide resin layer is suppressed even when laminated, the damage of the supporting base material is suppressed when the protective film is peeled off, and the foreign matter on the polyimide resin layer is further suppressed. It is an object of the present invention to provide a laminated substrate in which the occurrence of the above is suppressed, and a package in which a plurality of laminated substrates are loaded.

本発明者らは、鋭意検討した結果、以下の構成により上述の目的を達成できることを見出した。
本発明の第１の態様は、ガラス製の支持基材上に、ポリイミド樹脂層と、ポリイミド樹脂層を覆う保護フィルムとが積層された積層基板であって、ポリイミド樹脂層と保護フィルムとの第１の密着力をＦ１とし、支持基材と保護フィルムとの第２の密着力をＦ２とするとき、第１の密着力Ｆ１は、０．００１Ｎ／１０ｍｍ≦Ｆ１≦０．１７Ｎ／１０ｍｍであり、第２の密着力Ｆ２は、０．０５Ｎ／１０ｍｍ≦Ｆ２≦（Ｆ１（Ｎ／１０ｍｍ）＋０．３Ｎ／１０ｍｍ）である、積層基板を提供するものである。
保護フィルムの大きさは、支持基材の大きさ以上であることが好ましい。
保護フィルムの厚さは、２０μｍ以上であることが好ましい。
保護フィルムは、基材と、基材に積層され、かつポリイミド樹脂層に接する密着層とを有し、基材は、ポリエチレンにより構成されていることが好ましい。
支持基材とポリイミド樹脂層との密着力は、第１の密着力および第２の密着力のいずれよりも大きいことが好ましい。
支持基材とポリイミド樹脂層との間に、シランカップリング剤層が設けられていることが好ましい。
支持基材とポリイミド樹脂層との間に、シリコーン樹脂層が設けられていることが好ましい。
本発明の第２の態様は、パレットと、パレットに複数積載されている上述の第１の態様の積層基板とを有する、梱包体を提供するものである。
複数の積層基板は、相互に荷重がかかる状態でパレットに積載されていることが好ましい。
パレットは、底板と、底板に立設された背板とを有し、積層基板は支持基材を背板の表面に向けて、傾けた状態でパレットに積載されていることが好ましい。
積層基板の大きさは、短辺が８５０ｍｍ以上、長辺が１１００ｍｍ以上であることが好ましい。 As a result of diligent studies, the present inventors have found that the above object can be achieved by the following configuration.
The first aspect of the present invention is a laminated substrate in which a polyimide resin layer and a protective film covering the polyimide resin layer are laminated on a glass supporting base material, and the first aspect of the polyimide resin layer and the protective film is When the adhesion of 1 is F 1 and the second adhesion between the supporting base material and the protective film is F 2 , the first adhesion F 1 is 0.001N / 10mm ≤ F 1 ≤ 0.17N. It provides a laminated substrate which is / 10 mm and has a second adhesion F 2 of 0.05 N / 10 mm ≤ F 2 ≤ (F 1 (N / 10 mm) + 0.3 N / 10 mm).
The size of the protective film is preferably equal to or larger than the size of the supporting base material.
The thickness of the protective film is preferably 20 μm or more.
The protective film preferably has a base material and an adhesion layer laminated on the base material and in contact with the polyimide resin layer, and the base material is preferably made of polyethylene.
The adhesion between the supporting base material and the polyimide resin layer is preferably larger than either the first adhesion or the second adhesion.
It is preferable that a silane coupling agent layer is provided between the support base material and the polyimide resin layer.
It is preferable that a silicone resin layer is provided between the support base material and the polyimide resin layer.
A second aspect of the present invention provides a package having a pallet and a plurality of laminated substrates of the above-mentioned first aspect loaded on the pallet.
It is preferable that the plurality of laminated substrates are loaded on the pallet in a state where the loads are applied to each other.
The pallet preferably has a bottom plate and a back plate erected on the bottom plate, and the laminated substrate is preferably loaded on the pallet in an inclined state with the supporting base material facing the surface of the back plate.
The size of the laminated substrate is preferably 850 mm or more on the short side and 1100 mm or more on the long side.

本発明によれば、積層された際にもポリイミド樹脂層の表面にキズの発生が抑制され、保護フィルムを剥離する際に支持基材の破損が抑制され、さらに、ポリイミド樹脂層上での異物の発生が抑制された積層基板、および複数の積層基板が積載された梱包体を提供できる。 According to the present invention, the generation of scratches on the surface of the polyimide resin layer is suppressed even when laminated, the damage of the supporting base material is suppressed when the protective film is peeled off, and foreign matter on the polyimide resin layer is further suppressed. It is possible to provide a laminated substrate in which the occurrence of the above is suppressed, and a package in which a plurality of laminated substrates are loaded.

図１は本発明の実施形態の積層基板の第１の例を模式的に示す平面図である。FIG. 1 is a plan view schematically showing a first example of a laminated substrate according to an embodiment of the present invention. 図２は本発明の実施形態の積層基板の第１の例を模式的に示す断面図である。FIG. 2 is a cross-sectional view schematically showing a first example of the laminated substrate according to the embodiment of the present invention. 図３は本発明の実施形態の積層基板の第１の例の保護フィルムを模式的に示す断面図である。FIG. 3 is a cross-sectional view schematically showing a protective film of a first example of a laminated substrate according to an embodiment of the present invention. 図４は本発明の実施形態の積層基板の第２の例を模式的に示す平面図である。FIG. 4 is a plan view schematically showing a second example of the laminated substrate according to the embodiment of the present invention. 図５は本発明の実施形態の積層基板の第３の例を模式的に示す断面図である。FIG. 5 is a cross-sectional view schematically showing a third example of the laminated substrate according to the embodiment of the present invention. 図６は本発明の実施形態の梱包体の一例を模式的に示す側面図である。FIG. 6 is a side view schematically showing an example of the packaging body according to the embodiment of the present invention. 図７は本発明の実施形態の積層基板における埋設物の発生を模式的に説明する断面図である。FIG. 7 is a cross-sectional view schematically illustrating the generation of buried objects in the laminated substrate according to the embodiment of the present invention. 図８は本発明の実施形態の積層基板における埋設物の発生を模式的に説明する断面図である。FIG. 8 is a cross-sectional view schematically illustrating the generation of buried objects in the laminated substrate according to the embodiment of the present invention. 図９は本発明の実施形態の積層基板における埋設物の発生を模式的に説明する断面図である。FIG. 9 is a cross-sectional view schematically illustrating the generation of buried objects in the laminated substrate according to the embodiment of the present invention. 図１０は本発明の実施形態の積層基板における埋設物の一例を示すＳＥＭ像である。FIG. 10 is an SEM image showing an example of a buried object in the laminated substrate according to the embodiment of the present invention.

以下、本発明の実施形態について図面を参照して説明する。ただし、以下の実施形態は本発明を説明するための例示的なものであり、本発明は以下に示す実施形態に制限されることはない。なお、本発明の範囲を逸脱することなく、以下の実施形態に種々の変形および置換を加えることができる。
「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the following embodiments are exemplary for explaining the present invention, and the present invention is not limited to the embodiments shown below. In addition, various modifications and substitutions can be added to the following embodiments without departing from the scope of the present invention.
The numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

本発明の積層基板の特徴点としては、ポリイミド樹脂層を覆う保護フィルムを設けている点が挙げられる。特に、保護フィルムと、ポリイミド樹脂層および支持基材との間の密着力を調整することにより、所望の効果を得ている。
本発明者らは、特許文献２に記載されるバージンパルプからなる合紙を用いた際にポリイミド樹脂層表面にキズが生じる原因として、合紙とポリイミド樹脂層との間の密着力が低すぎる点が挙げられることを知見している。つまり、合紙とポリイミド樹脂層との間の密着力が弱いため、合紙とポリイミド樹脂層との間でこすれが生じ、ポリイミド樹脂層の表面でキズが発生している。一方で、ポリイミド樹脂層と保護フィルムとの密着力が強すぎると、保護フィルムを剥離する際に、保護フィルム由来の成分（例えば、密着層の材料）由来の異物がポリイミド樹脂層上に残存してしまう。
以上の点を考慮して、保護フィルムとポリイミド樹脂層との間の密着力が調整されている。
さらに、保護フィルムと支持基材との間の密着力が弱すぎると、保護フィルムが剥離して、ポリイミド樹脂層の外周部分に異物が付着しやすくなる。一方で、保護フィルムと支持基材との間の密着力が強すぎると、保護フィルムを剥離する際に、ポリイミド樹脂層部分と支持基材部分との間に剥離速度の差が生じ、保護フィルムの剥離時に支持基材に意図しない力がかかり、支持基材の破壊につながる。
以上の点を考慮して、保護フィルムと支持基材との間の密着力が調整されている。 A feature of the laminated substrate of the present invention is that a protective film is provided to cover the polyimide resin layer. In particular, the desired effect is obtained by adjusting the adhesive force between the protective film and the polyimide resin layer and the supporting base material.
The present inventors have too low an adhesive force between the interleaving paper and the polyimide resin layer as a cause of scratches on the surface of the polyimide resin layer when the interleaving paper made of virgin pulp described in Patent Document 2 is used. We know that there are some points. That is, since the adhesive force between the interleaving paper and the polyimide resin layer is weak, rubbing occurs between the interleaving paper and the polyimide resin layer, and scratches are generated on the surface of the polyimide resin layer. On the other hand, if the adhesion between the polyimide resin layer and the protective film is too strong, foreign matter derived from the protective film-derived component (for example, the material of the adhesive layer) remains on the polyimide resin layer when the protective film is peeled off. It ends up.
In consideration of the above points, the adhesive force between the protective film and the polyimide resin layer is adjusted.
Further, if the adhesive force between the protective film and the supporting base material is too weak, the protective film is peeled off and foreign matter easily adheres to the outer peripheral portion of the polyimide resin layer. On the other hand, if the adhesive force between the protective film and the supporting base material is too strong, when the protective film is peeled off, a difference in peeling speed occurs between the polyimide resin layer portion and the supporting base material portion, and the protective film An unintended force is applied to the supporting base material at the time of peeling, which leads to the destruction of the supporting base material.
In consideration of the above points, the adhesion between the protective film and the supporting base material is adjusted.

＜積層基板＞
［積層基板の第１の例］
図１は本発明の実施形態の積層基板の第１の例を模式的に示す平面図であり、図２は本発明の実施形態の積層基板の第１の例を模式的に示す断面図である。図３は本発明の実施形態の積層基板の第１の例の保護フィルムを模式的に示す断面図である。
第１の例の積層基板１０は、ガラス製の支持基材１２上に、ポリイミド樹脂層１４と、ポリイミド樹脂層１４を覆う保護フィルム１６とが積層されたものである。
図２に示すように、支持基材１２の表面１２ａにポリイミド樹脂層１４が設けられている。図１に示すように、ポリイミド樹脂層１４は、支持基材１２の表面１２ａよりも面積が小さく、支持基材１２の表面１２ａ全域に設けられていない。支持基材１２の表面１２ａの外縁部１２ｃ、すなわち、支持基材１２の額縁部分にはポリイミド樹脂層１４が設けられていない。
保護フィルム１６が支持基材１２上のポリイミド樹脂層１４を覆って配置されている。図２および図３に示すように、保護フィルム１６は、基材１８と、基材１８に積層された密着層１９とを有する。図２に示すように保護フィルム１６の密着層１９がポリイミド樹脂層１４の表面１４ａおよび支持基材１２の表面１２ａと接する。保護フィルム１６は、ポリイミド樹脂層１４を基板として利用する際には剥がされる。この場合、保護フィルム１６の密着層１９は、ポリイミド樹脂層１４の表面１４ａおよび支持基材１２の表面１２ａと同時に接した状態から剥がされることがある。 <Laminated board>
[First example of laminated substrate]
FIG. 1 is a plan view schematically showing a first example of a laminated substrate according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view schematically showing a first example of a laminated substrate according to an embodiment of the present invention. is there. FIG. 3 is a cross-sectional view schematically showing a protective film of a first example of a laminated substrate according to an embodiment of the present invention.
In the laminated substrate 10 of the first example, the polyimide resin layer 14 and the protective film 16 covering the polyimide resin layer 14 are laminated on the glass supporting base material 12.
As shown in FIG. 2, the polyimide resin layer 14 is provided on the surface 12a of the support base material 12. As shown in FIG. 1, the polyimide resin layer 14 has a smaller area than the surface 12a of the support base material 12, and is not provided on the entire surface 12a of the support base material 12. The polyimide resin layer 14 is not provided on the outer edge portion 12c of the surface 12a of the support base material 12, that is, the frame portion of the support base material 12.
The protective film 16 is arranged so as to cover the polyimide resin layer 14 on the support base material 12. As shown in FIGS. 2 and 3, the protective film 16 has a base material 18 and an adhesion layer 19 laminated on the base material 18. As shown in FIG. 2, the adhesion layer 19 of the protective film 16 is in contact with the surface 14a of the polyimide resin layer 14 and the surface 12a of the supporting base material 12. The protective film 16 is peeled off when the polyimide resin layer 14 is used as a substrate. In this case, the adhesive layer 19 of the protective film 16 may be peeled off from the state of being in contact with the surface 14a of the polyimide resin layer 14 and the surface 12a of the supporting base material 12 at the same time.

支持基材１２は、ポリイミド樹脂層１４を支持する部材であり、ポリイミド樹脂層１４を補強する補強板として機能する。また、支持基材１２は、積層基板１０の搬送の際の搬送基板としても機能する。
積層基板１０において、支持基材１２とポリイミド樹脂層１４とを引き剥がす方向に力を加えると、支持基材１２とポリイミド樹脂層１４とに分離される。
ポリイミド樹脂層１４は、電子デバイスの製造のために用いられる基板である。ポリイミド樹脂層１４の表面１４ａに、電子デバイスを構成するトランジスタ、コイルおよび抵抗等の電子素子、ならびに信号線等が形成される。
保護フィルム１６は、支持基材１２およびポリイミド樹脂層１４を保護するものであり、特に外部からの受けた力による打痕、およびキズ等がポリイミド樹脂層１４に生じないように保護する。保護フィルム１６は、例えば、図１に示す積層基板１０では支持基材１２と同じ大きさである。 The support base material 12 is a member that supports the polyimide resin layer 14, and functions as a reinforcing plate that reinforces the polyimide resin layer 14. The support base material 12 also functions as a transport substrate when transporting the laminated substrate 10.
In the laminated substrate 10, when a force is applied in the direction of peeling the support base material 12 and the polyimide resin layer 14, the support base material 12 and the polyimide resin layer 14 are separated from each other.
The polyimide resin layer 14 is a substrate used for manufacturing an electronic device. On the surface 14a of the polyimide resin layer 14, electronic elements such as transistors, coils and resistors constituting an electronic device, signal lines and the like are formed.
The protective film 16 protects the support base material 12 and the polyimide resin layer 14, and particularly protects the polyimide resin layer 14 from dents and scratches caused by external forces. The protective film 16 has the same size as the supporting base material 12 in the laminated substrate 10 shown in FIG. 1, for example.

積層基板１０では、ポリイミド樹脂層１４と保護フィルム１６との第１の密着力をＦ１とし、支持基材１２と保護フィルム１６との第２の密着力をＦ２とする。
第１の密着力Ｆ１は、０．００１Ｎ／１０ｍｍ≦Ｆ１≦０．１７Ｎ／１０ｍｍである。第２の密着力Ｆ２は、０．０５Ｎ／１０ｍｍ≦Ｆ２≦（Ｆ１（Ｎ／１０ｍｍ）＋０．３Ｎ／１０ｍｍ）である。
上述の第１の密着力Ｆ１および第２の密着力Ｆ２の測定は以下のようにして行う。まず、幅２５ｍｍの短冊状に切り出した保護フィルム１６を、ポリイミド樹脂層１４または支持基材１２に貼合する。次に、１ｃｍ２あたり１６ｇの荷重をかけた状態で、温度４０℃、相対湿度８０％の環境下に、５日間放置する。その後、９０°剥離試験を実施する。剥離時の引き上げ速度は、３００ｍｍ／ｍｉｎとする。安定的に剥離している領域の荷重から、単位幅（１０ｍｍ）当たりの保護フィルムを剥離する際の荷重を算出する。 In the laminated substrate 10, the first adhesive force between the polyimide resin layer 14 and the protective film 16 is F 1, and the second adhesive force between the supporting base material 12 and the protective film 16 is F 2 .
The first adhesion force F 1 is 0.001N / 10mm ≦ F 1 ≦ 0.17N / 10mm. The second adhesion force F 2 is 0.05 N / 10 mm ≦ F 2 ≦ (F 1 (N / 10 mm) + 0.3 N / 10 mm).
The above-mentioned first adhesion force F 1 and the second adhesion force F 2 are measured as follows. First, the protective film 16 cut out in a strip shape having a width of 25 mm is attached to the polyimide resin layer 14 or the supporting base material 12. Next, it is left for 5 days in an environment of a temperature of 40 ° C. and a relative humidity of 80% under a load of 16 g per 1 cm 2 . Then, a 90 ° peeling test is carried out. The pulling speed at the time of peeling is 300 mm / min. From the load in the region where the film is stably peeled off, the load for peeling the protective film per unit width (10 mm) is calculated.

上述のように、第１の密着力Ｆ１は、０．００１Ｎ／１０ｍｍ≦Ｆ１≦０．１７Ｎ／１０ｍｍである。第１の密着力Ｆ１が０．００１Ｎ／１０ｍｍ未満では、ポリイミド樹脂層１４と保護フィルム１６とが十分に密着しておらず、ポリイミド樹脂層１４と保護フィルム１６との間にこすれが発生し、ポリイミド樹脂層１４の表面１４ａにキズがつく。
第１の密着力Ｆ１が０．１７Ｎ／１０ｍｍを超えると、ポリイミド樹脂層１４と保護フィルム１６の密着力が強すぎて、ポリイミド樹脂層１４の表面１４ａに、保護フィルム１６の密着層１９の一部が残り、異物の発生につながる。特に、密着層が粘着剤を含む粘着層である場合、粘着剤に由来する糊残りが生じる。なお、異物（特に、糊残り）が発生すると、ポリイミド樹脂層１４の耐熱性が低下したり、ポリイミド樹脂層１４を用いて形成される電子デバイスに断線等の欠陥が生じることがある。さらには、第１の密着力Ｆ１が１．５Ｎ／１０ｍｍを超えるような、第１の密着力Ｆ１が大きすぎる場合、支持基材１２の破壊が生じる場合がある。
なかでも、ポリイミド樹脂層１４の表面１４ａでのキズの発生、および異物の発生がより抑制される点から、第１の密着力Ｆ１は０．００２〜０．１５Ｎ／１０ｍｍが好ましく、０．００３〜０．１４５Ｎ／１０ｍｍがより好ましい。 As described above, the first adhesion force F 1 is 0.001N / 10mm ≦ F 1 ≦ 0.17N / 10mm. When the first adhesion force F 1 is less than 0.001 N / 10 mm, the polyimide resin layer 14 and the protective film 16 are not sufficiently adhered to each other, and rubbing occurs between the polyimide resin layer 14 and the protective film 16. , The surface 14a of the polyimide resin layer 14 is scratched.
When the first adhesive force F 1 exceeds 0.17 N / 10 mm, the adhesive force between the polyimide resin layer 14 and the protective film 16 is too strong, and the adhesive layer 19 of the protective film 16 is attached to the surface 14a of the polyimide resin layer 14. A part remains, leading to the generation of foreign matter. In particular, when the adhesive layer is an adhesive layer containing an adhesive, adhesive residue derived from the adhesive is generated. When foreign matter (particularly, adhesive residue) is generated, the heat resistance of the polyimide resin layer 14 may be lowered, or defects such as disconnection may occur in the electronic device formed by using the polyimide resin layer 14. Furthermore, if the first adhesion force F 1 is too large such that the first adhesion force F 1 exceeds 1.5 N / 10 mm, the supporting base material 12 may be destroyed.
Among them, the generation of scratches on the surface 14a of the polyimide resin layer 14, and from the point of generation of foreign matter can be further suppressed, the first contact force F 1 is preferably 0.002~0.15N / 10mm, 0. More preferably, it is 003 to 0.145 N / 10 mm.

上述のように、第２の密着力Ｆ２は、０．０５Ｎ／１０ｍｍ≦Ｆ２≦（Ｆ１（Ｎ／１０ｍｍ）＋０．３Ｎ／１０ｍｍ）である。第２の密着力Ｆ２の上限値は、第１の密着力Ｆ１よりも大きい。
第２の密着力Ｆ２が０．０５Ｎ／１０ｍｍ未満では、保護フィルム１６と支持基材１２との密着力が弱すぎて、支持基材１２の外縁部１２ｃの保護フィルム１６が運搬中に捲れて、ポリイミド樹脂層１４の外周部分に異物が多量に付着する。この異物によりポリイミド樹脂層１４にキズ等が発生する可能性が高くなる。
第２の密着力Ｆ２がＦ１（Ｎ／１０ｍｍ）＋０．３Ｎ／１０ｍｍを超えると、保護フィルム１６と支持基材１２との密着力が強すぎて、保護フィルム１６を剥離する際に、ポリイミド樹脂層１４部分と支持基材１２部分との間に剥離速度の差が生じ、保護フィルム１６の剥離時に支持基材１２に意図しない力がかかり、支持基材１２の破壊につながる。
積層基板１０では、支持基材１２と保護フィルム１６との第２の密着力Ｆ２が上述の範囲であるため、保護フィルム１６を剥離するとき、スムーズに剥離でき、支持基材１２の損傷等が生じない。
なかでも、ポリイミド樹脂層１４の表面１４ａでの異物の発生、および支持基材１２の破損がより抑制される点から、第２の密着力Ｆ２は０．０６〜０．１８Ｎ／１０ｍｍが好ましく、０．０７〜０．１７Ｎ／１０ｍｍがより好ましい。 As described above, the second adhesion force F 2 is 0.05 N / 10 mm ≦ F 2 ≦ (F 1 (N / 10 mm) + 0.3 N / 10 mm). The upper limit of the second adhesion force F 2 is larger than that of the first adhesion force F 1 .
If the second adhesive force F 2 is less than 0.05 N / 10 mm, the adhesive force between the protective film 16 and the supporting base material 12 is too weak, and the protective film 16 on the outer edge portion 12c of the supporting base material 12 is rolled up during transportation. Therefore, a large amount of foreign matter adheres to the outer peripheral portion of the polyimide resin layer 14. There is a high possibility that the polyimide resin layer 14 will be scratched or the like due to this foreign matter.
When the second adhesive force F 2 exceeds F 1 (N / 10 mm) + 0.3 N / 10 mm, the adhesive force between the protective film 16 and the supporting base material 12 is too strong, and when the protective film 16 is peeled off, A difference in peeling speed occurs between the polyimide resin layer 14 portion and the support base material 12 portion, and an unintended force is applied to the support base material 12 when the protective film 16 is peeled off, leading to destruction of the support base material 12.
In the laminated substrate 10, since the second adhesion force F 2 between the support base material 12 and the protective film 16 is within the above range, when the protective film 16 is peeled off, it can be peeled off smoothly, and the support base material 12 is damaged or the like. Does not occur.
In particular, the second adhesion force F 2 is preferably 0.06 to 0.18 N / 10 mm from the viewpoint of further suppressing the generation of foreign matter on the surface 14a of the polyimide resin layer 14 and the damage of the supporting base material 12. , 0.07 to 0.17 N / 10 mm is more preferable.

なお、積層基板１０において、支持基材１２とポリイミド樹脂層１４との密着力は、上記第１の密着力Ｆ１、および第２の密着力Ｆ２のいずれよりも大きいことが好ましい。支持基材１２とポリイミド樹脂層１４との密着力を向上させる方法としては、後述するように、支持基材１２の表面を改質する方法（例えば、シランカップリング剤で改質する方法。つまり、支持基材１２とポリイミド樹脂層１４との間にシランカップリング剤層（シランカップリング剤を用いて形成される層）を設ける方法。）や、支持基材１２とポリイミド樹脂層１４との間に両者の密着性を向上させる層（例えば、後述するシリコーン樹脂層）を設ける方法が挙げられる。
なお、支持基材１２とポリイミド樹脂層１４との間にシランカップリング剤層およびシリコーン樹脂層のような層が設けられる場合、支持基材１２とシランカップリング剤層またはシリコーン樹脂層との密着力、および、ポリイミド樹脂層１４とシランカップリング剤層またはシリコーン樹脂層との密着力は、上記第１の密着力Ｆ１、および第２の密着力Ｆ２のいずれよりも大きいことが好ましい。 In the laminated substrate 10, the adhesion between the support base material 12 and the polyimide resin layer 14 is preferably larger than any of the first adhesion force F 1 and the second adhesion force F 2 . As a method for improving the adhesion between the support base material 12 and the polyimide resin layer 14, as described later, a method of modifying the surface of the support base material 12 (for example, a method of modifying with a silane coupling agent, that is, , A method of providing a silane coupling agent layer (a layer formed by using a silane coupling agent) between the support base material 12 and the polyimide resin layer 14 or the support base material 12 and the polyimide resin layer 14. A method of providing a layer (for example, a silicone resin layer described later) for improving the adhesion between the two can be mentioned.
When a layer such as a silane coupling agent layer and a silicone resin layer is provided between the support base material 12 and the polyimide resin layer 14, the support base material 12 and the silane coupling agent layer or the silicone resin layer are in close contact with each other. The force and the adhesive force between the polyimide resin layer 14 and the silane coupling agent layer or the silicone resin layer are preferably larger than any of the first adhesive force F 1 and the second adhesive force F 2 .

［積層基板の第１の例の製造方法］
第１の例である積層基板１０を製造する方法としては、支持基材１２の表面１２ａ上に、ポリイミド樹脂層１４を積層させる方法が好ましい。なかでも、支持基材１２の表面１２ａ上にポリイミド樹脂層１４を積層させる前に、支持基材１２の表面１２ａ上に公知のシランカップリング剤を塗布し、その後、シランカップリング剤が塗布された支持基材１２の表面１２ａ上にポリイミド樹脂層１４を積層することが好ましい。この場合、支持基材１２とポリイミド樹脂層１４との間に、シランカップリング剤層が設けられている。支持基材１２の表面１２ａ上にポリイミド樹脂層１４が形成された状態で、支持基材１２の表面１２ａに密着層１９を向けて保護フィルム１６を配置し、ポリイミド樹脂層１４を覆って保護フィルム１６を支持基材１２に貼り付ける。これにより、積層基板１０を製造できる。 [Manufacturing method of the first example of a laminated substrate]
As a method for producing the laminated substrate 10 which is the first example, a method of laminating the polyimide resin layer 14 on the surface 12a of the supporting base material 12 is preferable. Above all, before laminating the polyimide resin layer 14 on the surface 12a of the support base material 12, a known silane coupling agent is applied on the surface 12a of the support base material 12, and then the silane coupling agent is applied. It is preferable to laminate the polyimide resin layer 14 on the surface 12a of the supporting base material 12. In this case, a silane coupling agent layer is provided between the support base material 12 and the polyimide resin layer 14. With the polyimide resin layer 14 formed on the surface 12a of the support base material 12, the protective film 16 is arranged with the adhesion layer 19 facing the surface 12a of the support base material 12, and the protective film 16 covers the polyimide resin layer 14. 16 is attached to the support base material 12. As a result, the laminated substrate 10 can be manufactured.

［積層基板の第２の例］
図４は本発明の実施形態の積層基板の第２の例を模式的に示す平面図である。なお、図４に示す第２の例の積層基板１０において、図１および図２に示す第１の例の積層基板１０と同一構成物には同一符号を付して、その詳細な説明は省略する。
第２の例の積層基板１０は、図１および図２に示す積層基板１０と比べて、保護フィルム１６の大きさが支持基材１２よりも大きいこと以外は、図１および図２に示す積層基板１０と同じである。
第２の例の積層基板１０のように、保護フィルム１６の大きさが支持基材１２よりも大きいことにより、保護フィルム１６を剥離する際に保護フィルム１６の一端部を把持しやすくなる。 [Second example of laminated substrate]
FIG. 4 is a plan view schematically showing a second example of the laminated substrate according to the embodiment of the present invention. In the laminated substrate 10 of the second example shown in FIG. 4, the same components as the laminated substrate 10 of the first example shown in FIGS. 1 and 2 are designated by the same reference numerals, and detailed description thereof will be omitted. To do.
The laminated substrate 10 of the second example is laminated as shown in FIGS. 1 and 2 except that the size of the protective film 16 is larger than that of the supporting base material 12 as compared with the laminated substrate 10 shown in FIGS. 1 and 2. It is the same as the substrate 10.
Since the size of the protective film 16 is larger than that of the supporting base material 12 as in the laminated substrate 10 of the second example, it becomes easy to grip one end of the protective film 16 when the protective film 16 is peeled off.

［積層基板の第２の例の製造方法］
第２の例の積層基板１０は、保護フィルム１６に支持基材１２よりも大きいものを用いて、保護フィルム１６を、ポリイミド樹脂層１４を覆って支持基材１２に貼り付けた点以外は、第１の例の積層基板１０と同様の方法で製造することができる。 [Manufacturing method of the second example of the laminated substrate]
The laminated substrate 10 of the second example uses a protective film 16 larger than the supporting base material 12, except that the protective film 16 is attached to the supporting base material 12 by covering the polyimide resin layer 14. It can be manufactured in the same manner as the laminated substrate 10 of the first example.

［積層基板の第３の例］
図５は本発明の実施形態の積層基板の第３の例を模式的に示す断面図である。なお、図５に示す第３の例の積層基板１０において、図１および図２に示す第１の例の積層基板１０と同一構成物には同一符号を付して、その詳細な説明は省略する。
第３の例の積層基板１０は、図１および図２に示す積層基板１０と比べて、支持基材１２とポリイミド樹脂層１４との間にシリコーン樹脂層１３を有すること以外は、図１および図２に示す積層基板１０と同じである。 [Third example of laminated substrate]
FIG. 5 is a cross-sectional view schematically showing a third example of the laminated substrate according to the embodiment of the present invention. In the laminated substrate 10 of the third example shown in FIG. 5, the same components as the laminated substrate 10 of the first example shown in FIGS. 1 and 2 are designated by the same reference numerals, and detailed description thereof will be omitted. To do.
The laminated substrate 10 of the third example has a silicone resin layer 13 between the supporting base material 12 and the polyimide resin layer 14, as compared with the laminated substrate 10 shown in FIGS. 1 and 2, except that the laminated substrate 10 has a silicone resin layer 13 in FIG. It is the same as the laminated substrate 10 shown in FIG.

第３の例の積層基板１０では、支持基材１２と、シリコーン樹脂層１３と、ポリイミド樹脂層１４とがこの順で積層されている。支持基材１２の表面１２ａにシリコーン樹脂層１３が設けられ、シリコーン樹脂層１３の表面１３ａにポリイミド樹脂層１４が設けられている。シリコーン樹脂層１３とポリイミド樹脂層１４とは同じ大きさであるが、支持基材１２の表面１２ａと比べて小さい。
第３の例の積層基板１０では、支持基材１２およびシリコーン樹脂層１３は、ポリイミド樹脂層１４を補強する補強板として機能する。 In the laminated substrate 10 of the third example, the supporting base material 12, the silicone resin layer 13, and the polyimide resin layer 14 are laminated in this order. The silicone resin layer 13 is provided on the surface 12a of the support base material 12, and the polyimide resin layer 14 is provided on the surface 13a of the silicone resin layer 13. The silicone resin layer 13 and the polyimide resin layer 14 have the same size, but are smaller than the surface 12a of the support base material 12.
In the laminated substrate 10 of the third example, the supporting base material 12 and the silicone resin layer 13 function as reinforcing plates for reinforcing the polyimide resin layer 14.

積層基板１０に加熱処理が施された場合、シリコーン樹脂層１３とポリイミド樹脂層１４との間の密着力よりも、支持基材１２とシリコーン樹脂層１３との間の密着力の方が大きくなることが好ましい。これは、加熱処理によって、支持基材１２のヒドロキシ基とシリコーン樹脂層１３のヒドロキシ基とが結合すること等によって生じ得る。
その結果、支持基材１２とポリイミド樹脂層１４とを引き剥がす方向に力が加えられると、シリコーン樹脂層１３とポリイミド樹脂層１４との間で剥離する。これにより、ポリイミド樹脂層１４を分離できる。
なお、第３の例の積層基板１０では、保護フィルム１６の大きさについては制限されることはない。図１に示す積層基板１０と同様に保護フィルム１６と支持基材１２とが同じ大きさでもよく、図４に示す積層基板１０と同様に保護フィルム１６の大きさを支持基材１２よりも大きくしてもよい。 When the laminated substrate 10 is heat-treated, the adhesion between the supporting base material 12 and the silicone resin layer 13 is greater than the adhesion between the silicone resin layer 13 and the polyimide resin layer 14. Is preferable. This may occur due to the bonding of the hydroxy group of the support base material 12 and the hydroxy group of the silicone resin layer 13 by the heat treatment or the like.
As a result, when a force is applied in the direction of peeling the support base material 12 and the polyimide resin layer 14, the silicone resin layer 13 and the polyimide resin layer 14 are peeled off. As a result, the polyimide resin layer 14 can be separated.
In the laminated substrate 10 of the third example, the size of the protective film 16 is not limited. Similar to the laminated substrate 10 shown in FIG. 1, the protective film 16 and the supporting base material 12 may have the same size, and the size of the protective film 16 may be larger than that of the supporting base material 12 like the laminated substrate 10 shown in FIG. You may.

［積層基板の第３の例の製造方法］
第３の例の積層基板１０を製造する方法は、ポリイミド樹脂層１４の裏面（表面１４ａと反対側の面）にシリコーン樹脂層１３を形成する方法が好ましい。具体的には、硬化性シリコーンを含む硬化性組成物をポリイミド樹脂層１４の裏面に塗布し、得られた塗膜に対して硬化処理を施してシリコーン樹脂層１３を得た後、シリコーン樹脂層１３の裏面（表面１３ａと反対側の面）に支持基材１２を積層して、積層基板１０を製造する方法が好ましい。
より詳細には、第３の例の積層基板１０を製造する方法は、硬化性シリコーンの層をポリイミド樹脂層１４の裏面（表面１４ａと反対側の面）に形成し、ポリイミド樹脂層１４の裏面にシリコーン樹脂層１３を形成する工程（樹脂層形成工程）と、シリコーン樹脂層１３の裏面（表面１３ａと反対側の面）に支持基材１２を積層する工程（積層工程）と、保護フィルム１６を貼り付ける工程（貼合工程）とを、少なくとも有する。以下、上述の各工程について詳述する。 [Manufacturing method of the third example of the laminated substrate]
As a method for producing the laminated substrate 10 of the third example, a method of forming the silicone resin layer 13 on the back surface (the surface opposite to the surface 14a) of the polyimide resin layer 14 is preferable. Specifically, a curable composition containing a curable silicone is applied to the back surface of the polyimide resin layer 14, and the obtained coating film is cured to obtain a silicone resin layer 13, and then the silicone resin layer is obtained. A method of manufacturing the laminated substrate 10 by laminating the support base material 12 on the back surface (the surface opposite to the surface 13a) of 13 is preferable.
More specifically, in the method of manufacturing the laminated substrate 10 of the third example, a curable silicone layer is formed on the back surface of the polyimide resin layer 14 (the surface opposite to the surface surface 14a), and the back surface of the polyimide resin layer 14 is formed. A step of forming the silicone resin layer 13 on the surface (resin layer forming step), a step of laminating the support base material 12 on the back surface (the surface opposite to the surface 13a) of the silicone resin layer 13 (lamination step), and a protective film 16 It has at least a step of pasting (bonding step). Hereinafter, each step described above will be described in detail.

（樹脂層形成工程）
樹脂層形成工程は、硬化性シリコーンの層をポリイミド樹脂層１４の裏面に形成し、ポリイミド樹脂層１４の裏面にシリコーン樹脂層１３を形成する工程である。本工程によって、ポリイミド樹脂層１４とシリコーン樹脂層１３とをこの順で備えるシリコーン樹脂層付き基板が得られる。
シリコーン樹脂層付き基板は、ロール状に巻いたポリイミド樹脂層１４の裏面にシリコーン樹脂層１３を形成してから再びロール状に巻き取る、いわゆるロール・ツー・ロール方式での製造が可能であり、生産効率に優れる。
本工程において、ポリイミド樹脂層１４の裏面に硬化性シリコーンの層を形成するためには、上述した硬化性組成物を、ポリイミド樹脂層１４の裏面に塗布する。次いで、硬化性シリコーンの層に対して硬化処理を施すことにより硬化層を形成することが好ましい。
ポリイミド樹脂層１４の裏面に硬化性組成物を塗布する方法の具体例としては、スプレーコート法、ダイコート法、スピンコート法、ディップコート法、ロールコート法、バーコート法、スクリーン印刷法、およびグラビアコート法が挙げられる。
次いで、ポリイミド樹脂層１４の裏面に塗布された硬化性シリコーンを硬化させて、シリコーン樹脂層１３を形成する。 (Resin layer forming process)
The resin layer forming step is a step of forming a curable silicone layer on the back surface of the polyimide resin layer 14 and forming the silicone resin layer 13 on the back surface of the polyimide resin layer 14. By this step, a substrate with a silicone resin layer including the polyimide resin layer 14 and the silicone resin layer 13 in this order can be obtained.
The substrate with a silicone resin layer can be manufactured by a so-called roll-to-roll method in which the silicone resin layer 13 is formed on the back surface of the polyimide resin layer 14 wound in a roll shape and then wound again in a roll shape. Excellent production efficiency.
In this step, in order to form a curable silicone layer on the back surface of the polyimide resin layer 14, the above-mentioned curable composition is applied to the back surface of the polyimide resin layer 14. Next, it is preferable to form a cured layer by subjecting the curable silicone layer to a curing treatment.
Specific examples of the method of applying the curable composition to the back surface of the polyimide resin layer 14 include a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, and a gravure. The coat method can be mentioned.
Next, the curable silicone applied to the back surface of the polyimide resin layer 14 is cured to form the silicone resin layer 13.

シリコーン樹脂層１３を形成するための硬化の方法は特に制限されず、使用される硬化性シリコーンの種類によって適宜最適な処理が実施される。例えば、縮合反応型シリコーンおよび付加反応型シリコーンを用いる場合は、硬化処理としては熱硬化処理が好ましい。
熱硬化処理の条件は、ポリイミド樹脂層１４の耐熱性の範囲内で実施され、例えば、熱硬化させる温度条件は、５０〜４００℃が好ましく、１００〜３００℃がより好ましい。加熱時間は、１０〜３００分が好ましく、２０〜１２０分がより好ましい。
シリコーン樹脂層１３については後に説明する。 The curing method for forming the silicone resin layer 13 is not particularly limited, and the optimum treatment is appropriately carried out depending on the type of curable silicone used. For example, when a condensation reaction type silicone and an addition reaction type silicone are used, a thermosetting treatment is preferable as the curing treatment.
The conditions of the thermosetting treatment are carried out within the range of heat resistance of the polyimide resin layer 14, and for example, the temperature conditions for thermosetting are preferably 50 to 400 ° C, more preferably 100 to 300 ° C. The heating time is preferably 10 to 300 minutes, more preferably 20 to 120 minutes.
The silicone resin layer 13 will be described later.

（積層工程）
積層工程は、シリコーン樹脂層１３の表面に支持基材１２を積層する工程である。支持基材１２をシリコーン樹脂層１３の裏面上に積層する方法の具体例としては、常圧環境下でシリコーン樹脂層１３の裏面上に支持基材１２を重ねる方法が挙げられる。必要に応じて、シリコーン樹脂層１３の裏面上に支持基材１２を重ねた後、ロールやプレスを用いてシリコーン樹脂層１３に支持基材１２を圧着させてもよい。ロールまたはプレスによる圧着により、シリコーン樹脂層１３と支持基材１２との間に混入している気泡が比較的容易に除去されるので好ましい。
真空ラミネート法または真空プレス法により圧着すると、気泡の混入が抑制され、かつ、良好な密着が実現でき、好ましい。真空下で圧着することにより、微小な気泡が残存した場合でも、加熱処理により気泡が成長しにくいという利点もある。
支持基材１２を積層する際には、シリコーン樹脂層１３に接触する支持基材１２の表面を十分に洗浄し、クリーン度の高い環境で積層することが好ましい。 (Laminating process)
The laminating step is a step of laminating the supporting base material 12 on the surface of the silicone resin layer 13. Specific examples of the method of laminating the support base material 12 on the back surface of the silicone resin layer 13 include a method of laminating the support base material 12 on the back surface of the silicone resin layer 13 under a normal pressure environment. If necessary, the support base material 12 may be laminated on the back surface of the silicone resin layer 13, and then the support base material 12 may be pressure-bonded to the silicone resin layer 13 using a roll or a press. Crimping with a roll or press is preferable because air bubbles mixed between the silicone resin layer 13 and the supporting base material 12 are relatively easily removed.
Crimping by a vacuum laminating method or a vacuum pressing method is preferable because it suppresses the mixing of air bubbles and can realize good adhesion. By crimping under vacuum, there is an advantage that even if minute bubbles remain, the bubbles are unlikely to grow due to the heat treatment.
When laminating the support base material 12, it is preferable that the surface of the support base material 12 in contact with the silicone resin layer 13 is sufficiently washed and then laminated in an environment with a high degree of cleanliness.

（貼合工程）
貼合工程は、支持基材１２の表面１２ａに密着層１９を向けて保護フィルム１６を配置し、ポリイミド樹脂層１４を覆って保護フィルム１６を支持基材１２に貼り付ける。これにより、積層基板１０が得られる。 (Lasting process)
In the bonding step, the protective film 16 is arranged with the adhesion layer 19 facing the surface 12a of the support base material 12, and the protective film 16 is attached to the support base material 12 by covering the polyimide resin layer 14. As a result, the laminated substrate 10 is obtained.

＜梱包体＞
図６は本発明の実施形態の梱包体の一例を模式的に示す側面図である。図６に示す梱包体２０において、図１および図２に示す第１の例の積層基板１０と同一構成物には同一符号を付して、その詳細な説明は省略する。
梱包体２０は、上述の図１に示す複数の積層基板１０と、複数の積層基板１０が積層されて積載されるパレット２２とを有する。
積層基板１０が、１２００ｍｍ×１０００ｍｍ（Ｇ５サイズ）以上では、積層基板同士が完全に離れた状態でケース内に梱包することが難しく、後述のように複数の積層基板１０を相互に荷重がかかる状態でパレット２２に積載して、積層基板１０を梱包することが好ましい。
積層基板１０は四角形であり、積層基板１０の大きさとしては、短辺が８５０ｍｍ以上、長辺が１１００ｍｍ以上であることが好ましく、より好ましくは短辺が１２００ｍｍ以上、長辺が１３００ｍｍ以上であり、さらに好ましくは短辺が１４００ｍｍ以上、長辺が１７００ｍｍ以上である。積層基板１０の大きさの上限値としては、３０００ｍｍ×３０００ｍｍであることが好ましい。 <Packing body>
FIG. 6 is a side view schematically showing an example of the packaging body according to the embodiment of the present invention. In the packaging body 20 shown in FIG. 6, the same components as those of the laminated substrate 10 of the first example shown in FIGS. 1 and 2 are designated by the same reference numerals, and detailed description thereof will be omitted.
The packing body 20 has a plurality of laminated substrates 10 shown in FIG. 1 described above, and a pallet 22 on which the plurality of laminated substrates 10 are laminated and loaded.
When the laminated substrate 10 is 1200 mm × 1000 mm (G5 size) or more, it is difficult to pack the laminated substrates in a case in a state where they are completely separated from each other, and a state in which a plurality of laminated substrates 10 are mutually loaded as described later. It is preferable to load the laminated substrate 10 on the pallet 22 and pack the laminated substrate 10.
The laminated substrate 10 is a quadrangle, and the size of the laminated substrate 10 is preferably 850 mm or more on the short side and 1100 mm or more on the long side, and more preferably 1200 mm or more on the short side and 1300 mm or more on the long side. More preferably, the short side is 1400 mm or more and the long side is 1700 mm or more. The upper limit of the size of the laminated substrate 10 is preferably 3000 mm × 3000 mm.

パレット２２は、底板２４と、背板２６とを有し、底板２４に背板２６が立設されている。底板２４の表面２４ａと背板２６の表面２６ａとは直交している。積層基板１０の支持基材１２を背板２６の表面２６ａに向けて、例えば、最もパレット２２側の積層基板１０を、支持基材１２を底板２４の表面２４ａと背板２６の表面２６ａとに渡して、積層基板１０を傾けた状態でパレット２２に積層される。積層基板１０の支持基材１２の裏面１２ｂと底板２４の表面２４ａとのなす角βの角度は、例えば、４５°〜８５°である。
積層基板１０の保護フィルム１６上に、別の積層基板１０の支持基材１２を接して重ねて、複数の積層基板１０が接触して積層される。
パレット２２は、ポリプロピレン樹脂等の樹脂で構成されるが、特に限定されない。
複数の積層基板１０は、相互に荷重がかかる状態であれば、相互に直接接触させてパレット２２に積載してもよく、また、後述のように積層基板１０間に合紙を設けて、複数の積層基板１０をパレット２２に積載してもよい。
また、支持基材１２の裏面１２ｂと隣接する積層基板１０の保護フィルム１６の表面とを分離することを目的として、合紙を間に入れてもよい。合紙を入れることで、支持基材１２の裏面１２ｂと隣接する積層基板１０の保護フィルム１６の表面との密着を低減し、パレット２２から積層基板１０を取る場合に、容易に１枚ずつ取ることができる。 The pallet 22 has a bottom plate 24 and a back plate 26, and the back plate 26 is erected on the bottom plate 24. The surface 24a of the bottom plate 24 and the surface 26a of the back plate 26 are orthogonal to each other. The supporting base material 12 of the laminated substrate 10 is directed toward the surface 26a of the back plate 26, for example, the laminated substrate 10 on the pallet 22 side most is used, and the supporting base material 12 is placed on the surface 24a of the bottom plate 24 and the surface 26a of the back plate 26. It is handed over and laminated on the pallet 22 in a state where the laminated substrate 10 is tilted. The angle β formed by the back surface 12b of the support base material 12 of the laminated substrate 10 and the surface surface 24a of the bottom plate 24 is, for example, 45 ° to 85 °.
The support base material 12 of another laminated substrate 10 is brought into contact with and laminated on the protective film 16 of the laminated substrate 10, and the plurality of laminated substrates 10 are brought into contact with each other and laminated.
The pallet 22 is made of a resin such as polypropylene resin, but is not particularly limited.
The plurality of laminated substrates 10 may be directly contacted with each other and loaded on the pallet 22 as long as the loads are applied to each other, and a plurality of laminated substrates 10 may be provided with interleaving paper as described later. The laminated substrate 10 of the above may be loaded on the pallet 22.
Further, an interleaving paper may be inserted for the purpose of separating the back surface 12b of the support base material 12 and the front surface of the protective film 16 of the adjacent laminated substrate 10. By inserting the interleaving paper, the adhesion between the back surface 12b of the supporting base material 12 and the front surface of the protective film 16 of the adjacent laminated substrate 10 is reduced, and when the laminated substrate 10 is taken from the pallet 22, it is easily taken one by one. be able to.

なお、パレット２２は、底板２４と背板２６とを有する構成としたが、複数の積層基板１０を積層して積載することができれば、その構成は、特に限定されない。
パレット２２に複数の積層基板１０が相互に荷重がかかる状態で積載された梱包体２０の形態で、積層基板１０が搬送される。このとき、複数の積層基板１０のうち、最も背板２６側の積層基板１０には最も大きな荷重がかかり、かつ搬送時の振動により積層基板１０同士が擦れる。上述のように保護フィルム１６を設けることにより、積層基板１０に荷重がかかっても、積層基板１０同士が擦れても、ポリイミド樹脂層１４に、打痕がつくこと、およびキズがつくこと、さらには異物が付着することが抑制される。 The pallet 22 has a bottom plate 24 and a back plate 26, but the configuration is not particularly limited as long as a plurality of laminated substrates 10 can be stacked and loaded.
The laminated substrate 10 is conveyed in the form of a package 20 in which a plurality of laminated substrates 10 are loaded on the pallet 22 in a state where a load is applied to each other. At this time, the largest load is applied to the laminated substrate 10 on the back plate 26 side of the plurality of laminated substrates 10, and the laminated substrates 10 rub against each other due to vibration during transportation. By providing the protective film 16 as described above, even if a load is applied to the laminated substrates 10 or the laminated substrates 10 rub against each other, the polyimide resin layer 14 is dented and scratched, and further. Is suppressed from adhering foreign matter.

積層基板１０では、支持基材１２と保護フィルム１６との第２の密着力Ｆ２が上述の範囲であるため、一般環境中で、梱包体２０の輸送を行っても、保護フィルム１６と支持基材１２との剥離が生じず、ポリイミド樹脂層１４の外周部分に異物が多量に付着することがなく、欠点が増加しない。
パレット２２に積載される積層基板１０は、図１に示す第１の例の積層基板１０に限定されるものではなく、上述の第２の例の積層基板１０および上述の第３の例の積層基板１０でもよい。
また、積層基板１０は、例えば、日本国特許第４２５１２９０号公報に記載されているガラス板梱包箱（図１〜図１７参照）を利用して梱包できる。 In the laminated substrate 10, since the second adhesive force F 2 between the support base material 12 and the protective film 16 is within the above range, the protective film 16 and the protective film 16 are supported even when the package 20 is transported in a general environment. Peeling from the base material 12 does not occur, a large amount of foreign matter does not adhere to the outer peripheral portion of the polyimide resin layer 14, and defects do not increase.
The laminated substrate 10 loaded on the pallet 22 is not limited to the laminated substrate 10 of the first example shown in FIG. 1, and the laminated substrate 10 of the second example described above and the laminated substrate 10 of the third example described above are laminated. The substrate 10 may be used.
Further, the laminated substrate 10 can be packed by using, for example, a glass plate packing box (see FIGS. 1 to 17) described in Japanese Patent No. 4251290.

ガラス板梱包箱は、具体的には、積層基板１０を並べて載置する台座と、この台座を載置する底板と、底板上に立てて配設される前板、後板および両側板と、上部を塞ぐ天板で構成される。
ガラス板梱包箱は、底板の上部前縁および両側縁に、前板および両側板を嵌め込むための取付部材を備える。取付部材は、底面板に、対向する１対の側板が設けられており、対向する側板の間に、前板および両側板が嵌め込まれる。取付部材は上述の構成以外に、底板に、上方が開口した溝を設けて、この溝に前板および両側板を嵌め込む構造としてもよい。
また、底受け板および背受け板には、積層基板を載置した際の損傷を防止するために、それぞれクッション材が貼り付けられてもよい。
また、台座に複数の積層基板を載置した後、複数の積層基板からなる収納体の前側を樹脂製等の保護板で覆い、両角部にアングル材を配設し、これらをバンドで結束してもよい。このバンドは長さ調節可能なベルト部材の端部に備わる固定金具をトグルクランプに係合させる等して収納体を確実に結束する。このように、バンドを用いて収納体を結束することにより、簡単な機構でしっかりと全体を固定できる。また、保護板をクッション性を有する部材とすれば、積層基板をバンドで結束後、トグルクランプをさらに強固に結束できる。 Specifically, the glass plate packing box includes a pedestal on which the laminated substrates 10 are placed side by side, a bottom plate on which the pedestal is placed, and a front plate, a rear plate, and both side plates arranged upright on the bottom plate. It consists of a top plate that closes the top.
The glass plate packing box is provided with mounting members for fitting the front plate and both side plates on the upper front edge and both side edges of the bottom plate. The mounting member is provided with a pair of side plates facing each other on the bottom plate, and the front plate and both side plates are fitted between the side plates facing each other. In addition to the above-described configuration, the mounting member may have a structure in which a groove with an upper opening is provided in the bottom plate, and the front plate and both side plates are fitted into the groove.
Further, cushioning materials may be attached to the bottom support plate and the back support plate, respectively, in order to prevent damage when the laminated substrate is placed.
Further, after mounting a plurality of laminated substrates on the pedestal, the front side of the storage body composed of the plurality of laminated substrates is covered with a protective plate made of resin or the like, angle members are arranged at both corners, and these are bound by a band. You may. This band securely binds the stored body by engaging the fixing bracket provided at the end of the belt member whose length can be adjusted with the toggle clamp. By bundling the storage body with the band in this way, the whole can be firmly fixed by a simple mechanism. Further, if the protective plate is a member having a cushioning property, the toggle clamp can be bound more firmly after the laminated substrate is bound by the band.

以下、積層基板１０を構成する支持基材１２、ポリイミド樹脂層１４、シリコーン樹脂層１３、および保護フィルム１６について詳述する。 Hereinafter, the supporting base material 12, the polyimide resin layer 14, the silicone resin layer 13, and the protective film 16 constituting the laminated substrate 10 will be described in detail.

＜支持基材＞
ガラス製の支持基材１２は、ポリイミド樹脂層１４を支持して補強する部材であり、かつ搬送基板として機能する。支持基材１２は、例えば、ガラス板で構成される。
ガラスの種類としては、無アルカリホウケイ酸ガラス、ホウケイ酸ガラス、ソーダライムガラス、高シリカガラス、その他の酸化ケイ素を主な成分とする酸化物系ガラスが好ましい。酸化物系ガラスとしては、酸化物換算による酸化ケイ素の含有量が４０〜９０質量％のガラスが好ましい。
ガラス板として、より具体的には、無アルカリホウケイ酸ガラスからなるガラス板（ＡＧＣ株式会社製商品名「ＡＮ１００」）が挙げられる。
ガラス板の製造方法としては、通常、ガラス原料を溶融し、溶融ガラスを板状に成形する方法が挙げられる。このような成形方法は、一般的なものであってよく、例えば、フロート法、フュージョン法、およびスロットダウンドロー法が挙げられる。 <Supporting base material>
The glass support base material 12 is a member that supports and reinforces the polyimide resin layer 14, and also functions as a transport substrate. The support base material 12 is composed of, for example, a glass plate.
As the type of glass, non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glass containing silicon oxide as a main component are preferable. As the oxide-based glass, glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.
More specifically, a glass plate made of non-alkali borosilicate glass (trade name "AN100" manufactured by AGC Inc.) can be mentioned.
Examples of the method for manufacturing a glass plate include a method in which a glass raw material is melted and molten glass is formed into a plate shape. Such molding methods may be general and include, for example, the float method, the fusion method, and the slot down draw method.

支持基材１２の厚さは、ポリイミド樹脂層１４よりも厚くてもよいし、薄くてもよい。積層基板１０の取り扱い性の点から、支持基材１２の厚さはポリイミド樹脂層１４よりも厚いことが好ましい。
支持基材１２は、補強板および搬送基板としての機能が要求されるものであることから、フレキシブルではないことが好ましい。そのため、支持基材１２の厚さは、０．３ｍｍ以上が好ましく、０．５ｍｍ以上がより好ましい。一方、支持基材１２の厚さは１．０ｍｍ以下が好ましい。 The thickness of the support base material 12 may be thicker or thinner than that of the polyimide resin layer 14. From the viewpoint of handleability of the laminated substrate 10, the thickness of the supporting base material 12 is preferably thicker than that of the polyimide resin layer 14.
The support base material 12 is preferably not flexible because it is required to function as a reinforcing plate and a transport substrate. Therefore, the thickness of the support base material 12 is preferably 0.3 mm or more, and more preferably 0.5 mm or more. On the other hand, the thickness of the support base material 12 is preferably 1.0 mm or less.

＜ポリイミド樹脂層＞
ポリイミド樹脂層１４は、ポリイミド樹脂からなり、例えば、ポリイミドフィルムが用いられる。ポリイミドフィルムの市販品の具体例としては、東洋紡株式会社製の「ゼノマックス」、宇部興産株式会社製の「ユーピレックス２５Ｓ」が挙げられる。
電子デバイスを構成する高精細な配線等を形成するために、ポリイミド樹脂層１４の表面１４ａは平滑であることが好ましい。具体的には、ポリイミド樹脂層１４の表面１４ａの表面粗度Ｒａは、５０ｎｍ以下が好ましく、３０ｎｍ以下がより好ましく、１０ｎｍ以下がさらに好ましい。表面粗度Ｒａの下限としては、０．０１ｎｍ以上が挙げられる。
ポリイミド樹脂層１４の厚さは、製造工程でのハンドリング性の点から、１μｍ以上が好ましく、５μｍ以上がより好ましく、１０μｍ以上がさらに好ましい。柔軟性の点から、ポリイミド樹脂層１４の厚さは１ｍｍ以下が好ましく、０．２ｍｍ以下がより好ましい。
ポリイミド樹脂層１４の熱膨張係数と支持基材１２の熱膨張係数との差は、小さい方が加熱後または冷却後の反りを抑制できるため好ましい。具体的には、ポリイミド樹脂層１４と支持基材１２との熱膨張係数の差は、０〜９０×１０-６／℃が好ましく、０〜３０×１０-６／℃がより好ましい。 <Polyimide resin layer>
The polyimide resin layer 14 is made of a polyimide resin, and for example, a polyimide film is used. Specific examples of commercially available polyimide films include "Xenomax" manufactured by Toyobo Co., Ltd. and "UPIREX 25S" manufactured by Ube Industries, Ltd.
The surface 14a of the polyimide resin layer 14 is preferably smooth in order to form high-definition wiring and the like constituting the electronic device. Specifically, the surface roughness Ra of the surface 14a of the polyimide resin layer 14 is preferably 50 nm or less, more preferably 30 nm or less, still more preferably 10 nm or less. The lower limit of the surface roughness Ra is 0.01 nm or more.
The thickness of the polyimide resin layer 14 is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, from the viewpoint of handleability in the manufacturing process. From the viewpoint of flexibility, the thickness of the polyimide resin layer 14 is preferably 1 mm or less, more preferably 0.2 mm or less.
The difference between the coefficient of thermal expansion of the polyimide resin layer 14 and the coefficient of thermal expansion of the supporting base material 12 is preferably small because warpage after heating or cooling can be suppressed. Specifically, the difference in the coefficient of thermal expansion between the polyimide resin layer 14 and the supporting base material 12 is preferably 0 to 90 × 10 -6 / ° C, more preferably 0 to 30 × 10 -6 / ° C.

ポリイミド樹脂層１４の面積（表面１４ａの面積）は、特に制限されないが、保護フィルム１６を配置するため、支持基材１２の面積よりも小さいことが好ましい。一方、ポリイミド樹脂層１４の面積は、電子デバイスの生産性の点から、３００ｃｍ２以上が好ましい。
ポリイミド樹脂層１４の形状は、特に制限されず、矩形状であっても円形状であってもよい。ポリイミド樹脂層１４には、オリエンテーションフラット（基板の外周に形成された平坦部分）、およびノッチ（基板の外周縁に形成された、少なくとも１つのＶ型の切欠き）が形成されていてもよい。 The area of the polyimide resin layer 14 (the area of the surface 14a) is not particularly limited, but is preferably smaller than the area of the supporting base material 12 in order to arrange the protective film 16. On the other hand, the area of the polyimide resin layer 14 is preferably 300 cm 2 or more from the viewpoint of productivity of electronic devices.
The shape of the polyimide resin layer 14 is not particularly limited, and may be rectangular or circular. The polyimide resin layer 14 may be formed with an orientation flat (a flat portion formed on the outer periphery of the substrate) and a notch (at least one V-shaped notch formed on the outer peripheral edge of the substrate).

＜保護フィルム＞
保護フィルム１６は、図３に示すように基材１８と密着層１９と有する積層構造であることが好ましい。
保護フィルム１６の厚さは、外部から受けた力の影響を低減するために２０μｍ以上であることが好ましく、３０μｍ以上であることがより好ましく、５０μｍ以上であることが更に好ましい。保護フィルム１６の厚さの上限値としては、５００μｍ以下であることが好ましく、より好ましくは３００μｍ以下、更に好ましくは１００μｍ以下である。
保護フィルム１６の厚さとは、基材１８と密着層１９と有する積層構造である場合には、基材１８と密着層１９との合計の厚さである。保護フィルム１６の厚さの上限としては、厚すぎると、保護フィルムを剥離する際に過大な力が必要となる場合があるため、５００μｍ以下が好ましい。
保護フィルム１６の厚さは、５点以上の任意の位置における保護フィルム１６の厚さを接触式膜厚測定装置で測定し、それらを算術平均したものである。
また、保護フィルム１６の基材１８は、ポリエステル樹脂（例えば、ポリエチレンテレフタレート（ＰＥＴ））、ポリオレフィン樹脂（例えば、ポリエチレン（ＰＥ）、およびポリプロピレン等）、ポリウレタン樹脂等の樹脂で構成されることが好ましい。このうち、保護フィルム１６の基材１８を構成する樹脂としては、ポリオレフィンが好ましく、ポリエチレンまたはポリプロピレンがより好ましい。
密着層１９は、上述の第１の密着力Ｆ１、および第２の密着力Ｆ２を満たせば、特に限定されるものではない。密着層１９としては、公知の粘着層を用いてもよい。粘着層を構成する粘着剤の具体例としては、（メタ）アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤が挙げられる。
また、密着層１９は樹脂で構成されていてもよく、樹脂の具体例としては、酢酸ビニル樹脂、エチレン−酢酸ビニル共重合体樹脂、塩化ビニル−酢酸ビニル共重合樹脂、（メタ）アクリル樹脂、ブチラール樹脂、ポリウレタン樹脂、ポリスチレンエラストマー等が挙げられる。
なお、（メタ）アクリルとは、アクリルとメタクリルとを含む概念である。 <Protective film>
As shown in FIG. 3, the protective film 16 preferably has a laminated structure having a base material 18 and an adhesion layer 19.
The thickness of the protective film 16 is preferably 20 μm or more, more preferably 30 μm or more, and further preferably 50 μm or more in order to reduce the influence of the force received from the outside. The upper limit of the thickness of the protective film 16 is preferably 500 μm or less, more preferably 300 μm or less, and further preferably 100 μm or less.
The thickness of the protective film 16 is the total thickness of the base material 18 and the adhesion layer 19 in the case of a laminated structure having the base material 18 and the adhesion layer 19. The upper limit of the thickness of the protective film 16 is preferably 500 μm or less because if it is too thick, an excessive force may be required when peeling the protective film.
The thickness of the protective film 16 is obtained by measuring the thickness of the protective film 16 at any position of 5 points or more with a contact-type film thickness measuring device and arithmetically averaging them.
Further, the base material 18 of the protective film 16 is preferably composed of a resin such as a polyester resin (for example, polyethylene terephthalate (PET)), a polyolefin resin (for example, polyethylene (PE) and polypropylene), and a polyurethane resin. .. Of these, as the resin constituting the base material 18 of the protective film 16, polyolefin is preferable, and polyethylene or polypropylene is more preferable.
The adhesion layer 19 is not particularly limited as long as it satisfies the above-mentioned first adhesion force F 1 and the second adhesion force F 2 . As the adhesive layer 19, a known adhesive layer may be used. Specific examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include (meth) acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives.
The adhesive layer 19 may be made of a resin, and specific examples of the resin include vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, and (meth) acrylic resin. Butyral resin, polyurethane resin, polystyrene elastomer and the like can be mentioned.
In addition, (meth) acrylic is a concept including acrylic and methacrylic.

なお、保護フィルム１６の種類によって、ポリイミド樹脂層１４の表面１４ａに埋設物の発生のしやすさが変わってくる。以下、そのメカニズムについて詳述する。
ここで、図７〜図９は本発明の実施形態の積層基板における埋設物の発生を模式的に説明する断面図である。また、図１０は本発明の実施形態の積層基板における埋設物の一例を示すＳＥＭ像である。なお、図７〜図１０において、図１および図２に示す積層基板１０と同一構成物には、同一符号を付して、その詳細な説明は省略する。
図７に示すように、ポリイミド樹脂層１４の表面１４ａと保護フィルム１６との間に異物Ｄがある場合、保護フィルム１６が硬いと、図８に示すように保護フィルム１６が変形しにくく、ポリイミド樹脂層１４中に異物Ｄが埋まってしまう。この結果、ポリイミド樹脂層１４に埋設物が生じる。具体的には、図１０に示すＳＥＭ像のように、ポリイミド樹脂層１４に異物Ｄが埋まり、この異物Ｄが埋設物となる。
一方、保護フィルム１６が柔らかいと、図９に示すように保護フィルム１６が変形し、保護フィルム１６側に異物Ｄが付着し、ポリイミド樹脂層１４には異物Ｄが付着せず、ポリイミド樹脂層１４中に異物Ｄが埋まることもない。これにより、ポリイミド樹脂層１４の表面１４ａと保護フィルム１６との間に異物Ｄを挟んで積層してしまっても、ポリイミド樹脂層１４の欠点の発生が抑制される。このことから保護フィルム１６の基材１８は、柔らかいものであることが好ましい。
なお、保護フィルム１６の基材１８の柔らかさとは、異物Ｄの大きさ、または異物Ｄの硬さ等との相対的な関係により決定されるものである。
なお、上述の保護フィルム１６の柔らかさについては、後述のように実施例の例４〜６を評価した。 The ease with which buried objects are generated on the surface 14a of the polyimide resin layer 14 varies depending on the type of the protective film 16. The mechanism will be described in detail below.
Here, FIGS. 7 to 9 are cross-sectional views schematically illustrating the generation of buried objects in the laminated substrate according to the embodiment of the present invention. Further, FIG. 10 is an SEM image showing an example of a buried object in the laminated substrate according to the embodiment of the present invention. In FIGS. 7 to 10, the same components as the laminated substrate 10 shown in FIGS. 1 and 2 are designated by the same reference numerals, and detailed description thereof will be omitted.
As shown in FIG. 7, when there is a foreign substance D between the surface 14a of the polyimide resin layer 14 and the protective film 16, if the protective film 16 is hard, the protective film 16 is not easily deformed as shown in FIG. Foreign matter D is buried in the resin layer 14. As a result, an embedded object is formed in the polyimide resin layer 14. Specifically, as shown in the SEM image shown in FIG. 10, the foreign matter D is embedded in the polyimide resin layer 14, and the foreign matter D becomes a buried object.
On the other hand, when the protective film 16 is soft, the protective film 16 is deformed as shown in FIG. 9, foreign matter D adheres to the protective film 16 side, foreign matter D does not adhere to the polyimide resin layer 14, and the polyimide resin layer 14 does not adhere. Foreign matter D is not buried inside. As a result, even if the foreign matter D is sandwiched between the surface 14a of the polyimide resin layer 14 and the protective film 16 and laminated, the occurrence of defects of the polyimide resin layer 14 is suppressed. For this reason, the base material 18 of the protective film 16 is preferably soft.
The softness of the base material 18 of the protective film 16 is determined by the relative relationship with the size of the foreign matter D, the hardness of the foreign matter D, and the like.
Regarding the softness of the protective film 16 described above, Examples 4 to 6 of Examples were evaluated as described later.

＜シリコーン樹脂層＞
シリコーン樹脂層１３は、主に、シリコーン樹脂からなるものである。シリコーン樹脂の構造は特に制限されない。シリコーン樹脂は、通常、硬化処理によってシリコーン樹脂となり得る硬化性シリコーンを硬化（架橋硬化）して得られる。
硬化性シリコーンの具体例としては、その硬化機構により、縮合反応型シリコーン、付加反応型シリコーン、紫外線硬化型シリコーン、および電子線硬化型シリコーンが挙げられる。硬化性シリコーンの重量平均分子量は、５，０００〜６０，０００が好ましく、５，０００〜３０，０００がより好ましい。 <Silicone resin layer>
The silicone resin layer 13 is mainly made of a silicone resin. The structure of the silicone resin is not particularly limited. The silicone resin is usually obtained by curing (crosslink curing) a curable silicone that can become a silicone resin by a curing treatment.
Specific examples of the curable silicone include a condensation reaction type silicone, an addition reaction type silicone, an ultraviolet curable silicone, and an electron beam curable silicone depending on the curing mechanism. The weight average molecular weight of the curable silicone is preferably 5,000 to 60,000, more preferably 5,000 to 30,000.

シリコーン樹脂層１３の製造方法としては、ポリイミド樹脂層１４の裏面（表面１４ａと反対側の面）に上述のシリコーン樹脂となる硬化性シリコーンを含む硬化性組成物を塗布して、必要に応じて溶媒を除去して、塗膜を形成して、塗膜中の硬化性シリコーンを硬化させて、シリコーン樹脂層１３とする方法が好ましい。
硬化性組成物は、硬化性シリコーンの他に、溶媒、白金触媒（硬化性シリコーンとして付加反応型シリコーンを用いる場合）、レベリング剤、および金属化合物等を含んでいてもよい。金属化合物に含まれる金属元素の具体例としては、３ｄ遷移金属、４ｄ遷移金属、ランタノイド系金属、ビスマス、アルミニウム、およびスズが挙げられる。金属化合物の含有量は、適宜調整される。 As a method for producing the silicone resin layer 13, a curable composition containing the above-mentioned curable silicone to be a silicone resin is applied to the back surface (the surface opposite to the surface 14a) of the polyimide resin layer 14, and if necessary. A method of removing the solvent to form a coating film and curing the curable silicone in the coating film to form the silicone resin layer 13 is preferable.
The curable composition may contain, in addition to the curable silicone, a solvent, a platinum catalyst (when an addition reaction type silicone is used as the curable silicone), a leveling agent, a metal compound and the like. Specific examples of the metal element contained in the metal compound include 3d transition metal, 4d transition metal, lanthanoid metal, bismuth, aluminum, and tin. The content of the metal compound is adjusted as appropriate.

シリコーン樹脂層１３の厚さは、１００μｍ以下が好ましく、５０μｍ以下がより好ましく、３０μｍ以下がさらに好ましい。一方、シリコーン樹脂層１３の厚さは、１μｍ超が好ましく、４μｍ以上がより好ましい。上述の厚さは、５点以上の任意の位置におけるシリコーン樹脂層１３の厚さを接触式膜厚測定装置で測定し、それらを算術平均したものである。 The thickness of the silicone resin layer 13 is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. On the other hand, the thickness of the silicone resin layer 13 is preferably more than 1 μm, more preferably 4 μm or more. The above-mentioned thickness is obtained by measuring the thickness of the silicone resin layer 13 at an arbitrary position of 5 points or more with a contact-type film thickness measuring device and arithmetically averaging them.

＜積層基板の用途＞
積層基板１０の用途としては、後述の表示デバイス、受信センサーパネル、太陽電池、薄膜２次電池、および集積回路等が挙げられる。保護フィルム１６が剥がされた状態でポリイミド樹脂層が大気雰囲気下にて、例えば、４５０℃以上の高温条件に、２０分間以上曝される場合もある。
表示デバイスの具体例としては、ＬＣＤ、ＯＬＥＤ、電子ペーパー、プラズマディスプレイパネル、フィールドエミッションパネル、量子ドットＬＥＤパネル、マイクロＬＥＤディスプレイパネル、およびＭＥＭＳ（Ｍｉｃｒｏ Ｅｌｅｃｔｒｏ Ｍｅｃｈａｎｉｃａｌ Ｓｙｓｔｅｍｓ）シャッターパネルが挙げられる。
受信センサーパネルの具体例としては、電磁波受信センサーパネル、Ｘ線受光センサーパネル、紫外線受光センサーパネル、可視光線受光センサーパネル、および赤外線受光センサーパネルが挙げられる。受信センサーパネルに用いる場合、樹脂等の補強シート等によってポリイミド樹脂層が補強されていてもよい。 <Use of laminated substrate>
Applications of the laminated substrate 10 include display devices, receiving sensor panels, solar cells, thin-film secondary batteries, integrated circuits, and the like, which will be described later. With the protective film 16 peeled off, the polyimide resin layer may be exposed to an air atmosphere, for example, a high temperature condition of 450 ° C. or higher for 20 minutes or longer.
Specific examples of the display device include an LCD, an OLED, an electronic paper, a plasma display panel, a field emission panel, a quantum dot LED panel, a micro LED display panel, and a MEMS (Micro Electro Mechanical Systems) shutter panel.
Specific examples of the receiving sensor panel include an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet receiving sensor panel, a visible light receiving sensor panel, and an infrared receiving sensor panel. When used for a receiving sensor panel, the polyimide resin layer may be reinforced with a reinforcing sheet such as resin.

上述したように、本発明の積層基板から保護フィルムを剥離した後、得られた支持基材とポリイミド樹脂層とを含む積層体を用いて、ポリイミド樹脂層と電子デバイス用部材とを含む電子デバイスが製造される。
電子デバイスの製造方法としては、例えば、得られた支持基材とポリイミド樹脂層とを含む積層体中のポリイミド樹脂層上に電子デバイス用部材を形成して、得られた電子デバイス用部材付き積層体から、支持基材を剥離して、ポリイミド樹脂層と電子デバイス用部材とを有する電子デバイスを得る方法が挙げられる。
なお、上記電子デバイス用部材は、電子デバイスの少なくとも一部を構成する部材である。 As described above, after peeling the protective film from the laminated substrate of the present invention, an electronic device including a polyimide resin layer and a member for an electronic device is used by using the obtained laminate containing the support base material and the polyimide resin layer. Is manufactured.
As a method for manufacturing an electronic device, for example, a member for an electronic device is formed on a polyimide resin layer in a laminate including the obtained support base material and a polyimide resin layer, and the obtained laminate with the member for the electronic device is formed. Examples thereof include a method of peeling a support base material from a body to obtain an electronic device having a polyimide resin layer and a member for an electronic device.
The electronic device member is a member that constitutes at least a part of the electronic device.

以下に、実施例等により本発明を具体的に説明するが、本発明はこれらの例によって制限されるものではない。後述する例１〜６は実施例であり、例７〜１６は比較例である。 Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited to these examples. Examples 1 to 6 described later are examples, and examples 7 to 16 are comparative examples.

＜評価＞
（外周部異物の評価）
外周部異物の評価においては、各例において、保護フィルムを設ける前に、オルボテック社製光学式検査装置を用いて予めポリイミド樹脂層の外周部１０ｍｍ幅の額縁領域の表面に存在している欠点の位置情報および画像を取得した。そして、各例において得られた積層基板の保護フィルム上に、１６ｇ／ｃｍ２の荷重をかけた状態で、温度４０℃、相対湿度８０％の雰囲気に５日間放置した。その後、保護フィルムを剥がし、再度オルボテック社製光学式検査装置を用いてポリイミド樹脂層の外周部１０ｍｍ幅の額縁領域の表面に存在している欠点の位置情報および画像を取得した。
保護フィルムを設ける前後の画像を比較し、額縁領域の異物の有無を評価した。異物以外に、糊残りやキズの欠点が発生する可能性があるため、異物を示す画像を予め定義しておき、画像の比較の際に、異物を示す画像を参照しての異物の有無を評価した。
画像の比較の結果、外周部に異物があれば「有り」とし、外周部に異物がなければ「無し」とした。 <Evaluation>
(Evaluation of foreign matter on the outer circumference)
In the evaluation of the outer peripheral foreign matter, in each example, there is a defect that the outer peripheral portion of the polyimide resin layer has a 10 mm wide frame region surface in advance using an optical inspection device manufactured by Orbotech before the protective film is provided. Position information and images were acquired. Then, the protective film of the laminated substrate obtained in each example was left to stand in an atmosphere having a temperature of 40 ° C. and a relative humidity of 80% for 5 days under a load of 16 g / cm 2 . Then, the protective film was peeled off, and the position information and the image of the defect existing on the surface of the frame region of the outer peripheral portion of the polyimide resin layer having a width of 10 mm were acquired again using an optical inspection device manufactured by Orbotech.
The images before and after the protective film was installed were compared to evaluate the presence or absence of foreign matter in the frame area. In addition to foreign matter, there is a possibility that adhesive residue and scratches may occur. Therefore, an image showing foreign matter is defined in advance, and when comparing the images, the presence or absence of foreign matter is checked by referring to the image showing foreign matter. evaluated.
As a result of comparing the images, if there was a foreign substance on the outer peripheral portion, it was evaluated as "present", and if there was no foreign substance on the outer peripheral portion, it was evaluated as "absent".

（糊残りの評価）
糊残りの評価においては、各例において、保護フィルムを設ける前に、オルボテック社製光学式検査装置を用いて予めポリイミド樹脂層の表面に存在している欠点の位置情報および画像を取得した。そして、各例において得られた積層基板の保護フィルム上に、１６ｇ／ｃｍ２の荷重をかけた状態で、温度４０℃、相対湿度８０％の雰囲気に５日間放置した。その後、保護フィルムを剥がし、再度オルボテック社製光学式検査装置を用いてポリイミド樹脂層の表面に存在している欠点の位置情報および画像を取得した。
保護フィルムを設ける前後の画像を比較し、糊残りの有無を評価する。糊残り以外に、キズ等が付く可能性があるため、糊残りを示す画像を予め定義しておき、画像の比較の際に、糊残りを示す画像を参照して糊残りの有無を評価した。
画像の比較の結果、糊残りがあれば「有り」とし、糊残りがなければ「無し」とした。 (Evaluation of adhesive residue)
In the evaluation of the adhesive residue, in each example, the position information and the image of the defect existing on the surface of the polyimide resin layer were acquired in advance using an optical inspection device manufactured by Orbotech Co., Ltd. before the protective film was provided. Then, the protective film of the laminated substrate obtained in each example was left to stand in an atmosphere having a temperature of 40 ° C. and a relative humidity of 80% for 5 days under a load of 16 g / cm 2 . Then, the protective film was peeled off, and the position information and the image of the defect existing on the surface of the polyimide resin layer were acquired again using an optical inspection device manufactured by Orbotech.
The images before and after the protective film is installed are compared to evaluate the presence or absence of adhesive residue. Since there is a possibility of scratches other than the adhesive residue, an image showing the adhesive residue was defined in advance, and when comparing the images, the presence or absence of the adhesive residue was evaluated by referring to the image showing the adhesive residue. ..
As a result of comparing the images, if there was adhesive residue, it was evaluated as "yes", and if there was no adhesive residue, it was evaluated as "none".

（キズの評価）
キズの評価においては、各例において、保護フィルムを設ける前に、オルボテック社製光学式検査装置を用いて予めポリイミド樹脂層の表面に存在している欠点の位置情報および画像を取得した。
そして、各例において得られた積層基板の保護フィルム上に、厚さ２．８ｍｍのガラス板を２３枚積み重ねて荷重をかけた状態で、温度４０℃、相対湿度８０％の雰囲気に５日間放置した。その後、保護フィルムを剥がし、ポリイミド樹脂層の表面を、再度オルボテック社製光学式検査装置を用いてポリイミド樹脂層の表面の画像を取得した。
荷重をかける前後の画像を比較し、キズの有無を評価した。キズ以外に、糊残り等が生じる可能性があるため、キズを示す画像を予め定義しておき、画像の比較の際に、キズを示す画像を参照してキズの有無を評価した。
画像の比較の結果、キズがあれば「有り」とし、キズがなければ「無し」とした。 (Evaluation of scratches)
In the evaluation of scratches, in each example, before the protective film was provided, the position information and the image of the defect existing on the surface of the polyimide resin layer were acquired in advance by using an optical inspection device manufactured by Orbotech.
Then, 23 glass plates having a thickness of 2.8 mm were stacked on the protective film of the laminated substrate obtained in each example and left in an atmosphere of a temperature of 40 ° C. and a relative humidity of 80% for 5 days. did. Then, the protective film was peeled off, and an image of the surface of the polyimide resin layer was obtained again using an optical inspection device manufactured by Orbotech.
The images before and after applying the load were compared to evaluate the presence or absence of scratches. Since there is a possibility that adhesive residue or the like may occur in addition to the scratches, an image showing the scratches was defined in advance, and when comparing the images, the presence or absence of the scratches was evaluated by referring to the image showing the scratches.
As a result of comparing the images, if there was a scratch, it was evaluated as "yes", and if there was no scratch, it was evaluated as "none".

（支持基材破損の評価）
各例において得られた積層基板から保護フィルムを剥離した際に、支持基材の破損が生じた場合を「有り」として、破損が生じない場合を「無し」とした。 (Evaluation of damage to supporting base material)
When the protective film was peeled off from the laminated substrate obtained in each example, the case where the supporting base material was damaged was defined as "yes", and the case where no damage occurred was defined as "absent".

（耐熱試験の評価）
保護フィルム剥離後の積層基板の耐熱性評価を以下のように実施した。
糊残り評価に用いた積層基板に、プラズマＣＶＤ法を用いて、窒化ケイ素膜（ＳｉＮｘ）を厚さ２００ｎｍ成膜した。その後、窒素雰囲気で、５００℃、１０分間加熱を行った。加熱後、ポリイミド樹脂層が支持基材から剥がれがない場合、耐熱性を「○」、剥がれがあった場合、耐熱性を「×」と評価した。 (Evaluation of heat resistance test)
The heat resistance of the laminated substrate after the protective film was peeled off was evaluated as follows.
A silicon nitride film (SiNx) having a thickness of 200 nm was formed on the laminated substrate used for the evaluation of adhesive residue by using a plasma CVD method. Then, it was heated at 500 ° C. for 10 minutes in a nitrogen atmosphere. When the polyimide resin layer was not peeled off from the supporting base material after heating, the heat resistance was evaluated as “◯”, and when there was peeling, the heat resistance was evaluated as “x”.

（埋設異物の評価）
保護フィルムの種類によって、ポリイミド樹脂層に異物が埋設するかどうかの評価は以下のように実施した。
まず、保護フィルムを設ける前に、意図的にポリイミド樹脂層の上に異物を載せるために、常圧常温環境にポリイミド樹脂層を放置したのち、オルボテック社製光学式検査装置で欠点（異物）の検査を実施した。その後、ポリイミド樹脂層の上に保護フィルムを設け、厚さ２．８ｍｍのガラス板を２３枚積み重ねて荷重をかけた状態で、温度４０℃、相対湿度８０％の雰囲気に５日間放置した。次に、保護フィルムを剥がし、ポリイミド樹脂層の表面を、再度オルボテック社製光学式検査装置を用いてポリイミド樹脂層の表面の欠点（異物）検査を実施した。保護フィルム貼合前後のオルボテック社製光学式検査装置の欠点の分布を比較することで、貼合前にポリイミド樹脂層上に存在していた異物が、保護フィルム剥離後に残留しているかどうかを確認した後、残留している異物に関して、光学顕微鏡及び走査型電子顕微鏡（ＳＥＭ）を用いて異物の表面観察を実施した。光学顕微鏡による画像と走査型電子顕微鏡により画像とを比較することにより、埋設異物かどうかの判定を行った。 (Evaluation of buried foreign matter)
The evaluation of whether or not foreign matter is embedded in the polyimide resin layer depending on the type of protective film was carried out as follows.
First, before the protective film is provided, in order to intentionally place a foreign substance on the polyimide resin layer, the polyimide resin layer is left in a normal pressure normal temperature environment, and then a defect (foreign substance) is found in an optical inspection device manufactured by Orbotech. An inspection was carried out. Then, a protective film was provided on the polyimide resin layer, and 23 glass plates having a thickness of 2.8 mm were stacked and loaded, and the mixture was left in an atmosphere having a temperature of 40 ° C. and a relative humidity of 80% for 5 days. Next, the protective film was peeled off, and the surface of the polyimide resin layer was again inspected for defects (foreign matter) on the surface of the polyimide resin layer using an optical inspection device manufactured by Orbotech. By comparing the distribution of defects of the Orbotech optical inspection device before and after bonding the protective film, it is confirmed whether foreign matter that was present on the polyimide resin layer before bonding remains after the protective film is peeled off. After that, the surface of the remaining foreign matter was observed using an optical microscope and a scanning electron microscope (SEM). By comparing the image obtained by the optical microscope with the image obtained by the scanning electron microscope, it was determined whether or not the foreign matter was buried.

（長期保管に関する評価）
保護フィルムを貼合し、貼合面に荷重がかかった状態で保管された場合に、ポリイミド樹脂層表面に糊残りやキズが発生するかどうかの確認を実施した。各例において、長期保管試験用の積層基板を、３枚ずつ準備した。各例において、保護フィルムを設ける前に、オルボテック社製光学式検査装置を用いて予めポリイミド樹脂層の表面に存在している欠点の位置情報および画像を取得した。そして、ポリイミド樹脂層の上に保護フィルムを設け、各例において得られた積層基板の保護フィルム上に、１６ｇ／ｃｍ２の荷重をかけた状態で、温度４０℃、相対湿度８０％の雰囲気に５日間放置した。その後、常温、常圧の環境下に取り出し、１６ｇ／ｃｍ２の荷重をかけた状態で放置した。温度４０℃、相対湿度８０％の雰囲気に放置した期間と、常温、常圧に取り出した後に放置した期間の和が、２か月、４か月、６か月となるそれぞれの時期において、保護フィルムが貼合された積層基板１枚から荷重を取り除き、保護フィルムを剥がし、再度オルボテック社製光学式検査装置を用いてポリイミド樹脂層の表面に存在している欠点の位置情報および画像を取得した。糊残りやキズを示す画像を予め定義しておき、画像の比較の際に、糊残りやキズを示す画像を参照して糊残りやキズの有無を評価した。
保護フィルムを設ける前後の画像を比較し、糊残りやキズの有無の評価を行った。 (Evaluation regarding long-term storage)
When the protective film was attached and stored under a load on the bonded surface, it was confirmed whether or not adhesive residue or scratches were generated on the surface of the polyimide resin layer. In each example, three laminated substrates for a long-term storage test were prepared. In each example, before the protective film was provided, the position information and the image of the defect existing on the surface of the polyimide resin layer were acquired in advance by using an optical inspection device manufactured by Orbotech. Then, a protective film is provided on the polyimide resin layer, and a load of 16 g / cm 2 is applied on the protective film of the laminated substrate obtained in each example to create an atmosphere having a temperature of 40 ° C. and a relative humidity of 80%. It was left for 5 days. Then, it was taken out in an environment of normal temperature and pressure, and left in a state where a load of 16 g / cm2 was applied. The sum of the period left in an atmosphere with a temperature of 40 ° C and a relative humidity of 80% and the period left after taking out at normal temperature and pressure is 2 months, 4 months, and 6 months, respectively. The load was removed from one laminated substrate to which the film was attached, the protective film was peeled off, and the position information and images of defects existing on the surface of the polyimide resin layer were obtained again using an optical inspection device manufactured by Orbotech. .. Images showing adhesive residue and scratches were defined in advance, and when comparing the images, the presence or absence of adhesive residue and scratches was evaluated with reference to the image showing adhesive residue and scratches.
The images before and after the protective film was installed were compared to evaluate the presence or absence of adhesive residue and scratches.

以下、例１〜１６について説明する。
＜例１＞
（硬化性シリコーンの調製）
１Ｌのフラスコに、トリエトキシメチルシラン（１７９ｇ）、トルエン（３００ｇ）、酢酸（５ｇ）を加えて、混合物を２５℃で２０分間撹拌後、さらに、６０℃に加熱して１２時間反応させた。得られた反応粗液を２５℃に冷却後、水（３００ｇ）を用いて、反応粗液を３回洗浄した。
洗浄された反応粗液にクロロトリメチルシラン（７０ｇ）を加えて、混合物を２５℃で２０分間撹拌後、さらに、５０℃に加熱して１２時間反応させた。得られた反応粗液を２５℃に冷却後、水（３００ｇ）を用いて、反応粗液を３回洗浄した。
洗浄された反応粗液からトルエンを減圧留去し、スラリー状態にした後、真空乾燥機で終夜乾燥することにより、白色のオルガノポリシロキサン化合物である硬化性シリコーン１を得た。硬化性シリコーン１は、Ｔ単位の個数：Ｍ単位の個数＝８７：１３（モル比）であった。
なお、Ｍ単位は、（Ｒ）3ＳｉＯ1/2で表される１官能オルガノシロキシ単位を意味する。Ｔ単位は、ＲＳｉＯ3/2（Ｒは、水素原子または有機基を表す）で表される３官能オルガノシロキシ単位を意味する。 Examples 1 to 16 will be described below.
<Example 1>
(Preparation of curable silicone)
Triethoxymethylsilane (179 g), toluene (300 g) and acetic acid (5 g) were added to a 1 L flask, and the mixture was stirred at 25 ° C. for 20 minutes and then heated to 60 ° C. for 12 hours. The obtained crude reaction solution was cooled to 25 ° C., and then the crude reaction solution was washed 3 times with water (300 g).
Chlorotrimethylsilane (70 g) was added to the washed crude reaction solution, and the mixture was stirred at 25 ° C. for 20 minutes and then heated to 50 ° C. for 12 hours. The obtained crude reaction solution was cooled to 25 ° C., and then the crude reaction solution was washed 3 times with water (300 g).
Toluene was distilled off from the washed crude reaction solution under reduced pressure to form a slurry, which was then dried overnight in a vacuum dryer to obtain curable silicone 1 which is a white organopolysiloxane compound. The number of T units: the number of M units = 87:13 (molar ratio) of the curable silicone 1.
The M unit means a monofunctional organosiloxy unit represented by (R) 3 SiO 1/2 . The T unit means a trifunctional organosiloxy unit represented by RSiO 3/2 (R represents a hydrogen atom or an organic group).

（硬化性組成物の調製）
硬化性シリコーン１と、溶媒としてヘキサンを混合し、さらに金属化合物として２−エチルヘキサン酸ビスマス（III）を添加した。溶媒量は、固形分濃度が５０質量％となるように調整した。また、金属化合物の添加量は、金属元素が樹脂１００質量部に対して、０．０１質量部となるように調整した。得られた混合液を、孔径０．４５μｍのフィルタを用いてろ過することにより、硬化性組成物を得た。 (Preparation of curable composition)
Hexane was mixed with curable silicone 1 as a solvent, and bismuth 2-ethylhexanoate (III) was further added as a metal compound. The amount of solvent was adjusted so that the solid content concentration was 50% by mass. The amount of the metal compound added was adjusted so that the amount of the metal element was 0.01 part by mass with respect to 100 parts by mass of the resin. The obtained mixed solution was filtered using a filter having a pore size of 0.45 μm to obtain a curable composition.

（積層基板の作製）
調製した硬化性組成物を、厚さ０．０１５ｍｍのポリイミドフィルム（東洋紡株式会社製商品名「ゼノマックス」）に塗布し、ホットプレートを用いて１４０℃で１０分間加熱することにより、シリコーン樹脂層を形成した。シリコーン樹脂層の厚さは、１０μｍであった。
続いて、水系ガラス洗浄剤（株式会社パーカーコーポレーション製「ＰＫ―ＬＧＣ２１３」）で洗浄後、純水で洗浄した２００×２００ｍｍ、厚さ０．５ｍｍのガラス板「ＡＮ１００」（支持基材）をシリコーン樹脂層上に置き、貼合装置を用いて貼り合わせ、積層体を作製した。
次に、得られた積層体を窒素雰囲気下５００℃で３０分加熱した。その後、エアブローを実施して、ポリイミドフィルムの表面から細かいほこりを除去した。
得られた積層体のポリイミドフィルム側に保護フィルム１を貼り合わせて、積層基板を得た。使用した保護フィルム１としては、厚さが５５μｍのパナック株式会社 パナプロテクト（登録商標）ＥＴＫ５０Ｂ（商品名）を用いた。保護フィルム１は、基材（厚み５０μｍ、ＰＥＴフィルム）と粘着層とを有していた。 (Manufacturing of laminated substrate)
The prepared curable composition is applied to a polyimide film having a thickness of 0.015 mm (trade name "Xenomax" manufactured by Toyobo Co., Ltd.) and heated at 140 ° C. for 10 minutes using a hot plate to obtain a silicone resin layer. Was formed. The thickness of the silicone resin layer was 10 μm.
Subsequently, after cleaning with a water-based glass cleaning agent (“PK-LGC213” manufactured by Parker Corporation), a 200 × 200 mm, 0.5 mm thick glass plate “AN100” (supporting base material) washed with pure water is silicone. It was placed on a resin layer and bonded using a bonding device to prepare a laminated body.
Next, the obtained laminate was heated at 500 ° C. for 30 minutes in a nitrogen atmosphere. Then, air blow was carried out to remove fine dust from the surface of the polyimide film.
The protective film 1 was attached to the polyimide film side of the obtained laminate to obtain a laminated substrate. As the protective film 1 used, Panac Co., Ltd. Panaprotect (registered trademark) ETK50B (trade name) having a thickness of 55 μm was used. The protective film 1 had a base material (thickness 50 μm, PET film) and an adhesive layer.

＜例２〜１６＞
保護フィルムの種類を変更した以外は、例１と同様の手順に従って、例２〜例１６の積層基板を得た。
なお、例２では保護フィルム２として、厚さが６５μｍのパナック株式会社 パナプロテクト（登録商標）ＰＸ５０Ｔ０１Ａ１５（商品名）を用いた。保護フィルム２は、基材（厚み５０μｍ、ＰＥＴフィルム）と粘着層とを有していた。
例３では保護フィルム３として、厚さが５５μｍの藤森工業株式会社 マスタック（登録商標）ＰＣ−７５１（商品名）を用いた。保護フィルム３は、基材（厚み５０μｍ、ＰＥＴフィルム）と粘着層とを有していた。
例４では保護フィルム４として、厚さが６５μｍの基材（ＰＥＴフィルム）と粘着層とを有するフィルムを用いた。
例５では保護フィルム５として、厚さが７０μｍの株式会社サンエー化研 ＰＡＣ−３−７０（商品名）を用いた。保護フィルム５は、ＬＤＰＥ（低密度ポリエチレン）フィルムとエチレン−酢酸ビニル共重合体層との共押し出しフィルムであった。 <Examples 2 to 16>
Laminated substrates of Examples 2 to 16 were obtained according to the same procedure as in Example 1 except that the type of protective film was changed.
In Example 2, Panac Co., Ltd. PanaProtect (registered trademark) PX50T01A15 (trade name) having a thickness of 65 μm was used as the protective film 2. The protective film 2 had a base material (thickness 50 μm, PET film) and an adhesive layer.
In Example 3, as the protective film 3, Fujimori Kogyo Co., Ltd. Massac (registered trademark) PC-751 (trade name) having a thickness of 55 μm was used. The protective film 3 had a base material (thickness 50 μm, PET film) and an adhesive layer.
In Example 4, as the protective film 4, a film having a base material (PET film) having a thickness of 65 μm and an adhesive layer was used.
In Example 5, Sun A. Kaken Co., Ltd. PAC-3-70 (trade name) having a thickness of 70 μm was used as the protective film 5. The protective film 5 was a coextruded film of an LDPE (low density polyethylene) film and an ethylene-vinyl acetate copolymer layer.

例６では保護フィルム６として、厚さが３０μｍのフタムラ化学株式会社 ＦＳＡ（登録商標）０１０Ｍ（商品名）を用いた。保護フィルム６は、２軸延伸ポリプロピレン（ＯＰＰ）を基材（厚み３０μｍ）とする、自己粘着性保護フィルムであった。
例７では保護フィルム７として、厚さが５７μｍのパナック株式会社 パナプロテクト（登録商標）ＳＴ５０（商品名）を用いた。保護フィルム７は、基材（厚み５０μｍ、ＰＥＴフィルム）と粘着層とを有していた。
例８では保護フィルム８として、厚さが８０μｍのパナック株式会社 パナプロテクト（登録商標）ＧＣ５０（商品名）を用いた。保護フィルム８は、基材（厚み５０μｍ、ＰＥＴフィルム）と粘着層とを有していた。
例９では保護フィルム９として、厚さが６３μｍのパナック株式会社 パナプロテクト（登録商標）ＧＳ５０（商品名）を用いた。保護フィルム９は、基材（厚み５０μｍ、ＰＥＴフィルム）と粘着層とを有していた。
例１０では保護フィルム１０として、厚さが６０μｍのパナック株式会社 パナプロテクト（登録商標）ＧＮ５０（商品名）を用いた。保護フィルム１０は、基材（厚み５０μｍ、ＰＥＴフィルム）と粘着層とを有していた。 In Example 6, Futamura Chemical Co., Ltd. FSA (registered trademark) 010M (trade name) having a thickness of 30 μm was used as the protective film 6. The protective film 6 was a self-adhesive protective film using biaxially stretched polypropylene (OPP) as a base material (thickness 30 μm).
In Example 7, as the protective film 7, Panac Co., Ltd. Panaprotect (registered trademark) ST50 (trade name) having a thickness of 57 μm was used. The protective film 7 had a base material (thickness 50 μm, PET film) and an adhesive layer.
In Example 8, Panac Co., Ltd. PanaProtect (registered trademark) GC50 (trade name) having a thickness of 80 μm was used as the protective film 8. The protective film 8 had a base material (thickness 50 μm, PET film) and an adhesive layer.
In Example 9, Panac Co., Ltd. PanaProtect (registered trademark) GS50 (trade name) having a thickness of 63 μm was used as the protective film 9. The protective film 9 had a base material (thickness 50 μm, PET film) and an adhesive layer.
In Example 10, Panac Co., Ltd. Panaprotect (registered trademark) GN50 (trade name) having a thickness of 60 μm was used as the protective film 10. The protective film 10 had a base material (thickness 50 μm, PET film) and an adhesive layer.

例１１では保護フィルム１１として、厚さが６０μｍの株式会社サンエー化研 ＪＡ１６Ｆ（商品名）を用いた。保護フィルム１１は、基材（ＬＤＰＥフィルム）と粘着層とを有していた。
例１２では保護フィルム１２として、厚さが６０μｍの株式会社サンエー化研 Ｙ１６Ｆ（商品名）を用いた。保護フィルム１２は、基材（ＬＤＰＥフィルム）と粘着層とを有していた。
例１３では保護フィルム１３として、厚さが７４μｍの株式会社サンエー化研 Ｐ２７（商品名）を用いた。保護フィルム１３は、基材（ＰＥフィルム）と粘着層とを有していた。
例１４では保護フィルム１４として、厚さが５０μｍの株式会社サンエー化研 Ｂ３５（商品名）を用いた。保護フィルム１４は、基材（ＰＥフィルム）と粘着層とを有していた。
例１５では保護フィルム１５として、厚さ５０μｍのバージンパルプ合紙を用いた。保護フィルム１５は、粘着層を有していなかった。
例１６では保護フィルム１６として、厚み５０μｍのＰＥＴフィルムを用いた。保護フィルム１６は、粘着層を有していなかった。 In Example 11, Sun A. Kaken Co., Ltd. JA16F (trade name) having a thickness of 60 μm was used as the protective film 11. The protective film 11 had a base material (LDPE film) and an adhesive layer.
In Example 12, Sun A. Kaken Co., Ltd. Y16F (trade name) having a thickness of 60 μm was used as the protective film 12. The protective film 12 had a base material (LDPE film) and an adhesive layer.
In Example 13, Sun A. Kaken Co., Ltd. P27 (trade name) having a thickness of 74 μm was used as the protective film 13. The protective film 13 had a base material (PE film) and an adhesive layer.
In Example 14, Sun A. Kaken Co., Ltd. B35 (trade name) having a thickness of 50 μm was used as the protective film 14. The protective film 14 had a base material (PE film) and an adhesive layer.
In Example 15, a virgin pulp interleaving paper having a thickness of 50 μm was used as the protective film 15. The protective film 15 did not have an adhesive layer.
In Example 16, a PET film having a thickness of 50 μm was used as the protective film 16. The protective film 16 did not have an adhesive layer.

各例の積層基板における第１の密着力および第２の密着力は、表１および表２にまとめて示す。各密着力の測定方法は上述した通りである。
表１および表２中の「粘着剤」欄は、保護フィルム中の粘着層中の粘着剤の種類を表し、「アクリル系」は粘着剤がアクリル系粘着剤であることを意味し、「シリコーン系」は粘着剤がシリコーン系粘着剤であることを意味する。 The first adhesion force and the second adhesion force in the laminated substrate of each example are collectively shown in Tables 1 and 2. The method for measuring each adhesion force is as described above.
The "adhesive" column in Tables 1 and 2 indicates the type of adhesive in the adhesive layer in the protective film, and "acrylic" means that the adhesive is an acrylic adhesive, and "silicone". "System" means that the pressure-sensitive adhesive is a silicone-based pressure-sensitive adhesive.

＜評価結果のまとめ＞
上述の表１および表２に示すように、所定の要件を満たす例１〜６では所望の効果が得られた。
なお、例１〜６においては、保護フィルムとポリイミド樹脂層との第１の密着力が０．００１Ｎ／１０ｍｍ以上０．１７Ｎ／１０ｍｍ以下であるため、大気環境中で輸送を行っても、保護フィルムとポリイミド樹脂層との剥離が生じず、ポリイミド樹脂層の端部に欠点が増加することが認められなかった。さらには、例１〜６は、支持基材と保護フィルムとの第２の密着力Ｆ２が、０．０５Ｎ／１０ｍｍ≦Ｆ２≦（Ｆ１（Ｎ／１０ｍｍ）＋０．３Ｎ／１０ｍｍ）であるため、保護フィルム剥離時にスムーズな剥離ができ、支持基材へのダメージが発生しなかった。
なお、例４〜６について、保護フィルムを１００ｍｍ×１００ｍｍの大きさに切出し、粘着面とは反対側が向き合うように二つ折りにした。次に、ガラス基板を使用して、二つ折りしたものに１６ｇ／ｃｍ２の荷重をかけた。荷重をかけた状態で３０分放置した後、ガラス基板を取り外した。そして、保護フィルムがどの程度復元するかを確認した。例５、６に関しては、折れ曲がり状態（０°）が維持されたが、例４に関しては、保護フィルムがある程度復元して、９０°となった。このことから、例４では、保護フィルムの復元力が比較的強く、異物に追従して変形しにくいため、異物がポリイミド樹脂層に押し付けられたと推察される。
また、例５、６について、長期保管試験を実施したが、長期保管２か月後、４か月後、６か月後のいずれの保管期間についても、糊残り、キズは見られなかった。 <Summary of evaluation results>
As shown in Tables 1 and 2 above, the desired effects were obtained in Examples 1 to 6 satisfying the predetermined requirements.
In Examples 1 to 6, since the first adhesion between the protective film and the polyimide resin layer is 0.001 N / 10 mm or more and 0.17 N / 10 mm or less, it is protected even when transported in an air environment. No peeling of the film and the polyimide resin layer occurred, and no increase in defects was observed at the end of the polyimide resin layer. Further, in Examples 1 to 6, the second adhesion force F 2 between the supporting base material and the protective film is 0.05 N / 10 mm ≤ F 2 ≤ (F 1 (N / 10 mm) + 0.3 N / 10 mm). Therefore, smooth peeling was possible when the protective film was peeled off, and damage to the supporting base material did not occur.
For Examples 4 to 6, the protective film was cut out to a size of 100 mm × 100 mm and folded in half so that the side opposite to the adhesive surface faced each other. Next, using a glass substrate, a load of 16 g / cm 2 was applied to the folded product. After leaving it for 30 minutes under a load, the glass substrate was removed. Then, it was confirmed how much the protective film was restored. In Examples 5 and 6, the bent state (0 °) was maintained, but in Example 4, the protective film was restored to some extent to 90 °. From this, in Example 4, it is presumed that the foreign matter was pressed against the polyimide resin layer because the restoring force of the protective film was relatively strong and it was difficult to be deformed by following the foreign matter.
In addition, a long-term storage test was carried out for Examples 5 and 6, and no adhesive residue or scratches were observed in any of the storage periods of 2 months, 4 months, and 6 months after the long-term storage.

１０ 積層基板
１２ 支持基材
１２ａ 表面
１２ｂ 裏面
１２ｃ 外縁部
１３ シリコーン樹脂層
１３ａ 表面
１４ ポリイミド樹脂層
１４ａ 表面
１６ 保護フィルム
１８ 基材
１９ 密着層
２０ 梱包体
２２ パレット
２４ 底板
２４ａ 表面
２６ 背板
２６ａ 表面
Ｄ 異物
β 角 10 Laminated substrate 12 Supporting substrate 12a Surface 12b Back surface 12c Outer edge 13 Silicone resin layer 13a Surface 14 Polyimide resin layer 14a Surface 16 Protective film 18 Base material 19 Adhesive layer 20 Packing body 22 Pallet 24 Bottom plate 24a Surface 26 Back plate 26a Surface D Foreign matter β angle

Claims (11)

ガラス製の支持基材上に、ポリイミド樹脂層と、前記ポリイミド樹脂層を覆う保護フィルムとが積層された積層基板であって、
前記ポリイミド樹脂層と前記保護フィルムとの第１の密着力をＦ１とし、前記支持基材と前記保護フィルムとの第２の密着力をＦ２とするとき、
前記第１の密着力Ｆ１は、０．００１Ｎ／１０ｍｍ≦Ｆ１≦０．１７Ｎ／１０ｍｍであり、
前記第２の密着力Ｆ２は、０．０５Ｎ／１０ｍｍ≦Ｆ２≦（Ｆ１（Ｎ／１０ｍｍ）＋０．３Ｎ／１０ｍｍ）である、積層基板。 A laminated substrate in which a polyimide resin layer and a protective film covering the polyimide resin layer are laminated on a glass supporting base material.
When the first adhesive force between the polyimide resin layer and the protective film is F 1, and the second adhesive force between the supporting base material and the protective film is F 2 .
The first adhesion force F 1 is 0.001 N / 10 mm ≤ F 1 ≤ 0.17 N / 10 mm.
The second adhesion force F 2 is 0.05 N / 10 mm ≦ F 2 ≦ (F 1 (N / 10 mm) + 0.3 N / 10 mm). 前記保護フィルムの大きさは、前記支持基材の大きさ以上である、請求項１に記載の積層基板。 The laminated substrate according to claim 1, wherein the size of the protective film is equal to or larger than the size of the supporting base material. 前記保護フィルムの厚さは、２０μｍ以上である、請求項１または２に記載の積層基板。 The laminated substrate according to claim 1 or 2, wherein the protective film has a thickness of 20 μm or more. 前記保護フィルムは、基材と、前記基材に積層され、かつ前記ポリイミド樹脂層に接する密着層とを有し、前記基材は、ポリエチレンにより構成されている、請求項１〜３のいずれか１項に記載の積層基板。 Any one of claims 1 to 3, wherein the protective film has a base material and an adhesion layer laminated on the base material and in contact with the polyimide resin layer, and the base material is made of polyethylene. The laminated substrate according to item 1. 前記支持基材と前記ポリイミド樹脂層との密着力は、前記第１の密着力および前記第２の密着力のいずれよりも大きい、請求項１〜４のいずれか１項に記載の積層基板。 The laminated substrate according to any one of claims 1 to 4, wherein the adhesion between the support base material and the polyimide resin layer is larger than either the first adhesion force or the second adhesion force. 前記支持基材と前記ポリイミド樹脂層との間に、シランカップリング剤層が設けられている、請求項１〜５のいずれか１項に記載の積層基板。 The laminated substrate according to any one of claims 1 to 5, wherein a silane coupling agent layer is provided between the supporting base material and the polyimide resin layer. 前記支持基材と前記ポリイミド樹脂層との間に、シリコーン樹脂層が設けられている、請求項１〜５のいずれか１項に記載の積層基板。 The laminated substrate according to any one of claims 1 to 5, wherein a silicone resin layer is provided between the supporting base material and the polyimide resin layer. パレットと、前記パレットに複数積載されている請求項１〜７のいずれか１項に記載の積層基板とを有する、梱包体。 A packaging body having a pallet and a laminated substrate according to any one of claims 1 to 7, which is loaded on the pallet in plurality. 複数の前記積層基板は、相互に荷重がかかる状態で前記パレットに積載されている、請求項８に記載の梱包体。 The packaging body according to claim 8, wherein the plurality of laminated substrates are loaded on the pallet in a state where a load is applied to each other. 前記パレットは、底板と、前記底板に立設された背板とを有し、
前記積層基板は前記支持基材を前記背板の表面に向けて、傾けた状態で前記パレットに積載されている、請求項８または９に記載の梱包体。 The pallet has a bottom plate and a back plate erected on the bottom plate.
The packaging body according to claim 8 or 9, wherein the laminated substrate is loaded on the pallet in a state where the supporting base material is tilted toward the surface of the back plate. 前記積層基板の大きさは、短辺が８５０ｍｍ以上、長辺が１１００ｍｍ以上である、請求項８〜１０のいずれか１項に記載の梱包体。 The package according to any one of claims 8 to 10, wherein the size of the laminated substrate is 850 mm or more on a short side and 1100 mm or more on a long side.
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