TWI627148B - Manufacturing method of glass laminated body and manufacturing method of electronic device - Google Patents

Manufacturing method of glass laminated body and manufacturing method of electronic device Download PDF

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Publication number
TWI627148B
TWI627148B TW103144170A TW103144170A TWI627148B TW I627148 B TWI627148 B TW I627148B TW 103144170 A TW103144170 A TW 103144170A TW 103144170 A TW103144170 A TW 103144170A TW I627148 B TWI627148 B TW I627148B
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glass
substrate
support substrate
manufacturing
layer
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TW103144170A
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Chinese (zh)
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TW201536710A (en
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Yuichi Hino
Yutaka Otsubo
Takuya Nagano
Hiroshi Utsugi
Tatsuzo MIYAGOE
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Asahi Glass Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B38/0008Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B38/10Removing layers, or parts of layers, mechanically or chemically
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/10Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Fluid Mechanics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

本發明係關於一種玻璃積層體之製造方法,其係依序具有支持基板、聚矽氧樹脂層及玻璃基板之玻璃積層體之製造方法,且其包含:加熱步驟,其係對包含具有第1主面及第2主面之支持基板以及配置於上述支持基板之上述第1主面上之硬化性聚矽氧組合物層的附硬化性層之支持基板自上述支持基板之上述第2主面側利用複數個支持銷進行支持,對上述附硬化性層之支持基板實施加熱處理而形成聚矽氧樹脂層;積層步驟,其係於上述加熱步驟後,於上述聚矽氧樹脂層上積層玻璃基板;及表面處理步驟,其係於上述積層步驟後,或於上述加熱步驟後且上述積層步驟前,至少對上述支持基板之上述第2主面實施選自由電暈處理、電漿處理、及UV臭氧處理所組成之群中之至少1種處理。 The present invention relates to a method for manufacturing a glass laminate, which is a method for manufacturing a glass laminate having a supporting substrate, a polysiloxane resin layer, and a glass substrate in this order, and includes a heating step for The support substrate of the main surface and the second main surface, and the support substrate with a hardening layer of the curable polysiloxane composition layer disposed on the first main surface of the support substrate are from the second main surface of the support substrate. On the side, a plurality of support pins are used for support, and the support substrate with a hardening layer is heated to form a polysiloxane resin layer. The lamination step is a step of laminating glass on the polysiloxane resin layer after the heating step. A substrate; and a surface treatment step after the above lamination step, or after the heating step and before the lamination step, at least the second main surface of the support substrate is selected from corona treatment, plasma treatment, and At least one of a group consisting of UV ozone treatment.

Description

玻璃積層體之製造方法及電子裝置之製造方法 Manufacturing method of glass laminated body and manufacturing method of electronic device

本發明係關於一種玻璃積層體之製造方法、及電子裝置之製造方法。 The present invention relates to a method for manufacturing a glass laminate and a method for manufacturing an electronic device.

近年來,太陽電池(PV)、液晶面板(LCD)、有機EL(Electroluminescence,電致發光)面板(OLED)等裝置(電子設備)之薄型化、輕量化不斷進展,該等裝置所使用之玻璃基板之薄板化正不斷發展。若因薄板化導致玻璃基板之強度不足,則於裝置之製造步驟中,玻璃基板之操作性降低。 In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL (Electroluminescence) panels (OLEDs) have become thinner and lighter, and the glass used in these devices The thinning of the substrate is continuously developing. If the strength of the glass substrate is insufficient due to thinning, the operability of the glass substrate is reduced in the manufacturing steps of the device.

最近,為了應對上述課題,而提出有如下方法,即準備積層有玻璃基板與補強板之玻璃積層體,於玻璃積層體之玻璃基板上形成顯示裝置等電子裝置用構件後,將補強板自玻璃基板分離(例如,參照專利文獻1)。補強板具有支持基板、及固定於該支持基板上之聚矽氧樹脂層,且將聚矽氧樹脂層與玻璃基板以可剝離之方式進行密接。於玻璃積層體之聚矽氧樹脂層與玻璃基板之界面將補強板剝離,自玻璃基板分離之補強板可與新的玻璃基板積層,而作為玻璃積層體進行再利用。 Recently, in order to cope with the above-mentioned problems, a method has been proposed in which a glass laminate having a glass substrate and a reinforcing plate is prepared, and a member for electronic devices such as a display device is formed on the glass substrate of the glass laminate, and the reinforcing plate is removed from the glass The substrate is separated (for example, refer to Patent Document 1). The reinforcing plate has a support substrate and a silicone resin layer fixed on the support substrate, and the silicone resin layer and the glass substrate are adhered in a peelable manner. The reinforcing plate is peeled off at the interface between the polysiloxane resin layer of the glass laminate and the glass substrate. The reinforcing plate separated from the glass substrate can be laminated with a new glass substrate and reused as a glass laminate.

再者,亦有對所形成之玻璃積層體為了研磨玻璃基板之表面而實施研磨處理之情形(專利文獻2)。 Furthermore, there may be a case where the formed glass laminate is subjected to a polishing treatment in order to polish the surface of a glass substrate (Patent Document 2).

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]國際公開第2007/018028號 [Patent Document 1] International Publication No. 2007/018028

[專利文獻2]日本專利特開2013-149713號 [Patent Document 2] Japanese Patent Laid-Open No. 2013-149713

另一方面,自先前已知有將表面配置有塗膜之支持基板載置於複數個支持銷之頂部而進行加熱乾燥之方法。 On the other hand, a method of heating and drying a support substrate on which a coating film is disposed on the top of a plurality of support pins has been known from the past.

本發明者等人依據專利文獻1所記載之方法而製作補強板時,將表面配置有藉由加熱而成為聚矽氧樹脂層之塗膜的支持基板載置於複數個支持銷之頂部而進行加熱乾燥,形成聚矽氧樹脂層後,於聚矽氧樹脂層上積層玻璃基板而製作玻璃積層體。其後,使所獲得之玻璃積層體中之支持基板側朝向特定之基板側,將玻璃積層體載置於特定之基板上,如專利文獻1或2所記載般,於玻璃積層體中之玻璃基板上形成電子裝置用構件、或對玻璃基板表面進行研磨處理。其後,於欲自特定之基板卸除玻璃積層體時,特定之基板與支持基板密接,玻璃積層體被固定於特定之基板上而無法容易地卸除。因此,引起由製程時間之長期化引起之生產性之降低、或電子裝置之製造良率之降低。 When the present inventors produced a reinforcing plate in accordance with the method described in Patent Document 1, a support substrate on which a coating film that becomes a polysiloxane layer by heating was placed on the surface was placed on top of a plurality of support pins. After heating and drying to form a polysiloxane resin layer, a glass substrate is laminated on the polysiloxane resin layer to prepare a glass laminate. Thereafter, the support substrate side in the obtained glass laminate is directed toward a specific substrate side, and the glass laminate is placed on a specific substrate, as described in Patent Document 1 or 2, in the glass in the glass laminate A member for an electronic device is formed on a substrate, or a surface of a glass substrate is polished. Thereafter, when the glass laminate is to be removed from a specific substrate, the specific substrate is in close contact with the support substrate, and the glass laminate is fixed to the specific substrate and cannot be easily removed. Therefore, a reduction in productivity due to a prolonged process time or a reduction in the manufacturing yield of an electronic device is caused.

本發明係鑒於上述課題而完成者,其目的在於提供一種玻璃積層體之製造方法,該製造方法可製造使支持基板側朝向各種基板上載置後可容易自該基板剝離之玻璃積層體。 This invention was made in view of the said subject, and an object of this invention is to provide the manufacturing method of the glass laminated body which can manufacture the glass laminated body which can be easily peeled from a board | substrate after mounting a support substrate side toward various boards.

又,本發明之目的亦在於提供一種使用藉由該玻璃積層體之製造方法製造之玻璃積層體的電子裝置之製造方法。 Another object of the present invention is to provide a method for manufacturing an electronic device using a glass laminate manufactured by the method for manufacturing a glass laminate.

本發明者等人為解決上述課題而進行努力研究,結果完成本發明。 The present inventors have made intensive studies in order to solve the above problems, and as a result, have completed the present invention.

即,本發明之第1態樣係一種玻璃積層體之製造方法,其係依序具有支持基板、聚矽氧樹脂層及玻璃基板之玻璃積層體之製造方法, 且其包含:加熱步驟,其係對包含具有第1主面及第2主面之支持基板以及配置於支持基板之第1主面上之硬化性聚矽氧組合物層的附硬化性層之支持基板自支持基板之第2主面側利用複數個支持銷進行支持,對附硬化性層之支持基板實施加熱處理而形成聚矽氧樹脂層;積層步驟,其係於加熱步驟後,於聚矽氧樹脂層上積層玻璃基板;及表面處理步驟,其係於積層步驟後,或於加熱步驟後且積層步驟前,至少對支持基板之第2主面實施選自由電暈處理、電漿處理、及UV(Ultra Violet,紫外線)臭氧處理所組成之群中之至少1種處理。 That is, the first aspect of the present invention is a method for manufacturing a glass laminate, which is a method for manufacturing a glass laminate having a support substrate, a polysiloxane resin layer, and a glass substrate in this order. In addition, the method includes a heating step for adding a hardening layer including a supporting substrate having a first main surface and a second main surface, and a hardening polysiloxane composition layer disposed on the first main surface of the supporting substrate. The support substrate is supported by a plurality of support pins from the second main surface side of the support substrate. The support substrate with a hardening layer is subjected to a heat treatment to form a polysiloxane resin layer; the lamination step is performed after the heating step, A glass substrate is laminated on the siloxane resin layer; and a surface treatment step is performed after the lamination step, or after the heating step and before the lamination step, at least the second main surface of the supporting substrate is selected from corona treatment and plasma treatment. And UV (Ultra Violet, ultraviolet) ozone treatment of at least one of the group consisting of.

於第1態樣中,較佳為於硬化性聚矽氧組合物層中至少含有具有烯基之有機烯基聚矽氧烷、及具有鍵結於矽原子之氫原子之有機氫聚矽氧烷。 In the first aspect, the hardenable polysiloxane composition layer preferably contains at least an organic alkenyl polysiloxane having an alkenyl group and an organic hydrogen polysiloxane having a hydrogen atom bonded to a silicon atom. alkyl.

於第1態樣中,加熱步驟較佳為依序包含於第1溫度下實施加熱處理之第1加熱步驟、及於較第1溫度高之第2溫度下實施加熱處理之第2加熱步驟。 In the first aspect, the heating step preferably includes a first heating step in which a heat treatment is performed at a first temperature, and a second heating step in which a heat treatment is performed at a second temperature higher than the first temperature.

於第1態樣中,附硬化性層之支持基板係藉由將包含硬化性聚矽氧與溶劑之硬化性聚矽氧組合物塗佈於支持基板之第1主面上而形成,且 第1溫度較佳為滿足溶劑之初餾點-30℃≦第1溫度≦溶劑之初餾點+30℃。 In the first aspect, the supporting substrate with a hardening layer is formed by applying a hardening polysiloxane composition containing a hardening polysiloxane and a solvent to the first main surface of the supporting substrate, and The first temperature preferably satisfies the initial boiling point of the solvent -30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C.

於第1態樣中,較佳為於積層步驟後實施表面處理步驟。 In the first aspect, the surface treatment step is preferably performed after the lamination step.

於第1態樣中,較佳為於表面處理步驟中,使複數對包含隔著積層步驟中所獲得之玻璃積層體被搬送之搬送路徑相對向之高壓電極與接地電極的電極對沿著玻璃積層體之搬送方向進行排列,將鄰接之電極對中之一者之高壓電極配置於隔著搬送路徑之一側,將另一者之高壓電極配置於隔著搬送路徑之另一側,且一面將玻璃積層體沿著搬送路徑進行搬送,一面向高壓電極施加高頻電壓,而對玻璃積層體實施 電暈處理。 In the first aspect, preferably, in the surface treatment step, a plurality of pairs of electrode pairs including the high-voltage electrode and the ground electrode opposite to each other through the transport path through which the glass laminate obtained in the lamination step is transported are along the glass. Arrange the conveying direction of the laminated body, arrange the high-voltage electrode of one of the adjacent electrode pairs on one side across the conveyance path, and arrange the other high-voltage electrode on the other side across the conveyance path, and one side The glass laminate is transported along the conveyance path, and a high-frequency voltage is applied to the high-voltage electrode, and the glass laminate is applied. Corona treatment.

本發明之第2態樣係一種電子裝置之製造方法,其包含:構件形成步驟,其係於藉由上述第1態樣之製造方法製造之玻璃積層體之玻璃基板的表面上形成電子裝置用構件,而獲得附電子裝置用構件之積層體;及分離步驟,其係自附電子裝置用構件之積層體去除具有聚矽氧樹脂層及支持基板之附樹脂層之支持基板,而獲得具有玻璃基板與電子裝置用構件之電子裝置。 A second aspect of the present invention is a method for manufacturing an electronic device, including a component forming step for forming an electronic device on a surface of a glass substrate of a glass laminate manufactured by the manufacturing method of the first aspect. To obtain a laminated body with a member for an electronic device; and a separation step of removing a supporting substrate having a polysiloxane resin layer and a supporting layer with a resin layer from the laminated body with an electronic device member and obtaining a glass having Electronic device of substrate and member for electronic device.

根據本發明,可提供一種玻璃積層體之製造方法,該製造方法可製造使支持基板側朝向各種基板上載置後可容易自該基板剝離之玻璃積層體。 According to the present invention, it is possible to provide a method for manufacturing a glass laminate, which can manufacture a glass laminate that can be easily peeled from the substrate after the support substrate side is placed toward various substrates.

又,根據本發明,亦可提供一種使用藉由該玻璃積層體之製造方法製造之玻璃積層體的電子裝置之製造方法。 In addition, according to the present invention, it is possible to provide a method for manufacturing an electronic device using the glass laminated body manufactured by the glass laminated body manufacturing method.

10‧‧‧支持基板 10‧‧‧ support substrate

10a‧‧‧支持基板之第2主面 10a‧‧‧ 2nd main surface of supporting substrate

12‧‧‧硬化性聚矽氧組合物層 12‧‧‧ hardening polysiloxane composition layer

14‧‧‧附硬化性層之支持基板 14‧‧‧ Support substrate with hardening layer

16‧‧‧聚矽氧樹脂層 16‧‧‧Polysiloxane layer

16a‧‧‧聚矽氧樹脂層中之與支持基板側相反側之表面 16a‧‧‧ The surface of the polysiloxane layer opposite to the support substrate side

18‧‧‧附樹脂層之支持基板 18‧‧‧ Support substrate with resin layer

20‧‧‧玻璃基板 20‧‧‧ glass substrate

20a‧‧‧玻璃基板之第1主面 20a‧‧‧The first main surface of the glass substrate

20b‧‧‧玻璃基板之第2主面 20b‧2nd main surface of glass substrate

22‧‧‧電子裝置用構件 22‧‧‧ Components for electronic devices

24‧‧‧附電子裝置用構件之積層體 24‧‧‧ Laminated body with components for electronic devices

26‧‧‧電子裝置 26‧‧‧Electronic device

50‧‧‧支持台 50‧‧‧ support desk

52‧‧‧支持銷 52‧‧‧Support sales

60‧‧‧電暈處理裝置 60‧‧‧Corona treatment device

62‧‧‧第1高壓電極 62‧‧‧The first high voltage electrode

64‧‧‧第1接地電極 64‧‧‧The first ground electrode

66‧‧‧第2高壓電極 66‧‧‧Second high voltage electrode

68‧‧‧第2接地電極 68‧‧‧ 2nd ground electrode

70‧‧‧第1電極對 70‧‧‧ 1st electrode pair

72‧‧‧第2電極對 72‧‧‧ 2nd electrode pair

74‧‧‧搬送輥 74‧‧‧ transporting roller

76‧‧‧第1高頻電源 76‧‧‧1st high frequency power supply

78‧‧‧第2高頻電源 78‧‧‧ 2nd high frequency power supply

100‧‧‧玻璃積層體 100‧‧‧ glass laminate

X‧‧‧玻璃積層體 X‧‧‧ glass laminated body

圖1係表示本發明之玻璃積層體之製造方法之第1態樣的製造步驟之流程圖。 FIG. 1 is a flowchart showing manufacturing steps in a first aspect of a method for manufacturing a glass laminate according to the present invention.

圖2(A)、(B)及(C)係以步驟順序表示本發明之玻璃積層體之製造方法之第1態樣的模式剖面圖。 2 (A), (B), and (C) are schematic cross-sectional views showing a first aspect of the method for manufacturing a glass laminate of the present invention in the order of steps.

圖3係表示加熱步驟中之附硬化性層之支持基板之配置狀態之模式圖。 FIG. 3 is a schematic diagram showing an arrangement state of a supporting substrate with a hardening layer in a heating step.

圖4係表示電暈處理裝置之一實施形態之側視圖。 Fig. 4 is a side view showing an embodiment of the corona treatment device.

圖5係表示本發明之玻璃積層體之製造方法之第2態樣的製造步驟之流程圖。 FIG. 5 is a flowchart showing the manufacturing steps of the second aspect of the method for manufacturing a glass laminate of the present invention.

圖6(A)及(B)係以步驟順序表示本發明之電子裝置之製造方法之一實施形態的模式剖面圖。 6 (A) and 6 (B) are schematic sectional views showing an embodiment of a method for manufacturing an electronic device according to the present invention in the order of steps.

以下,針對本發明之較佳實施態樣,參照圖式進行說明,但本發明並不受以下之實施形態限制,於不脫離本發明之範圍之情況下,可於以下之實施形態中施加各種變化及置換。 Hereinafter, the preferred embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited by the following embodiments, and various kinds of embodiments can be applied to the following embodiments without departing from the scope of the present invention. Change and replacement.

本發明者等人對上述問題進行研究時發現,於加熱步驟後或製作玻璃積層體後(積層步驟後)聚矽氧樹脂附著於支持基板之第2主面(背面)側,其係上述問題之原因之一。 When the present inventors studied the above problems, they found that the silicone resin adhered to the second main surface (back surface) side of the support substrate after the heating step or after the glass laminate was produced (after the lamination step), which is the above problem One of the reasons.

更具體而言,於加熱步驟時,聚矽氧樹脂或其原料之一部分揮發,從而聚矽氧樹脂附著於支持銷所支持之支持基板之第2主面側。因此,使玻璃積層體之支持基板側朝向特定之基板側並將玻璃積層體載置於特定之基板上時,由於存在於該特定之基板與玻璃積層體中之支持基板之間的聚矽氧樹脂而使特定之基板與支持基板之剝離強度上升,從而兩者變得難以剝離。因此,發現於製作玻璃積層體後對支持基板之第2主面側實施各種處理而將聚矽氧樹脂去除,藉此可解決上述課題。 More specifically, during the heating step, the silicone resin or one of its raw materials is partially volatilized, so that the silicone resin adheres to the second main surface side of the support substrate supported by the support pin. Therefore, when the support substrate side of the glass laminate is directed toward a specific substrate side and the glass laminate is placed on a specific substrate, the polysilicon existing between the specific substrate and the support substrate in the glass laminate Resin increases the peeling strength of a specific substrate and a support substrate, making it difficult for both to peel. Therefore, it has been found that after the glass laminate is produced, various treatments are performed on the second main surface side of the support substrate to remove the silicone resin, thereby solving the above problems.

本發明之玻璃積層體之製造方法包含:對附硬化性層之支持基板實施加熱處理之加熱步驟;積層玻璃基板之積層步驟;及進行表面處理之表面處理步驟。再者,表面處理步驟係於上述積層步驟後,或者於上述加熱步驟後且上述積層步驟前實施。以下,將前者之態樣作為第1態樣,將後者之態樣作為第2態樣而進行說明。 The manufacturing method of the glass laminated body of the present invention includes: a heating step of applying a heat treatment to a supporting substrate with a hardenable layer; a step of laminating a laminated glass substrate; and a surface treatment step of performing a surface treatment. Moreover, the surface treatment step is performed after the above-mentioned lamination step, or after the above-mentioned heating step and before the above-mentioned lamination step. Hereinafter, the former aspect will be described as a first aspect, and the latter aspect will be described as a second aspect.

<<第1態樣>> << 1st aspect >>

圖1係表示本發明之玻璃積層體之製造方法之第1態樣的製造步驟之流程圖。如圖1所示般,第1態樣依序包含:加熱步驟S102、積層步驟S104、及表面處理步驟S106。 FIG. 1 is a flowchart showing manufacturing steps in a first aspect of a method for manufacturing a glass laminate according to the present invention. As shown in FIG. 1, the first aspect sequentially includes a heating step S102, a lamination step S104, and a surface treatment step S106.

以下,針對各步驟中所使用之材料及其程序進行詳述。首先,對加熱步驟S102進行詳述。 The materials and procedures used in each step are described in detail below. First, the heating step S102 will be described in detail.

<加熱步驟> <Heating step>

加熱步驟S102係如下步驟,即以複數個支持銷,將包含具有第1主面及第2主面之支持基板以及配置於支持基板之第1主面上之硬化性聚矽氧組合物層的附硬化性層之支持基板自支持基板之第2主面(與有硬化性聚矽氧組合物層之側相反側之面)側進行支持,對附硬化性層之支持基板實施加熱處理而形成聚矽氧樹脂層。更具體而言,針對圖2(A)中之包含支持基板10與硬化性聚矽氧組合物層12之附硬化性層之支持基板14,實施該步驟S102,藉此可獲得如圖2(B)所示般包含支持基板10與聚矽氧樹脂層16之附樹脂層之支持基板18。 The heating step S102 is a step of using a plurality of support pins to include a support substrate having a first main surface and a second main surface and a layer of a hardening polysiloxane composition disposed on the first main surface of the support substrate. The supporting substrate with a hardening layer is formed by supporting the second main surface of the supporting substrate (the surface opposite to the side having the hardening polysiloxane composition layer), and heating the supporting substrate with a hardening layer to form the supporting substrate. Silicone resin layer. More specifically, for the supporting substrate 14 with a hardening layer including the supporting substrate 10 and the hardening polysiloxane composition layer 12 in FIG. 2 (A), this step S102 is performed, thereby obtaining a graph as shown in FIG. 2 ( B) A support substrate 18 including a support substrate 10 and a silicone resin layer 16 with a resin layer as shown.

以下,首先對本步驟S102中所使用之構件、材料(支持基板、硬化性聚矽氧組合物層)進行詳述,其後,針對步驟S102之程序進行詳述。 In the following, first, the members and materials (supporting substrate, curable polysiloxane composition layer) used in this step S102 will be described in detail, and then the procedure of step S102 will be described in detail.

(支持基板) (Support substrate)

支持基板10具有第1主面與第2主面2個主面,且與下述之聚矽氧樹脂層16協動,支持並補強下述之玻璃基板20,而於下述之構件形成步驟(電子裝置用構件之製造步驟)中防止電子裝置用構件之製造時玻璃基板20之變形、損傷、破損等。又,於使用厚度較先前薄之玻璃基板之情形時,可藉由製成與先前之玻璃基板相同厚度之玻璃積層體,而於構件形成步驟中使用適合先前之厚度之玻璃基板之製造技術或製造設備,其亦為使用支持基板10之目的之一。 The supporting substrate 10 has two main surfaces, a first main surface and a second main surface. The supporting substrate 10 supports and reinforces the glass substrate 20 described below in cooperation with the silicone layer 16 described below. (Procedure for manufacturing electronic device member) In the manufacturing of the electronic device member, deformation, damage, breakage, etc. of the glass substrate 20 are prevented. In addition, in the case of using a thinner glass substrate than before, a glass laminate having the same thickness as the previous glass substrate can be used, and a manufacturing method suitable for the previous thickness of the glass substrate can be used in the component formation step or Manufacturing equipment is also one of the purposes of using the supporting substrate 10.

作為支持基板10,例如可使用玻璃板、塑膠板、SUS(Steel Use Stainless,日本不鏽鋼標準)板等金屬板、陶瓷板等。於構件形成步驟伴隨著熱處理之情形時,支持基板10較佳為由與玻璃基板20之線膨脹係數之差較小之材料形成,更佳為由與玻璃基板20相同之材料形成。即,支持基板10較佳為玻璃板。尤其是支持基板10較佳為包含與玻璃基板20相同之玻璃材料之玻璃板。 As the support substrate 10, for example, a metal plate such as a glass plate, a plastic plate, or a SUS (Steel Use Stainless) plate, a ceramic plate, or the like can be used. When the component forming step is accompanied by a heat treatment, the support substrate 10 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 20, and more preferably formed of the same material as the glass substrate 20. That is, the support substrate 10 is preferably a glass plate. In particular, the supporting substrate 10 is preferably a glass plate containing the same glass material as the glass substrate 20.

關於支持基板10之厚度,可厚於玻璃基板20,亦可薄於玻璃基 板20。較佳為基於玻璃基板20之厚度、樹脂層16之厚度、及玻璃積層體之厚度而選擇支持基板10之厚度。例如,現行之構件形成步驟係為了對厚度0.5mm之基板進行處理而設計者,於玻璃基板20之厚度與樹脂層16之厚度之和為0.1mm之情形時,將支持基板10之厚度設為0.4mm。支持基板10之厚度於通常之情形時較佳為0.2~5.0mm。 Regarding the thickness of the support substrate 10, it may be thicker than the glass substrate 20 or thinner than the glass substrate 板 20。 Plate 20. The thickness of the support substrate 10 is preferably selected based on the thickness of the glass substrate 20, the thickness of the resin layer 16, and the thickness of the glass laminate. For example, the current component forming step is designed for processing a substrate having a thickness of 0.5 mm. When the sum of the thickness of the glass substrate 20 and the thickness of the resin layer 16 is 0.1 mm, the thickness of the support substrate 10 is set to 0.4mm. The thickness of the support substrate 10 is preferably 0.2 to 5.0 mm in a normal case.

於支持基板10為玻璃板之情形時,關於玻璃板之厚度,就操作容易、難以破損等理由而言,較佳為0.08mm以上。又,關於玻璃板之厚度,就於電子裝置用構件形成後進行剝離時,期望有如不破損而適度彎曲之剛性之理由而言,較佳為1.0mm以下。 In the case where the support substrate 10 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons such as easy operation and difficulty in breakage. In addition, the thickness of the glass plate is preferably 1.0 mm or less for the reason that it is desired to have a rigidity that is moderately curved without being broken when the electronic device member is peeled off.

支持基板10與玻璃基板20之於25~300℃下之平均線膨脹係數(以下,簡稱為「平均線膨脹係數」)之差較佳為500×10-7/℃以下,更佳為300×10-7/℃以下,進而較佳為200×10-7/℃以下。若差過大,則於構件形成步驟中之加熱冷卻時,有玻璃積層體猛烈地彎曲,或玻璃基板20與下述之附樹脂層之支持基板18剝離之可能性。於玻璃基板20之材料與支持基板10之材料相同之情形時,可抑制上述問題產生。 The difference between the average linear expansion coefficient (hereinafter referred to as the "average linear expansion coefficient") of the support substrate 10 and the glass substrate 20 at 25 to 300 ° C is preferably 500 × 10 -7 / ° C or less, and more preferably 300 × 10 -7 / ° C or lower, more preferably 200 × 10 -7 / ° C or lower. If the difference is too large, the glass laminate may be violently bent during heating and cooling in the member forming step, or the glass substrate 20 and the supporting substrate 18 with a resin layer described below may peel off. When the material of the glass substrate 20 and the material of the support substrate 10 are the same, the above-mentioned problems can be suppressed from occurring.

(硬化性聚矽氧組合物層) (Hardening polysiloxane composition layer)

硬化性聚矽氧組合物層係可於本步驟S102中形成聚矽氧樹脂層之組合物之層。 The curable polysiloxane composition layer is a composition composition layer capable of forming a polysiloxane resin layer in step S102.

硬化性聚矽氧組合物層包含進行硬化而成為聚矽氧樹脂之硬化性聚矽氧。此種硬化性聚矽氧係根據其硬化機制而被分類為縮合反應型聚矽氧、加成反應型聚矽氧、紫外線硬化型聚矽氧及電子束硬化型聚矽氧,可使用上述中任一種之硬化型聚矽氧。該等中較佳為加成反應型聚矽氧。其原因在於:硬化反應容易進行,且形成聚矽氧樹脂層時之剝離性之程度良好,並且耐熱性亦較高。 The curable polysiloxane composition layer contains a curable polysiloxane that is cured to become a polysiloxane resin. This type of hardening polysiloxane is classified into condensation reaction type polysiloxane, addition reaction type polysiloxane, ultraviolet hardening type polysiloxane, and electron beam hardening type polysiloxane based on its hardening mechanism. Any type of hardened polysiloxane. Among these, an addition reaction type polysiloxane is preferable. The reason for this is that the hardening reaction is easy to proceed, the degree of peelability when the silicone resin layer is formed is good, and the heat resistance is also high.

加成反應型聚矽氧係含有主劑及交聯劑,且於鉑系觸媒等觸媒之存在下進行硬化之硬化性組合物。加成反應型聚矽氧之硬化係藉由 加熱處理而促進。加成反應型聚矽氧中之主劑較佳為具有鍵結於矽原子之烯基(乙烯基等)之有機聚矽氧烷(即,有機烯基聚矽氧烷;再者,較佳為直鏈狀),且烯基等成為交聯點。加成反應型聚矽氧中之交聯劑較佳為具有鍵結於矽原子之氫原子(氫化矽烷基)之有機聚矽氧烷(即,有機氫聚矽氧烷;再者,較佳為直鏈狀),且氫化矽烷基等成為交聯點。 The addition reaction type polysiloxane is a curable composition containing a main agent and a cross-linking agent and hardened in the presence of a catalyst such as a platinum catalyst. The hardening of the addition reaction type polysiloxane Promoted by heat treatment. The main agent in the addition reaction-type polysiloxane is preferably an organic polysiloxane (i.e., an organic alkenyl polysiloxane) having an alkenyl group (vinyl group, etc.) bonded to a silicon atom; It is linear), and the alkenyl group and the like become a crosslinking point. The cross-linking agent in the addition reaction type polysiloxane is preferably an organic polysiloxane (ie, an organohydrogen polysiloxane) having a hydrogen atom (hydrosilyl group) bonded to a silicon atom; more preferably, It is linear), and a hydrogenated silane group or the like becomes a crosslinking point.

加成反應型聚矽氧係藉由主劑與交聯劑之交聯點進行加成反應而進行硬化。再者,就源自交聯結構之耐熱性更優異之方面而言,有機氫聚矽氧烷之鍵結於矽原子之氫原子相對於有機烯基聚矽氧烷之烯基的莫耳比較佳為0.5~2。 The addition reaction type polysiloxane is hardened by the addition reaction of the crosslinking point of the main agent and the crosslinking agent. In addition, in terms of heat resistance derived from a cross-linked structure, the hydrogen atom bonded to the silicon atom of the organic hydrogen polysiloxane is compared with the mole of the organic alkenyl polysiloxane alkenyl group. It is preferably 0.5 ~ 2.

於硬化性聚矽氧組合物層所含有之硬化性聚矽氧為加成反應型聚矽氧之情形時,硬化性聚矽氧組合物層亦可進而含有觸媒(尤其是鉑族金屬系觸媒)、或反應抑制劑。 When the hardening polysiloxane contained in the hardening polysiloxane composition layer is an addition reaction type polysiloxane, the hardening polysiloxane composition layer may further contain a catalyst (especially a platinum group metal system Catalyst), or reaction inhibitor.

鉑族金屬系觸媒(矽氫化用鉑族金屬觸媒)係用以進行、促進上述有機烯基聚矽氧烷中之烯基、與上述有機氫聚矽氧烷中之氫原子之矽氫化反應之觸媒。作為鉑族金屬系觸媒,可列舉:鉑系、鈀系、銠系等觸媒,就經濟性、反應性之方面而言,尤佳為使用鉑系觸媒。 Platinum group metal catalysts (platinum metal catalysts for hydrosilylation) are used to promote and promote the hydrosilylation of alkenyl groups in the organic alkenyl polysiloxanes and hydrogen atoms in the organic hydrogen polysiloxanes. Catalyst for reaction. Examples of the platinum group metal catalyst include platinum-based, palladium-based, and rhodium-based catalysts. In terms of economy and reactivity, a platinum-based catalyst is particularly preferably used.

反應抑制劑(矽氫化用反應抑制劑)係抑制上述觸媒(尤其是鉑族金屬系觸媒)於常溫下之觸媒活性,而使硬化性聚矽氧組合物之使用壽命變長之所謂適用期延長劑(亦稱為延遲劑)。作為反應抑制劑,例如可列舉:各種有機氮化合物、有機磷化合物、乙炔系化合物、肟化合物、有機氯化合物等。尤佳為乙炔系化合物(例如乙炔醇類及乙炔醇之矽烷化物)。 Reaction inhibitors (reaction inhibitors for hydrosilylation) are so-called catalysts that inhibit the catalyst activity of the above catalysts (especially platinum group metal catalysts) at room temperature, thereby increasing the life of the hardening polysiloxane composition. Pot life extender (also known as delay agent). Examples of the reaction inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene-based compounds, oxime compounds, and organic chlorine compounds. Particularly preferred are acetylene-based compounds (for example, acetylene alcohols and silylates of acetylene alcohol).

於支持基板上形成硬化性聚矽氧組合物層之方法並無特別限制,可採用公知之方法。例如可列舉:將上述之包含硬化性聚矽氧之硬化性聚矽氧組合物塗佈於支持基板上之方法。再者,進行塗佈之方 法並無特別限制,可採用公知之方法。例如作為塗佈方法,可列舉:噴塗法、模具塗佈法、旋轉塗佈法、浸漬塗佈法、輥塗法、棒式塗佈法、網版印刷法、凹版塗佈法等。可自上述方法中,視硬化性聚矽氧組合物之種類而適當進行選擇。 The method for forming a hardenable polysiloxane composition layer on a support substrate is not particularly limited, and a known method can be adopted. For example, the method of apply | coating the above-mentioned curable polysiloxane containing curable polysiloxane to a support substrate is mentioned. Furthermore, the method of coating The method is not particularly limited, and a known method can be adopted. Examples of the coating method 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 coating method. From the above methods, it can be appropriately selected depending on the kind of the curable polysiloxane composition.

於硬化性聚矽氧組合物中,亦可視需要而包含溶劑。溶劑較佳為可容易地使各種成分溶解,且可容易地被揮發去除者。具體而言,例如可列示:乙酸丁酯、庚烷、2-庚酮、1-甲氧基-2-丙醇乙酸酯、甲苯、二甲苯、THF(Tetrahydrofuran,四氫呋喃)、氯仿等。其中,較佳為飽和烴,可自各種飽和烴(直鏈狀飽和烴、支鏈狀飽和烴、脂環式飽和烴)之1種或2種以上使用成為實際之各種飽和烴溶劑。例如可列舉:Isopar G(Exxon Mobil有限公司製造)、Isopar L(Exxon Mobil有限公司製造)、Isopar H(Exxon Mobil有限公司製造)、Isopar M(Exxon Mobil有限公司製造)、NORPAR 13(Exxon Mobil有限公司製造)、NORPAR 15(Exxon Mobil有限公司製造)、Exxsol D40(Exxon Mobil有限公司製造)、Exxsol D60(Exxon Mobil有限公司製造)、Exxsol D80(Exxon Mobil有限公司製造)、Neothiosol(中央化成股份有限公司製造)、IP Solvent 2028(出光興產股份有限公司製造)。 In the hardening polysiloxane composition, a solvent may be contained as needed. The solvent is preferably one that can easily dissolve various components and can be easily removed by evaporation. Specific examples include butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF (Tetrahydrofuran, tetrahydrofuran), and chloroform. Among them, saturated hydrocarbons are preferred, and one or two or more kinds of saturated hydrocarbons (straight-chain saturated hydrocarbons, branched-chain saturated hydrocarbons, and alicyclic saturated hydrocarbons) can be used as practical saturated hydrocarbon solvents. Examples include: Isopar G (made by Exxon Mobil Co., Ltd.), Isopar L (made by Exxon Mobil Co., Ltd.), Isopar H (made by Exxon Mobil Co., Ltd.), Isopar M (made by Exxon Mobil Co., Ltd.), NORPAR 13 (Exxon Mobil Co., Ltd.) (Made by the company), NORPAR 15 (made by Exxon Mobil Co., Ltd.), Exxsol D40 (made by Exxon Mobil Co., Ltd.), Exxsol D60 (made by Exxon Mobil Co., Ltd.), Exxsol D80 (made by Exxon Mobil Co., Ltd.), Neothiosol (Central Chemical Corporation Limited) (Manufactured by the company), IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.).

其中,就於如下述般以2個階段實施步驟S102之情形時於第1加熱階段溶劑容易揮發之方面而言,較佳為使用初餾點(大氣壓下)為210℃以下之溶劑。 Among them, in the case where step S102 is performed in two stages as described below, it is preferable to use a solvent having an initial boiling point (under atmospheric pressure) of 210 ° C. or lower in the first heating stage.

再者,硬化性聚矽氧組合物層之厚度並無特別限制,以可獲得下述之具有較佳厚度之聚矽氧樹脂層之方式適當進行調整。 In addition, the thickness of the curable polysiloxane composition layer is not particularly limited, and it is appropriately adjusted so that a polysiloxane resin layer having a preferable thickness described below can be obtained.

(步驟之順序) (Order of steps)

於本步驟S102中,以複數個支持銷,將附硬化性層之支持基板自支持基板之第2主面側進行支持而實施加熱處理。即,一面以支持銷支持附硬化性層之支持基板一面進行加熱。更具體而言,如圖3所 示般於支持台50上所間隔配置之複數個支持銷52之頂端(頂部)上配置附硬化性層之支持基板14,於該狀態下對附硬化性層之支持基板14實施加熱處理。再者,支持銷52係如圖3所示般支持附硬化性層之支持基板14中之支持基板10之第2主面10a。 In this step S102, a support substrate with a hardening layer is supported from the second main surface side of the support substrate by a plurality of support pins, and a heat treatment is performed. That is, the support substrate with the hardening layer is supported by the support pins while being heated. More specifically, as shown in Figure 3 As shown in the figure, a support substrate 14 with a hardening layer is disposed on the top (top) of a plurality of support pins 52 arranged at intervals on the support table 50. In this state, the support substrate 14 with a hardening layer is heat-treated. The support pin 52 supports the second main surface 10 a of the support substrate 10 in the support substrate 14 with a hardening layer as shown in FIG. 3.

於圖3中僅圖示3根支持銷52,但支持銷之數量並無特別限定,亦可為10根以上。又,支持銷52之配置位置並無特別限制,可隔著特定之間隔進行配置,亦可隨機配置。進而,支持銷52之形狀並無特別限制,亦可為圓柱狀、多角形狀等中之任一形狀。 Only three support pins 52 are shown in FIG. 3, but the number of support pins is not particularly limited, and may be ten or more. In addition, the arrangement position of the support pin 52 is not particularly limited, and it can be arranged at a specific interval or randomly. Furthermore, the shape of the support pin 52 is not particularly limited, and may be any of a cylindrical shape, a polygonal shape, and the like.

再者,如圖3所示般,支持銷52係與支持基板10之第2主面10a側之一部分接觸,因此於支持基板10之第2主面10a側存在未與支持銷52接觸之區域。 Furthermore, as shown in FIG. 3, the support pin 52 is in contact with a part of the second main surface 10 a side of the support substrate 10, and therefore, there is an area not in contact with the support pin 52 on the second main surface 10 a side of the support substrate 10 .

對附硬化性層之支持基板實施加熱處理之方法只要可於以上述支持銷支持附硬化性層之支持基板之狀態下進行加熱,則無特別限制,例如可使用於加熱室內設置有支持銷之烘箱等公知之加熱處理裝置。更具體而言,可列舉:使用包含加熱板之加熱處理裝置之方法(例如,於在配置於支持銷上之附硬化性層之支持基板中之硬化性聚矽氧組合物層之上部設置有加熱板之加熱處理裝置內進行加熱之方法)。 The method of heating the support substrate with a hardening layer is not particularly limited as long as it can be heated in a state where the support substrate with a hardening layer is supported by the above-mentioned support pins. For example, it can be used in a heating room provided with a support pin. A well-known heat treatment device such as an oven. More specifically, a method using a heat treatment device including a hot plate (for example, a method in which an upper portion of a hardening polysiloxane composition layer provided in a supporting substrate with a hardening layer disposed on a supporting pin is provided, is provided. A method of heating in a heating device of a hot plate).

使硬化性聚矽氧組合物層熱硬化之加熱條件係視所使用之硬化性聚矽氧之種類而適當選擇最佳之條件。其中,就硬化性聚矽氧之硬化速度及所形成之聚矽氧樹脂層之耐熱性等方面而言,較佳為於150~300℃(較佳為180~250℃)下進行10~120分鐘(較佳為30~60分鐘)加熱處理。 The heating conditions for thermally curing the curable polysiloxane composition layer are appropriately selected depending on the type of the curable polysiloxane used. Among them, in terms of the hardening speed of the hardening polysiloxane and the heat resistance of the formed polysiloxane resin layer, it is preferably performed at 150 to 300 ° C (preferably 180 to 250 ° C) for 10 to 120. Minute (preferably 30 to 60 minutes) heat treatment.

作為本步驟S102之較佳態樣,較佳為於不同之溫度條件下以2個階段實施加熱處理之態樣。即,更佳為包含:於第1溫度下實施加熱處理之步驟、與於較第1溫度高之第2溫度下實施加熱處理之步驟。藉 由以2個階段實施加熱處理,從而所形成之聚矽氧樹脂層16之表面面狀更優異,而與下述之玻璃基板20之密接性更為提高。再者,於以2個階段實施加熱處理之情形時,亦可利用不同之加熱處理裝置實施第1加熱步驟與第2加熱步驟。 As a preferred aspect of this step S102, a condition in which the heat treatment is performed in two stages under different temperature conditions is preferred. That is, it is more preferable to include a step of performing a heat treatment at a first temperature and a step of performing a heat treatment at a second temperature higher than the first temperature. borrow By performing the heat treatment in two stages, the surface shape of the formed silicone resin layer 16 is more excellent, and the adhesion with the glass substrate 20 described below is further improved. When the heat treatment is performed in two stages, the first heating step and the second heating step may be performed using different heat treatment devices.

再者,於附硬化性層之支持基板係藉由將包含硬化性聚矽氧與溶劑之硬化性聚矽氧組合物塗佈於支持基板上而形成之情形時,就溶劑之去除性更優異而硬化性聚矽氧組合物層之表面變得平坦,並且更為抑制硬化性聚矽氧之分解之方面而言,第1溫度較佳為溶劑之初餾點-30℃~溶劑之初餾點+30℃之範圍內。換言之,第1溫度較佳為滿足以下之關係式。 Furthermore, in the case where the support substrate with a hardening layer is formed by coating a hardening polysiloxane composition containing a hardening polysiloxane and a solvent on the support substrate, the removal property of the solvent is more excellent. On the other hand, the surface of the hardening polysiloxane composition layer becomes flat and the decomposition of the hardening polysiloxane is more suppressed. The first temperature is preferably -30 ° C to the initial distillation point of the solvent. Point within the range of + 30 ° C. In other words, the first temperature preferably satisfies the following relational expression.

式 溶劑之初餾點-30℃≦第1溫度≦溶劑之初餾點+30℃ The initial boiling point of the solvent -30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C

再者,所謂溶劑之初餾點,意指依據JIS K0066(1992)而測得之值。JIS K0066(1992)之內容係作為參照而併入本文中。 The initial boiling point of a solvent means a value measured in accordance with JIS K0066 (1992). The contents of JIS K0066 (1992) are incorporated herein by reference.

上述第1溫度與第2溫度之差並無特別限制,較佳為10℃以上,更佳為30℃以上。上限並無特別限制,通常較佳為100℃以下,更佳為70℃以下。 The difference between the first temperature and the second temperature is not particularly limited, but is preferably 10 ° C or higher, and more preferably 30 ° C or higher. The upper limit is not particularly limited, but is usually preferably 100 ° C or lower, and more preferably 70 ° C or lower.

又,第1溫度較佳為210℃以下。即,較佳為包含:於210℃以下實施加熱處理之第1加熱步驟、與於超過210℃之溫度下實施加熱處理之第2加熱步驟。若為210℃以下,則更為抑制溶劑之爆沸或聚矽氧樹脂之揮發,從而所形成之聚矽氧樹脂層16之表面面狀更優異。以下,針對上述溫度條件下之上述第1加熱步驟及上述第2加熱步驟進行詳述。 The first temperature is preferably 210 ° C or lower. That is, it is preferable to include a first heating step for performing a heat treatment at 210 ° C or lower, and a second heating step for performing a heat treatment at a temperature exceeding 210 ° C. If it is 210 ° C. or lower, the bumping of the solvent or the volatilization of the silicone resin is more suppressed, so that the surface shape of the formed silicone resin layer 16 is more excellent. Hereinafter, the first heating step and the second heating step under the temperature conditions will be described in detail.

第1加熱步驟係所謂預烘烤步驟,主要將殘留於硬化性聚矽氧組合物層12中之溶劑等揮發成分去除,而防止於下述之第2加熱步驟中溶劑爆沸。第1加熱步驟之溫度條件較佳為210℃以下,就聚矽氧樹脂層16之表面面狀更優異之方面而言,更佳為150~210℃。加熱時間係 根據所使用之材料而適當選擇最佳之條件,就生產性及溶劑之去除性之方面而言,較佳為1~5分鐘,更佳為2~3分鐘。 The first heating step is a so-called pre-baking step, which mainly removes volatile components such as solvents remaining in the curable polysiloxane composition layer 12 and prevents the solvent from boiling in the second heating step described below. The temperature condition of the first heating step is preferably 210 ° C. or lower, and in terms of the surface profile of the silicone resin layer 16 being more excellent, it is more preferably 150 to 210 ° C. Heating time The optimum conditions are appropriately selected according to the materials used. In terms of productivity and solvent removal, it is preferably 1 to 5 minutes, and more preferably 2 to 3 minutes.

第2加熱步驟係所謂後烘烤步驟,主要促進硬化性聚矽氧組合物層12之硬化而形成聚矽氧樹脂層16。第2加熱步驟之溫度條件較佳為超過210℃,就硬化性聚矽氧組合物層12之溶劑去除及硬化反應更優異之方面而言,更佳為超過210℃且為250℃以下。加熱時間係根據所使用之材料而適當選擇最佳之條件,就生產性及溶劑之去除性之方面而言,較佳為10~120分鐘,更佳為30~60分鐘。 The second heating step is a so-called post-baking step, which mainly promotes the hardening of the curable polysiloxane composition layer 12 to form a polysiloxane resin layer 16. The temperature condition in the second heating step is preferably more than 210 ° C. In terms of better solvent removal and hardening reaction of the curable polysiloxane composition layer 12, it is more preferably more than 210 ° C and 250 ° C or less. The heating time is appropriately selected according to the materials used. In terms of productivity and solvent removal, it is preferably 10 to 120 minutes, and more preferably 30 to 60 minutes.

經過本步驟S102而形成之聚矽氧樹脂層16係藉由於支持基板10上實施硬化性聚矽氧組合物層12之硬化反應而被固定於支持基板10之單面上,又,以可剝離之方式與下述之玻璃基板20進行密接。聚矽氧樹脂層16係防止玻璃基板20之錯位直至進行將玻璃基板20與支持基板10進行分離之操作,並且防止由於分離操作而容易地自玻璃基板20剝離,玻璃基板20等由於分離操作而破損。又,聚矽氧樹脂層16係被固定於支持基板10,於分離操作中未使聚矽氧樹脂層16與支持基板10剝離,可藉由分離操作而獲得附樹脂層之支持基板18。 The silicone resin layer 16 formed through this step S102 is fixed on one side of the support substrate 10 by the curing reaction of the hardening silicone composition layer 12 on the support substrate 10, and is peelable. This method is in close contact with the glass substrate 20 described below. The polysiloxane resin layer 16 prevents misalignment of the glass substrate 20 until the operation of separating the glass substrate 20 from the support substrate 10 is performed, and it is prevented from being easily peeled from the glass substrate 20 due to the separation operation. damaged. In addition, the polysiloxane resin layer 16 is fixed to the support substrate 10, and the polysiloxane resin layer 16 and the support substrate 10 are not separated during the separation operation. The support substrate 18 with a resin layer can be obtained by the separation operation.

聚矽氧樹脂層16之與玻璃基板20接觸之表面係以可剝離之方式密接於玻璃基板20之第1主面。本發明中,將該聚矽氧樹脂層16表面之可容易剝離之性質稱為易剝離性(剝離性)。 The surface of the silicone resin layer 16 that is in contact with the glass substrate 20 is closely adhered to the first main surface of the glass substrate 20 in a peelable manner. In the present invention, the easily peelable property of the surface of the silicone resin layer 16 is referred to as easy peelability (peelability).

於本發明中,對於上述固定與可剝離之密接而言,剝離強度(即,剝離所需要之應力)存在差異,固定意指相對於密接,剝離強度較大。又,所謂可剝離之密接,亦意指於可剝離之同時,於不產生所固定之面之剝離之情況下可剝離。具體而言,於本發明之玻璃積層體中,進行將玻璃基板20與支持基板10進行分離之操作之情形時,意指於密接之面剝離,於固定之面未剝離之情況。因此,於玻璃積層體中,若進行將玻璃基板20與支持基板10進行分離之操作,則玻璃積層 體被分成玻璃基板20與附樹脂層之支持基板18兩者。 In the present invention, there is a difference in peel strength (that is, the stress required for peeling) for the above-mentioned fixed and peelable adhesion. Fixation means that the peel strength is greater than the adhesion. In addition, the so-called peelable adhesion means peeling and peeling without causing peeling of the fixed surface. Specifically, when the operation of separating the glass substrate 20 from the support substrate 10 is performed in the glass laminate of the present invention, it means a case where it is peeled off on the surface that is in close contact, and it is not peeled off on the fixed surface. Therefore, in the glass laminate, if the operation of separating the glass substrate 20 and the support substrate 10 is performed, the glass laminate is laminated. The body is divided into both a glass substrate 20 and a support substrate 18 with a resin layer.

即,聚矽氧樹脂層16對支持基板10之第1主面之結合力相對高於聚矽氧樹脂層16對玻璃基板20之第1主面的結合力。 That is, the bonding force of the silicone resin layer 16 to the first main surface of the support substrate 10 is relatively higher than the bonding force of the silicone resin layer 16 to the first main surface of the glass substrate 20.

聚矽氧樹脂層16之厚度並無特別限定,較佳為2~100μm,更佳為3~50μm,進而較佳為7~20μm。若聚矽氧樹脂層16之厚度為上述範圍,則即便於聚矽氧樹脂層16與玻璃基板20之間存在氣泡或異物,亦可抑制玻璃基板20之變形缺陷之產生。又,若聚矽氧樹脂層16之厚度過厚,則有因形成需要時間及材料,故而不經濟,且耐熱性降低之情形。又,若聚矽氧樹脂層16之厚度過薄,則有聚矽氧樹脂層16與玻璃基板20之密接性降低之情形。 The thickness of the polysiloxane resin layer 16 is not particularly limited, but is preferably 2 to 100 μm, more preferably 3 to 50 μm, and even more preferably 7 to 20 μm. If the thickness of the silicone resin layer 16 is within the above range, even if there are bubbles or foreign matter between the silicone resin layer 16 and the glass substrate 20, the generation of deformation defects of the glass substrate 20 can be suppressed. Further, if the thickness of the silicone resin layer 16 is too thick, it may be uneconomical due to the time and material required for the formation, and the heat resistance may be reduced. When the thickness of the silicone resin layer 16 is too thin, the adhesion between the silicone resin layer 16 and the glass substrate 20 may be reduced.

<積層步驟> <Lamination step>

積層步驟S104係如下步驟,即於上述步驟S102中所獲得之聚矽氧樹脂層16之表面上積層玻璃基板20,而獲得依序包含支持基板10、聚矽氧樹脂層16、及玻璃基板20之玻璃積層體100。更具體而言,如圖2(C)所示般,以聚矽氧樹脂層16之與支持基板10側相反側之表面16a、與具有第1主面20a及第2主面20b之玻璃基板20之第1主面20a為積層面,將聚矽氧樹脂層16與玻璃基板20進行積層,而獲得玻璃積層體100。再者,如下所述,所獲得之玻璃積層體100係實施下述之表面處理步驟S106前之處理前玻璃積層體,而推測於玻璃積層體100之支持基板10之與聚矽氧樹脂層16側相反側之表面(支持基板10之第2主面10a)附著有聚矽氧樹脂或其原料。 The laminating step S104 is a step of laminating a glass substrate 20 on the surface of the polysiloxane resin layer 16 obtained in the above step S102 to obtain a support substrate 10, a polysiloxane resin layer 16, and a glass substrate 20 in this order. The glass laminate 100. More specifically, as shown in FIG. 2 (C), the surface 16a of the silicone resin layer 16 on the side opposite to the support substrate 10 side, and the glass substrate having the first main surface 20a and the second main surface 20b The first main surface 20 a of 20 is a build-up layer, and the polysiloxane resin layer 16 and the glass substrate 20 are laminated to obtain a glass laminate 100. Furthermore, as described below, the obtained glass laminate 100 is a glass laminate before the following surface treatment step S106 is performed, and it is estimated that the support substrate 10 and the polysiloxane layer 16 of the glass laminate 100 The surface opposite to the side (the second main surface 10a of the support substrate 10) is adhered with a silicone resin or a raw material thereof.

針對所使用之玻璃基板20,於下文進行詳述。 The glass substrate 20 to be used is described in detail below.

將玻璃基板20積層於聚矽氧樹脂層16上之方法並無特別限制,可採用公知之方法。 The method of laminating the glass substrate 20 on the silicone resin layer 16 is not particularly limited, and a known method can be adopted.

例如可列舉於常壓環境下於聚矽氧樹脂層16之表面上重疊玻璃基板20之方法。再者,亦可視需要,於聚矽氧樹脂層16之表面上重疊 玻璃基板20後,使用輥或加壓而使玻璃基板20壓接於聚矽氧樹脂層16。藉由利用輥或加壓之壓接,而相對容易去除混入聚矽氧樹脂層16與玻璃基板20之間之氣泡,故而較佳。 For example, a method of superposing the glass substrate 20 on the surface of the silicone resin layer 16 under a normal pressure environment can be mentioned. Furthermore, if necessary, it may be superposed on the surface of the polysiloxane layer 16 After the glass substrate 20, the glass substrate 20 is pressure-bonded to the silicone resin layer 16 using a roller or pressure. It is relatively easy to remove the air bubbles mixed between the silicone resin layer 16 and the glass substrate 20 by using a roller or a pressure contact, so it is preferable.

若藉由真空層壓法或真空加壓法而將聚矽氧樹脂層16與玻璃基板20進行壓接,則抑制氣泡之混入或確保良好之密接,故而更佳。亦有如下優點,即藉由於真空下進行壓接,即便於殘留有微小之氣泡之情形時,亦無由於加熱而氣泡成長之情況,而難以導致玻璃基板20之變形缺陷。 If the silicone resin layer 16 and the glass substrate 20 are pressure-bonded by a vacuum lamination method or a vacuum pressure method, it is more preferable to prevent the inclusion of bubbles or to ensure a good adhesion. There is also an advantage that by performing pressure bonding under vacuum, even when there are tiny bubbles remaining, there is no case where the bubbles grow due to heating and it is difficult to cause deformation defects of the glass substrate 20.

於積層玻璃基板20時,較佳為將與聚矽氧樹脂層16接觸之玻璃基板20之表面充分洗淨,而於潔淨度較高之環境下進行積層。潔淨度越高,玻璃基板20之平坦性變得越良好,故而較佳。 When the glass substrate 20 is laminated, it is preferable that the surface of the glass substrate 20 that is in contact with the polysiloxane resin layer 16 is sufficiently cleaned and laminated in an environment with high cleanliness. The higher the cleanliness, the better the flatness of the glass substrate 20 is, so it is preferable.

再者,積層玻璃基板20後,亦可視需要而進行預退火處理(加熱處理)。藉由進行該預退火處理,從而積層之玻璃基板20之對聚矽氧樹脂層16之密接性提高,可成為適當之剝離強度,而於下述之構件形成步驟時變得難以產生電子裝置用構件之錯位等,而電子裝置之生產性提高。 In addition, after the glass substrate 20 is laminated, a pre-annealing treatment (heating treatment) may be performed as necessary. By performing this pre-annealing treatment, the adhesion of the laminated glass substrate 20 to the silicone resin layer 16 is improved, and appropriate peeling strength can be achieved. However, it becomes difficult to produce electronic devices during the following member formation steps. Dislocation of components, etc., and the productivity of electronic devices is improved.

預退火處理之條件係視所使用之聚矽氧樹脂層16之種類而適當選擇最佳之條件,就使玻璃基板20與聚矽氧樹脂層16之間之剝離強度變得更適當之方面而言,較佳為於300℃以上(較佳為300~400℃)之溫度下進行5分鐘以上(較佳為5~30分鐘)加熱處理。 The conditions of the pre-annealing treatment are appropriately selected depending on the type of the silicone resin layer 16 used, so that the peeling strength between the glass substrate 20 and the silicone resin layer 16 becomes more appropriate. In other words, the heat treatment is preferably performed at a temperature of 300 ° C. or higher (preferably 300 to 400 ° C.) for 5 minutes or more (preferably 5 to 30 minutes).

(玻璃基板) (Glass base board)

玻璃基板20係其第1主面20a與聚矽氧樹脂層16接觸,且於其與聚矽氧樹脂層16側相反側之第2主面20b設置有電子裝置用構件。 The glass substrate 20 has a first main surface 20 a in contact with the silicone resin layer 16, and a second main surface 20 b on the side opposite to the silicone resin layer 16 side is provided with a member for an electronic device.

玻璃基板20之種類可為通常者,例如可列舉LCD(liquid crystal display,液晶顯示裝置)、OLED(Organic Light-Emitting Diode,有機發光二極體)等顯示裝置用之玻璃基板等。玻璃基板20之耐化學品 性、耐透濕性優異,且熱收縮率較低。作為熱收縮率之指標,可使用JIS R 3102(1995年修正)所規定之線膨脹係數。JIS R 3102(1995年修正)之內容係作為參照被併入本文中。 The type of the glass substrate 20 may be ordinary, and examples thereof include glass substrates for display devices such as an LCD (liquid crystal display) and an OLED (Organic Light-Emitting Diode). Chemical resistance of glass substrate 20 Excellent in moisture resistance and moisture permeability, and has a low thermal shrinkage. As an index of thermal shrinkage, a linear expansion coefficient prescribed by JIS R 3102 (revised in 1995) can be used. The contents of JIS R 3102 (as amended in 1995) are incorporated herein by reference.

若玻璃基板20之線膨脹係數較大,則因下述之構件形成步驟大多伴隨著加熱處理,故容易產生各種問題。例如於玻璃基板20上形成薄膜電晶體(TFT)之情形時,有如下之虞:若於加熱下將形成有TFT之玻璃基板20進行冷卻,則由於玻璃基板20之熱收縮而導致TFT之錯位變得過大。 When the linear expansion coefficient of the glass substrate 20 is large, since the following member formation steps are often accompanied by heat treatment, various problems are likely to occur. For example, when a thin film transistor (TFT) is formed on the glass substrate 20, there is a possibility that if the glass substrate 20 on which the TFT is formed is cooled under heating, the TFT will be displaced due to the thermal contraction of the glass substrate 20 Become too big.

玻璃基板20係使玻璃原料熔融並將熔融玻璃成形為板狀而獲得。此種成形方法可為通常者,例如可使用浮式法、熔融法、流孔下引法、富可法、魯伯法等。又,尤其是厚度較薄之玻璃基板20可利用將暫時成形為板狀之玻璃加熱至可成形之溫度,利用延伸等方法進行拉伸而使玻璃變薄之方法(再曳引法)進行成形而獲得。 The glass substrate 20 is obtained by melting glass raw materials and shaping the molten glass into a plate shape. Such a molding method may be a common one, and for example, a float method, a melt method, a downhole method, a Fuco method, a Ruber method, or the like can be used. In addition, in particular, the thin glass substrate 20 can be formed by heating the glass that has been temporarily formed into a plate shape to a formable temperature, and stretching it by a method such as stretching to thin the glass (retraction method). And get.

玻璃基板20之玻璃之種類並無特別限定,較佳為無鹼硼矽酸玻璃、硼矽酸玻璃、鈉鈣玻璃、高二氧化矽玻璃、其他以氧化矽為主要成分之氧化物系玻璃。作為氧化物系玻璃,較佳為利用氧化物換算之氧化矽之含量為40~90質量%之玻璃。 The type of glass of the glass substrate 20 is not particularly limited, and alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses containing silicon oxide as a main component are preferred. The oxide-based glass is preferably a glass having a silicon oxide content of 40 to 90% by mass based on oxide conversion.

作為玻璃基板20之玻璃,係採用適合電子裝置用構件之種類或其製造步驟之玻璃。例如液晶面板用之玻璃基板因鹼金屬成分之溶出容易對液晶產生影響,故由實質上不含有鹼金屬成分之玻璃(無鹼玻璃)(其中,包括通常鹼土金屬成分)構成。如上所述,玻璃基板20之玻璃係基於所適用之裝置之種類及其製造步驟而適當選擇。 As the glass of the glass substrate 20, a glass suitable for the type of a member for an electronic device or a manufacturing process thereof is used. For example, the glass substrate for a liquid crystal panel is likely to affect the liquid crystal due to the elution of an alkali metal component, and therefore is composed of a glass (alkali-free glass) that does not substantially contain an alkali metal component (including an alkaline earth metal component). As described above, the glass of the glass substrate 20 is appropriately selected based on the type of the device to be applied and its manufacturing steps.

關於玻璃基板20之厚度,就玻璃基板20之薄型化及/或輕量化之觀點而言,較佳為0.3mm以下,更佳為0.15mm以下,進而較佳為0.10mm以下。於玻璃基板20之厚度為0.3mm以下之情形時,可向玻璃基板20賦予良好之可撓性。於玻璃基板20之厚度為0.15mm以下之 情形時,可將玻璃基板20捲取成輥狀。 The thickness of the glass substrate 20 is preferably 0.3 mm or less, more preferably 0.15 mm or less, and still more preferably 0.10 mm or less from the viewpoint of thinning and / or lightening the glass substrate 20. When the thickness of the glass substrate 20 is 0.3 mm or less, good flexibility can be imparted to the glass substrate 20. The thickness of the glass substrate 20 is 0.15 mm or less In this case, the glass substrate 20 can be wound into a roll shape.

又,就玻璃基板20之製造容易,及玻璃基板20之操作容易等理由而言,玻璃基板20之厚度較佳為0.03mm以上。 In addition, for reasons such as easy manufacturing of the glass substrate 20 and easy handling of the glass substrate 20, the thickness of the glass substrate 20 is preferably 0.03 mm or more.

再者,玻璃基板20亦可包含2層以上,於該情形時,形成各層之材料可為同種材料,亦可為異種材料。又,於該情形時,「玻璃基板20之厚度」意指全部層之合計之厚度。 Furthermore, the glass substrate 20 may include two or more layers. In this case, the materials forming each layer may be the same material or different materials. In this case, the "thickness of the glass substrate 20" means the total thickness of all layers.

(玻璃積層體) (Glass laminate)

玻璃積層體100係具有支持基板10、玻璃基板20及存在於該等之間之聚矽氧樹脂層16之積層體。聚矽氧樹脂層16係其一面與支持基板10之第1主面接觸,並且其另一面與玻璃基板20之第1主面20a接觸。 The glass laminated body 100 is a laminated body which has a support substrate 10, a glass substrate 20, and a silicone resin layer 16 existing between them. The silicone resin layer 16 is in contact with the first main surface of the support substrate 10 on one side and in contact with the first main surface 20 a of the glass substrate 20 on the other side.

該玻璃積層體100係被使用至下述之構件形成步驟。即,該玻璃積層體100係被使用至於其玻璃基板20之第2主面20b表面上形成有液晶顯示裝置等電子裝置用構件為止。其後,形成有電子裝置用構件之玻璃積層體被分離為附樹脂層之支持基板18與電子裝置,附樹脂層之支持基板18不會成為構成電子裝置之部分。可於附樹脂層之支持基板18積層新的玻璃基板20而作為新的玻璃積層體100進行再利用。 This glass laminated body 100 is used in the following member formation steps. That is, the glass laminated body 100 is used until a member for electronic devices such as a liquid crystal display device is formed on the surface of the second main surface 20 b of the glass substrate 20. Thereafter, the glass laminated body on which the member for an electronic device is formed is separated into a supporting substrate 18 with a resin layer and an electronic device, and the supporting substrate 18 with a resin layer does not become a part constituting the electronic device. A new glass substrate 20 can be laminated on the support substrate 18 with a resin layer and reused as a new glass laminate 100.

支持基板10與聚矽氧樹脂層16之界面具有剝離強度(x),若向支持基板10與聚矽氧樹脂層16之界面施加超過剝離強度(x)之剝離方向之應力,則於支持基板10與聚矽氧樹脂層16之界面產生剝離。聚矽氧樹脂層16與玻璃基板20之界面具有剝離強度(y),若向聚矽氧樹脂層16與玻璃基板20之界面施加超過剝離強度(y)之剝離方向之應力,則於聚矽氧樹脂層16與玻璃基板20之界面產生剝離。 The interface between the support substrate 10 and the polysiloxane layer 16 has a peeling strength (x). If a stress exceeding the peeling direction (x) in the peeling direction is applied to the interface between the support substrate 10 and the polysiloxane layer 16, the support substrate 10 has a peel strength (x). Delamination occurred at the interface between 10 and the polysiloxane layer 16. The interface between the silicone resin layer 16 and the glass substrate 20 has peeling strength (y). If a stress exceeding the peeling direction (y) in the peeling direction is applied to the interface between the silicone resin layer 16 and the glass substrate 20, then the silicon The interface between the oxyresin layer 16 and the glass substrate 20 is peeled.

如上所述,於玻璃積層體100(亦意指下述之附電子裝置用構件之積層體)中,上述剝離強度(x)大於(高於)上述剝離強度(y)。因此,若向玻璃積層體100施加將支持基板10與玻璃基板20進行剝離之方向之應力,則玻璃積層體100係於聚矽氧樹脂層16與玻璃基板20之界面產 生剝離而分離為玻璃基板20與附樹脂層之支持基板18。 As described above, in the glass laminated body 100 (also referred to as a laminated body with a member for an electronic device described below), the peel strength (x) is greater (higher) than the peel strength (y). Therefore, if a stress is applied to the glass laminate 100 in the direction in which the support substrate 10 and the glass substrate 20 are peeled off, the glass laminate 100 is produced at the interface between the polysiloxane resin layer 16 and the glass substrate 20. The glass substrate 20 is peeled off and separated into a support substrate 18 with a resin layer.

即,聚矽氧樹脂層16係被固定於支持基板10上而形成附樹脂層之支持基板18,玻璃基板20以可剝離之方式密接於聚矽氧樹脂層16上。 That is, the silicone resin layer 16 is fixed on the support substrate 10 to form a support substrate 18 with a resin layer, and the glass substrate 20 is adhered to the silicone resin layer 16 in a peelable manner.

剝離強度(x)較佳為充分高於剝離強度(y)。提高剝離強度(x)意指可提高聚矽氧樹脂層16對支持基板10之附著力,且可維持於加熱處理後對玻璃基板20之相對較高之附著力。 The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the silicone resin layer 16 to the support substrate 10 can be improved, and a relatively high adhesion to the glass substrate 20 can be maintained after the heat treatment.

聚矽氧樹脂層16對支持基板10之附著力之提高係藉由如下方式達成,即如上述般使硬化性聚矽氧組合物層12於支持基板10上進行交聯硬化而形成聚矽氧樹脂層16。可利用交聯硬化時之接著力形成以較高之結合力結合於支持基板10之聚矽氧樹脂層16。 The improvement of the adhesion of the polysiloxane resin layer 16 to the support substrate 10 is achieved by crosslinking and hardening the curable polysiloxane composition layer 12 on the support substrate 10 as described above to form polysiloxane. Resin layer 16. The silicone resin layer 16 bonded to the supporting substrate 10 with a higher bonding force can be formed by using the adhesive force during the cross-linking curing.

另一方面,硬化性聚矽氧組合物層12之硬化物對玻璃基板20之結合力通常低於上述交聯硬化時所產生之結合力。 On the other hand, the bonding force of the cured product of the curable polysiloxane composition layer 12 to the glass substrate 20 is generally lower than the bonding force generated during the above-mentioned crosslinking and curing.

玻璃積層體100可用於各種用途,例如可列舉:製造下述之顯示裝置用面板、PV、薄膜2次電池、表面形成有電路之半導體晶圓等電子零件之用途等。再者,於該用途中,玻璃積層體100大多被暴露於高溫條件(例如360℃以上)下(例如1小時以上)。 The glass laminated body 100 can be used for various applications, and examples thereof include applications for manufacturing electronic components such as a panel for a display device described below, PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed on the surface. In addition, in this application, the glass laminate 100 is often exposed to high temperature conditions (for example, 360 ° C. or higher) (for example, 1 hour or longer).

此處,所謂顯示裝置用面板,包括LCD、OLED、電子紙、電漿顯示器面板、場發射面板、量子點LED面板、MEMS(Micro Electro Mechanical Systems,微電子機械系統)快門面板等。 Here, the so-called display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

<表面處理步驟> <Surface Treatment Step>

表面處理步驟S106係如下步驟,即針對至少支持基板之第2主面(與有聚矽氧樹脂層之側相反側之面)實施選自由電暈處理、電漿處理、及UV臭氧處理所組成之群中之至少1種處理。於第1態樣中,刻意地對上述中所形成之玻璃積層體中之支持基板之第2主面實施上述處理。更具體而言,對圖2(C)之支持基板10之第2主面10a實施上述處 理。藉由實施本步驟S106,而將於上述加熱步驟S102時揮發而附著於支持基板10之第2主面10a之聚矽氧樹脂或其原料成分等去除,而使支持基板10之第2主面10a潔淨化。即,藉由對上述積層步驟S104中所獲得之玻璃積層體實施上述處理,而可獲得經過處理之玻璃積層體。再者,亦可如下述般,於本步驟S106中,對玻璃積層體中之支持基板之第2主面、與玻璃積層體中之玻璃基板之露出表面一併實施上述處理。 The surface treatment step S106 is a step in which at least the second main surface of the supporting substrate (the surface opposite to the side having the silicone resin layer) is selected from the group consisting of corona treatment, plasma treatment, and UV ozone treatment. At least one treatment in the group. In the first aspect, the above-mentioned process is intentionally performed on the second main surface of the supporting substrate in the glass laminate formed in the above. More specifically, the above-mentioned processing is performed on the second main surface 10a of the support substrate 10 in FIG. 2 (C). Management. By implementing this step S106, the silicone resin or its raw material components which are volatilized and adhered to the second main surface 10a of the support substrate 10 during the heating step S102 described above are removed, so that the second main surface of the support substrate 10 is removed. 10a cleansing. That is, by performing the above-mentioned processing on the glass laminated body obtained in the above-mentioned laminating step S104, a processed glass laminated body can be obtained. In addition, as described below, in this step S106, the second main surface of the support substrate in the glass laminate and the exposed surface of the glass substrate in the glass laminate may be subjected to the above processing together.

作為本步驟S106中所實施之電暈處理(電暈洗淨),係實施公知之電暈處理。再者,所謂電暈處理,係藉由電暈放電照射而使塑膠膜、紙、及金屬箔等處理基材之表面改質之表面處理技術。若自高頻電源裝置將振盪之高頻.高電壓施加於高壓電極與接地電極之間,則產生電暈放電。 As the corona treatment (corona cleaning) performed in this step S106, a known corona treatment is performed. In addition, the so-called corona treatment is a surface treatment technology for modifying the surface of a treated substrate such as a plastic film, paper, and metal foil by corona discharge irradiation. If the high-frequency power device will oscillate the high frequency. When a high voltage is applied between the high voltage electrode and the ground electrode, a corona discharge is generated.

電暈處理之方法並無特別限制,例如較佳為如下方法,即向支持玻璃積層體之搬送輥、與與其對向設置之電極之間施加高電壓而進行電暈放電,並在此期間使玻璃積層體依序移動而進行表面處理。作為具體之電暈處理用裝置,可列舉:包含高頻電源(高頻振盪機)、高壓變壓器、及放電電極,且於其前後安裝有搬送玻璃積層體之搬送機之裝置。高頻振盪機之頻率並無特別限制,例如較佳為0.1~100kHz,較佳為最大輸出0.5~50kW左右者。玻璃積層體之搬送速度(處理速度)並無特別限制,較佳為1~10m/min。 The method of corona treatment is not particularly limited. For example, a method is preferred in which a corona discharge is performed by applying a high voltage between a transport roller supporting a glass laminate and an electrode disposed opposite to it, and during this period, The glass laminate is sequentially moved to perform surface treatment. Specific examples of the device for corona treatment include a device including a high-frequency power source (high-frequency oscillator), a high-voltage transformer, and a discharge electrode, and a glass-laminated glass-conveying device is mounted in front and rear of the device. The frequency of the high-frequency oscillator is not particularly limited. For example, it is preferably 0.1 to 100 kHz, and preferably the maximum output is about 0.5 to 50 kW. The conveyance speed (processing speed) of the glass laminate is not particularly limited, but is preferably 1 to 10 m / min.

再者,於積層步驟S104後實施表面處理步驟S106之情形時,較佳為使用以下所說明之電暈處理裝置。 When the surface treatment step S106 is performed after the lamination step S104, it is preferable to use a corona treatment device described below.

圖4係表示電暈處理裝置之一實施形態之側視圖。電暈處理裝置60至少包含:第1高壓電極62、第1接地電極64、第2高壓電極66、及第2接地電極68。第1高壓電極62與第1接地電極64係隔著特定間隔對向配置而構成第1電極對70,且於該等第1高壓電極62與第1接地電極 64之間形成有放電空間。又,第2高壓電極66與第2接地電極68係隔著特定間隔對向配置而構成第2電極對72,且於該等第2高壓電極66與第2接地電極68之間形成有放電空間。第1電極對70與第2電極對72係如圖4所示般,沿著將積層步驟S104中所獲得之依序具有支持基板、聚矽氧樹脂層及玻璃基板之玻璃積層體X進行搬送之方向鄰接配置。進而,如圖4所示般,玻璃積層體X係藉由搬送輥74進行搬送,且於第1高壓電極62與第1接地電極64之間、及第2高壓電極66與第2接地電極68之間移行。 Fig. 4 is a side view showing an embodiment of the corona treatment device. The corona treatment device 60 includes at least a first high-voltage electrode 62, a first ground electrode 64, a second high-voltage electrode 66, and a second ground electrode 68. The first high-voltage electrode 62 and the first ground electrode 64 are opposed to each other at a specific interval to form a first electrode pair 70. The first high-voltage electrode 62 and the first ground electrode A discharge space is formed between 64. In addition, the second high-voltage electrode 66 and the second ground electrode 68 are arranged to face each other with a predetermined interval therebetween to form a second electrode pair 72, and a discharge space is formed between the second high-voltage electrode 66 and the second ground electrode 68. . As shown in FIG. 4, the first electrode pair 70 and the second electrode pair 72 are conveyed along the glass laminate X having a support substrate, a polysiloxane resin layer, and a glass substrate in the order obtained in the lamination step S104. The directions are adjacent to each other. Further, as shown in FIG. 4, the glass laminate X is conveyed by a conveying roller 74 and is between the first high-voltage electrode 62 and the first ground electrode 64, and the second high-voltage electrode 66 and the second ground electrode 68. Move between.

又,第1高壓電極62係與第1高頻電源76連接而被施加高頻電壓。又,第2高壓電極66係與第2高頻電源78連接而被施加高頻電壓。再者,於圖4中,使用有第1高頻電源76與第2高頻電源78兩者,但並不限定於該態樣,第1高頻電源76與第2高頻電源78亦可使用(共用)同一電源。 The first high-voltage electrode 62 is connected to the first high-frequency power source 76 and is applied with a high-frequency voltage. The second high-voltage electrode 66 is connected to the second high-frequency power source 78 and is applied with a high-frequency voltage. Moreover, in FIG. 4, both the first high-frequency power supply 76 and the second high-frequency power supply 78 are used, but the present invention is not limited to this aspect, and the first high-frequency power supply 76 and the second high-frequency power supply 78 may be used. Use (share) the same power source.

進而,第1高壓電極62與第2高壓電極66係分別配置於圖4中之隔著搬送玻璃積層體X之路徑(搬送路徑)之上側(一側)與下側(另一側)。換言之,第1高壓電極62與第2高壓電極66係沿著玻璃積層體X之搬送方向交錯配置。 Further, the first high-voltage electrode 62 and the second high-voltage electrode 66 are respectively arranged on the upper side (one side) and the lower side (the other side) of the path (transport path) through which the glass laminate X is transported in FIG. 4. In other words, the first high-voltage electrodes 62 and the second high-voltage electrodes 66 are staggered along the transport direction of the glass laminate X.

若使用搬送輥74將玻璃積層體X向上述電暈處理裝置60進行搬送,則因第1高壓電極62與第2高壓電極66被分別配置於玻璃積層體X之搬送路徑之一側及另一側,故而可有效率地對所搬送之玻璃積層體X之兩面進行電暈處理。即,可對玻璃積層體X中之支持基板之第2主面(與聚矽氧樹脂層側相反側之面)、及玻璃基板之露出表面(與聚矽氧樹脂層側相反側之面)實施電暈處理。 When the glass laminate X is transferred to the corona processing device 60 using the transfer roller 74, the first high-voltage electrode 62 and the second high-voltage electrode 66 are respectively disposed on one side and the other of the conveyance path of the glass laminate X Side, so that both sides of the glass laminate X to be transported can be corona treated efficiently. That is, the second main surface of the support substrate in the glass laminate X (the surface opposite to the silicone resin layer side) and the exposed surface of the glass substrate (the surface opposite to the silicone resin layer side) can be applied. Corona treatment.

再者,高頻電源之條件、或玻璃積層體X之搬送速度(處理速度)之條件之較佳範圍係如上所述。 The preferable ranges of the conditions of the high-frequency power supply and the conditions of the conveyance speed (processing speed) of the glass laminate X are as described above.

又,於圖4中,第1高壓電極62被配置於圖式中之上側,第2高壓 電極66被配置於圖式中之下側,但並不限定於該態樣,上述位置關係亦可反轉。 In FIG. 4, the first high-voltage electrode 62 is disposed on the upper side in the drawing, and the second high-voltage electrode 62 The electrode 66 is arranged on the lower side in the drawing, but it is not limited to this aspect, and the above-mentioned positional relationship may be reversed.

又,於欲僅對玻璃積層體X之單側面(支持基板之第2主面)強力地實施電暈處理之情形時,亦可將第1高壓電極62及第2高壓電極66一起配置於圖式中之上側、或下側。 When the corona treatment is to be applied to only one side of the glass laminate X (the second main surface of the supporting substrate), the first high-voltage electrode 62 and the second high-voltage electrode 66 may be arranged together in the figure. In the formula, the upper side or the lower side.

進而,於圖4中,記載有包含第1電極對70與第2電極對72兩者之電暈處理裝置,但電極對之數量並不限定於該態樣。 Further, in FIG. 4, the corona treatment device including both the first electrode pair 70 and the second electrode pair 72 is described, but the number of electrode pairs is not limited to this aspect.

作為第1高壓電極62、第2高壓電極66、第1接地電極64、及第2接地電極68,可使用金屬電極、或被介電體被覆之電極,但為了穩定地進行用以電暈處理之放電,較佳為對向配置之第1高壓電極62及第1接地電極64之至少1者、及對向配置之第2高壓電極66及第2接地電極68之至少1者被介電體被覆。更佳為第1高壓電極62及第1接地電極64兩者、以及第2高壓電極66及第2接地電極68兩者被介電體覆蓋。藉此,可擴大高壓電極與接地電極間之間隔,而變得容易穩定地搬送玻璃積層體X。 As the first high-voltage electrode 62, the second high-voltage electrode 66, the first ground electrode 64, and the second ground electrode 68, a metal electrode or an electrode covered with a dielectric body may be used, but the corona treatment is performed in order to perform stably. The discharge is preferably at least one of the first high-voltage electrode 62 and the first ground electrode 64 arranged oppositely, and at least one of the second high-voltage electrode 66 and the second ground electrode 68 arranged oppositely. Covered. More preferably, both the first high-voltage electrode 62 and the first ground electrode 64 and both the second high-voltage electrode 66 and the second ground electrode 68 are covered with a dielectric body. Thereby, the gap between the high-voltage electrode and the ground electrode can be enlarged, and the glass laminated body X can be easily and stably transported.

再者,作為被介電體被覆之電極(介電體被覆電極),較佳為於不鏽鋼或鋁等金屬等導電性之芯材之表面塗佈陶瓷等而成之陶瓷電極。通常於對樹脂膜進行電暈處理之情形時等,可使用於金屬芯材塗佈橡膠材而成之橡膠電極作為介電體被覆電極,但由於重量與剛性之關係而直徑較粗,因此有如下情況,即電暈處理裝置60大型化,搬送輥間有空隙而於搬送較薄之玻璃積層體X時產生問題。陶瓷電極輕量且剛性較高,因此直徑小於橡膠電極,故而難以產生上述問題。 The dielectric-coated electrode (dielectric-coated electrode) is preferably a ceramic electrode obtained by coating ceramics or the like on the surface of a conductive core material such as stainless steel or aluminum. Generally, when corona treatment is performed on a resin film, a rubber electrode formed by coating a rubber material on a metal core material can be used as a dielectric-coated electrode. However, due to the relationship between weight and rigidity, the diameter is relatively large. In the case where the corona treatment device 60 is enlarged, there is a gap between the transport rollers, and a problem occurs when the thin glass laminate X is transported. The ceramic electrode is light in weight and high in rigidity, so its diameter is smaller than that of a rubber electrode, so it is difficult to cause the above problems.

又,對於橡膠電極而言,由於放電而橡膠覆膜容易損傷,故而難以固定電極並使用。因此,於橡膠電極上設置有轉動機構,通常一面轉動一面使用,但有裝置複雜且大型化之問題。關於陶瓷電極,即便於相同位置反覆進行放電亦難以損傷,因此無需設置上述之轉動機 構。 In addition, in the rubber electrode, the rubber film is easily damaged due to electric discharge, and it is difficult to fix and use the electrode. Therefore, a rotation mechanism is provided on the rubber electrode, and it is usually used while rotating, but there are problems that the device is complicated and large. Regarding the ceramic electrode, it is difficult to damage even if it is repeatedly discharged at the same position, so it is not necessary to install the above-mentioned rotating machine. 结构。 Structure.

電漿處理(電漿洗淨)有大氣壓(或常壓)電漿處理、及低壓低溫電漿處理。 Plasma treatment (plasma cleaning) includes atmospheric (or atmospheric) plasma treatment and low-pressure and low-temperature plasma treatment.

於常壓電漿處理中,向氣體施加放電能量,於常壓下進行游離而使電漿產生。作為其特徵,可列舉:因常壓製程故無需設為真空,且設備簡單,生產性亦較高。作為方式,主要有稀有氣體系常壓電漿、與控制施加電壓而進行輝光放電之脈衝方式常壓電漿,可使用上述方式中之任一種。 In the treatment of ordinary piezoelectric plasma, the discharge energy is applied to the gas, and the plasma is released under normal pressure. As its characteristics, there is no need to set a vacuum due to the normal pressing process, and the equipment is simple and the productivity is high. As the method, there are mainly a rare gas system normal piezoelectric slurry and a pulse type normal piezoelectric slurry that controls the application of a voltage to perform a glow discharge, and any of the above methods can be used.

於低壓低溫電漿處理中,使玻璃積層體通過可減壓之低溫電漿處理裝置內,使裝置內成為無機氣體之氛圍,於將壓力保持為0.001~10Torr、較佳為0.01~1Torr之狀態下向電極間施加頻率50Hz~13.6MHz之電力。藉由施加0.1~50kW之電力而進行輝光放電,而使無機氣體之低溫電漿產生。於其中設置玻璃積層體而對支持基板進行處理。於連續對玻璃積層體進行處理之情形時,一面使玻璃積層體依序移動一面對表面進行電漿處理。作為該無機氣體,可使用氦氣、氖氣、氬氣等稀有氣體、及氧氣、氮氣、空氣、二氧化碳氣體、氨氣等。該等氣體並不限於1種,亦可為2種以上氣體之混合物。 In the low-pressure and low-temperature plasma treatment, the glass laminate is passed through a pressure-reducing, low-temperature plasma treatment device, so that the inside of the device becomes an inorganic gas atmosphere, and the pressure is maintained at 0.001 to 10 Torr, preferably 0.01 to 1 Torr. Apply power between 50Hz to 13.6MHz between the electrodes. Glow discharge is performed by applying electric power of 0.1 to 50 kW, so that a low-temperature plasma of inorganic gas is generated. A glass laminate is disposed therein to process the support substrate. In the case where the glass laminated body is continuously processed, the glass laminated body is sequentially moved while facing the surface for plasma treatment. As the inorganic gas, rare gases such as helium, neon, and argon, and oxygen, nitrogen, air, carbon dioxide gas, ammonia gas, and the like can be used. These gases are not limited to one type, and may be a mixture of two or more types of gases.

於常壓電漿處理及低壓低溫電漿處理中之任一種處理中,電漿處理時間較佳為0.1~1,000秒,更佳為1~100秒。 In any one of the ordinary piezoelectric treatment and the low-pressure and low-temperature plasma treatment, the plasma treatment time is preferably 0.1 to 1,000 seconds, and more preferably 1 to 100 seconds.

所謂UV臭氧處理,係照射UV(紫外線),使空氣中之氧變為臭氧,藉由該臭氧及紫外線而使被照射面潔淨化之處理。 The so-called UV-ozone treatment is a treatment in which UV (ultraviolet rays) is irradiated to change oxygen in the air into ozone, and the surface to be irradiated is cleaned by the ozone and ultraviolet rays.

UV光源只要可藉由UV照射而使氧變為臭氧,則無特別限制。作為UV光源,可列舉低壓水銀燈。低壓水銀燈產生185nm與254nm之UV光,185nm線可使氧變為臭氧。照射時之照度係根據所使用之光源而不同,通常使用數十~數百mW/cm2者。又,亦可藉由集光或擴散而變更照度。照射時間係根據燈之照度及未處理層之種類而不同, 通常為1分鐘~24小時。處理溫度通常為10~200℃。又,UV之照射量(即,紫外線量)通常為1mJ/cm2以上,較佳為1~100000mJ/cm2,更佳為10~100000mJ/cm2The UV light source is not particularly limited as long as it can change oxygen to ozone by UV irradiation. Examples of the UV light source include a low-pressure mercury lamp. Low-pressure mercury lamps produce UV light at 185nm and 254nm. The 185nm line turns oxygen into ozone. The illuminance at the time of irradiation differs depending on the light source used, and usually several tens to hundreds of mW / cm 2 are used. It is also possible to change the illuminance by collecting or diffusing light. The irradiation time varies depending on the illuminance of the lamp and the type of the untreated layer, and is usually 1 minute to 24 hours. The processing temperature is usually 10 ~ 200 ℃. Further, the UV irradiation amount (i.e., an amount of ultraviolet rays) is generally 1mJ / cm 2 or more, preferably 1 ~ 100000mJ / cm 2, more preferably 10 ~ 100000mJ / cm 2.

藉由實施上述步驟S106,而將附著於支持基板10之第2主面10a側之附著物去除。 By performing step S106 described above, the adhered matter attached to the second main surface 10a side of the support substrate 10 is removed.

於上述步驟S106之處理前後之支持基板10之第2主面10a之水接觸角的差(處理前之水接觸角-處理後之水接觸角)較佳為30度以上,更佳為50度以上。上限並無特別限制,通常為70度以下。 The difference in the water contact angle (water contact angle before processing-water contact angle after processing) of the second main surface 10a of the support substrate 10 before and after the processing in step S106 is preferably 30 degrees or more, and more preferably 50 degrees the above. The upper limit is not particularly limited, and is usually 70 degrees or less.

<<第2態樣>> << 2nd aspect >>

圖5係表示本發明之玻璃積層體之製造方法之第2態樣中的製造步驟之流程圖。如圖5所示般,第2態樣依序包含:加熱步驟S102、表面處理步驟S106、及積層步驟S104。 Fig. 5 is a flowchart showing manufacturing steps in the second aspect of the method for manufacturing a glass laminate according to the present invention. As shown in FIG. 5, the second aspect sequentially includes a heating step S102, a surface treatment step S106, and a lamination step S104.

與上述之第1態樣相比,除表面處理步驟S106之實施順序不同以外,係與上述之第1態樣之各步驟與其處理之方法相同。更具體而言,於第2態樣中,於加熱步驟S102中製造附樹脂層之支持基板,繼而對該附樹脂層之支持基板中之支持基板之第2主面側實施上述之表面處理(例如,電暈處理),其後,於附樹脂層之支持基板中之聚矽氧樹脂層上積層玻璃基板而獲得玻璃積層體。於本實施態樣中亦可獲得所需之玻璃積層體。 Compared with the first aspect described above, except that the implementation order of the surface treatment step S106 is different, the steps of the first aspect described above are the same as the method of processing. More specifically, in the second aspect, the supporting substrate with a resin layer is manufactured in the heating step S102, and then the above-mentioned surface treatment is performed on the second main surface side of the supporting substrate in the supporting substrate with the resin layer ( For example, corona treatment), and thereafter, a glass substrate is laminated on a polysiloxane resin layer in a support substrate with a resin layer to obtain a glass laminate. The required glass laminate can also be obtained in this embodiment.

再者,若將上述之第1態樣與第2態樣進行比較,則較佳為第1態樣。於第1態樣之情形時,因於形成聚矽氧樹脂層後且於表面處理步驟S106前積層玻璃基板,故而雜質難以附著於聚矽氧樹脂層上,而玻璃基板之密接性更優異。 Furthermore, if the first aspect described above is compared with the second aspect, the first aspect is preferred. In the case of the first aspect, since the glass substrate is laminated after the polysiloxane resin layer is formed and before the surface treatment step S106, it is difficult for impurities to adhere to the polysiloxane resin layer, and the adhesion of the glass substrate is more excellent.

使用於上述之第1態樣及第2態樣中所獲得之玻璃積層體,而製造電子裝置(包含玻璃基板與電子裝置用構件之附構件之玻璃基板)。又,視需要,對玻璃積層體之玻璃基板實施研磨處理。 The glass laminates obtained in the first aspect and the second aspect described above are used to manufacture an electronic device (a glass substrate including a glass substrate and a member with a member for an electronic device). If necessary, the glass substrate of the glass laminate is subjected to a polishing treatment.

以下,對該等研磨步驟、及電子裝置製造步驟(構件形成步驟及分離步驟)之程序進行詳述。 Hereinafter, the procedures of these polishing steps and electronic device manufacturing steps (member formation steps and separation steps) will be described in detail.

<研磨步驟> <Grinding step>

研磨步驟係對所獲得之玻璃積層體100中之玻璃基板20之第2主面20b進行研磨之步驟。藉由設置本步驟,可將玻璃基板20之第2主面20b之微小之凹凸及損傷去除,而使供形成電子裝置用構件之面之平坦性提高。因此,可提高作為製品之電子裝置之可靠性。該效果對本發明中所使用之厚度為0.3mm以下之玻璃基板明顯。其原因在於:厚度0.3mm以下之玻璃基板難以單獨地進行研磨,從而難以於用於玻璃積層體100之製作前預先進行研磨。 The polishing step is a step of polishing the second main surface 20 b of the glass substrate 20 in the obtained glass laminate 100. By providing this step, the minute unevenness and damage of the second main surface 20b of the glass substrate 20 can be removed, and the flatness of the surface on which the member for an electronic device is formed can be improved. Therefore, the reliability of the electronic device as a product can be improved. This effect is significant for a glass substrate having a thickness of 0.3 mm or less used in the present invention. The reason is that it is difficult to individually polish a glass substrate having a thickness of 0.3 mm or less, and it is difficult to perform polishing in advance before manufacturing the glass laminate 100.

研磨之方法並無特別限制,可採用公知之方法,可使用機械研磨(物理研磨)或化學性研磨(化學研磨)。作為機械研磨,可使用吹送陶瓷研磨粒而進行研磨之噴砂方法、使用研磨片或磨石之研磨、及併用研磨粒與化學溶劑之化學機械研磨(CMP:Chemical Mechanical Polishing)法等。 The method of polishing is not particularly limited, and a known method can be adopted, and mechanical polishing (physical polishing) or chemical polishing (chemical polishing) can be used. As the mechanical polishing, a sandblasting method in which ceramic abrasive particles are blown and polished, a polishing method using a polishing sheet or a grindstone, and a chemical mechanical polishing (CMP) method in which abrasive particles and a chemical solvent are used in combination can be used.

又,作為化學研磨(亦有稱為濕式蝕刻之情況),可使用如下方法,即使用藥液對玻璃基板之表面進行研磨。 In addition, as chemical polishing (also referred to as wet etching), a method may be used in which the surface of the glass substrate is polished using a chemical solution.

其中,就研磨後之玻璃基板20之第2主面20b之平坦性及潔淨度更高之方面而言,較佳為化學機械研磨。再者,作為化學機械研磨所使用之研磨粒,可使用氧化鈰等公知之研磨粒。 Among them, chemical mechanical polishing is preferred in terms of higher flatness and cleanliness of the second main surface 20b of the glass substrate 20 after polishing. In addition, as the abrasive grains used in chemical mechanical polishing, known abrasive grains such as cerium oxide can be used.

<電子裝置(附構件之玻璃基板)及其製造方法> <Electronic device (glass substrate with member) and manufacturing method thereof>

本發明中,使用上述之玻璃積層體而製造包含玻璃基板與電子裝置用構件之電子裝置(附構件之玻璃基板)。 In the present invention, an electronic device (a glass substrate with a member) including a glass substrate and a member for an electronic device is manufactured using the aforementioned glass laminate.

該電子裝置之製造方法並無特別限定,就電子裝置之生產性優異之方面而言,較佳為如下方法,即於上述玻璃積層體中之玻璃基板上形成電子裝置用構件而製造附電子裝置用構件之積層體,以聚矽氧 樹脂層之玻璃基板側界面為剝離面,自所獲得之附電子裝置用構件之積層體分離為電子裝置與附樹脂層之支持基板。 The manufacturing method of the electronic device is not particularly limited. In terms of excellent productivity of the electronic device, a method is preferred in which a member for an electronic device is formed on a glass substrate in the glass laminate described above to manufacture the electronic device. Polysilicon The glass substrate side interface of the resin layer is a peeling surface, and it is separated from the obtained laminated body with a member for an electronic device into a support substrate with an electronic device and a resin layer.

以下,將於上述玻璃積層體中之玻璃基板上形成電子裝置用構件而製造附電子裝置用構件之積層體的步驟稱為構件形成步驟,將以聚矽氧樹脂層之玻璃基板側界面為剝離面,自附電子裝置用構件之積層體分離為電子裝置與附樹脂層之支持基板之步驟稱為分離步驟。 Hereinafter, the step of forming an electronic device member on the glass substrate in the above-mentioned glass laminated body to produce a laminated body with an electronic device member is referred to as a member forming step, and the glass substrate side interface of the silicone resin layer is peeled On the other hand, the step of separating the laminated body from a member for attaching an electronic device into an electronic device and a supporting substrate with a resin layer is called a separating step.

以下,針對各步驟中所使用之材料及程序進行詳述。 The materials and procedures used in each step are described in detail below.

(構件形成步驟) (Member formation step)

構件形成步驟係於上述積層步驟中所獲得之玻璃積層體100中之玻璃基板20上形成電子裝置用構件之步驟。更具體而言,如圖6(A)所示般於玻璃基板20之第2主面20b(露出表面)上形成電子裝置用構件22而獲得附電子裝置用構件之積層體24。 The component formation step is a step of forming a component for an electronic device on the glass substrate 20 in the glass laminate 100 obtained in the above-mentioned lamination step. More specifically, as shown in FIG. 6 (A), a member 22 for an electronic device is formed on the second main surface 20b (exposed surface) of the glass substrate 20 to obtain a laminated body 24 with a member for an electronic device.

首先,針對本步驟中所使用之電子裝置用構件22進行詳述,其後對步驟之程序進行詳述。 First, the electronic device member 22 used in this step will be described in detail, and then the procedure of the step will be described in detail.

(電子裝置用構件(功能性元件)) (Member (functional element) for electronic device)

電子裝置用構件22係形成於玻璃積層體100中之玻璃基板20上,且係構成電子裝置之至少一部分之構件。更具體而言,作為電子裝置用構件22,可列舉顯示裝置用面板、太陽電池、薄膜2次電池、或表面形成有電路之半導體晶圓等電子零件等所使用之構件(例如顯示裝置用構件、太陽電池用構件、薄膜2次電池用構件、電子零件用電路)。 The electronic device member 22 is a member formed on the glass substrate 20 in the glass laminate 100 and constitutes at least a part of the electronic device. More specifically, as the member 22 for an electronic device, members used in electronic parts such as a panel for a display device, a solar cell, a thin film secondary battery, or a semiconductor wafer with a circuit formed on the surface (for example, a member for a display device) , Solar battery components, thin film secondary battery components, and electronic component circuits).

例如,作為太陽電池用構件,就矽型而言,可列舉正極之氧化錫等透明電極、由p層/i層/n層表示之矽層、及負極之金屬等,除上述以外,亦可列舉對應於化合物型、色素增感型、量子點型等之各種構件等。 For example, as the solar cell member, the silicon type includes transparent electrodes such as tin oxide of a positive electrode, a silicon layer represented by a p-layer / i-layer / n-layer, and a metal of a negative electrode. Various members corresponding to a compound type, a dye-sensitized type, a quantum dot type, and the like are listed.

又,作為薄膜2次電池用構件,對於鋰離子型而言,可列舉正極 及負極之金屬或金屬氧化物等透明電極、電解質層之鋰化合物、集電層之金屬、作為密封層之樹脂等,除上述以外,亦可列舉對應於鎳氫型、聚合物型、陶瓷電解質型等之各種構件等。 Moreover, as a member for a thin film secondary battery, for a lithium ion type, a positive electrode can be mentioned In addition to the above, transparent electrodes such as metals and metal oxides, lithium compounds in the electrolyte layer, metals in the current collector layer, and resins used as sealing layers can be used in addition to the nickel-hydrogen, polymer, and ceramic electrolytes. Various components such as models.

又,作為電子零件用電路,對於CCD(Charge Coupled Device,電荷耦合元件)或CMOS(Complementary Metal Oxide Semiconductor,互補金氧半導體)而言,可列舉導電部之金屬、絕緣部之氧化矽或氮化矽等,除上述以外,亦可列舉對應於壓力感測器、加速度感測器等各種感測器或剛性印刷基板、軟性印刷基板、剛性軟性印刷基板等之各種構件等。 In addition, as a circuit for an electronic component, for a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), a metal of a conductive portion, silicon oxide or nitride of an insulating portion can be cited. In addition to the above, silicon and the like may include various members corresponding to various sensors such as a pressure sensor and an acceleration sensor, or various components such as a rigid printed circuit board, a flexible printed circuit board, and a rigid flexible printed circuit board.

(步驟之順序) (Order of steps)

上述之附電子裝置用構件之積層體24之製造方法並無特別限定,視電子裝置用構件之構成構件之種類,利用先前公知之方法,於玻璃積層體100之玻璃基板20之第2主面20b上形成電子裝置用構件22。 The manufacturing method of the above-mentioned laminated body 24 with a member for an electronic device is not particularly limited, and depending on the type of the constituent member of the electronic device member, the second principal surface of the glass substrate 20 of the glass laminated body 100 is previously known by a known method. An electronic device member 22 is formed on 20b.

再者,電子裝置用構件22亦可並非最終形成於玻璃基板20之第2主面20b之構件之全部(以下稱為「全部構件」),而為全部構件之一部分(以下稱為「部分構件」)。亦可將自聚矽氧樹脂層16剝離之附部分構件之玻璃基板於其後之步驟中製成附全部構件之玻璃基板(相當於下述之電子裝置)。 Furthermore, the electronic device member 22 may not be all the members (hereinafter referred to as "all members") that are finally formed on the second main surface 20b of the glass substrate 20, but may be a part of all members (hereinafter referred to as "partial members" "). The glass substrate with a part of the components peeled from the silicone resin layer 16 may also be made into a glass substrate with all the components (equivalent to the electronic device described below) in a subsequent step.

又,對於自聚矽氧樹脂層16剝離之附全部構件之玻璃基板而言,亦可於其剝離面(第1主面20a)形成其他電子裝置用構件。又,亦可將附全部構件之積層體組合,其後自附全部構件之積層體將附樹脂層之支持基板18剝離而製造電子裝置。進而,亦可使用2片附全部構件之積層體而組裝電子裝置,其後自附全部構件之積層體將2片附樹脂層之支持基板18剝離,而製造具有2片玻璃基板之電子裝置。 In addition, for a glass substrate with all the members peeled from the silicone resin layer 16, other members for electronic devices may be formed on the peeling surface (first main surface 20 a). Alternatively, the laminated body with all the members may be combined, and then the support substrate 18 with the resin layer may be peeled off from the laminated body with all the members to manufacture an electronic device. Furthermore, an electronic device may be assembled using two laminated bodies with all components, and then the two supporting substrates 18 with resin layers may be peeled off from the laminated body with all components, and an electronic device having two glass substrates may be manufactured.

例如,若以製造OLED之情形為例,則為了於玻璃積層體100之 玻璃基板20之與聚矽氧樹脂層16側相反側之表面上(相當於玻璃基板20之第2主面20b)形成有機EL構造體,而進行如下各種層形成或處理,即形成透明電極;進而於形成有透明電極之面上蒸鍍電洞注入層.電洞傳輸層.發光層.電子傳輸層等;形成背面電極;及使用密封板進行密封等。作為該等層形成或處理,具體而言,例如可列舉:成膜處理、蒸鍍處理、密封板之接著處理等。 For example, if the case of manufacturing an OLED is taken as an example, An organic EL structure is formed on the surface of the glass substrate 20 opposite to the polysiloxane layer 16 side (equivalent to the second main surface 20b of the glass substrate 20), and the following various layers are formed or processed to form a transparent electrode; Further, a hole injection layer is evaporated on the surface where the transparent electrode is formed. Hole transmission layer. Light emitting layer. Electron transport layer, etc .; forming a back electrode; and sealing using a sealing plate. Specific examples of such layer formation or treatment include a film formation treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate.

又,例如於製造TFT-LCD之情形時,該製造方法具有TFT形成步驟、CF形成步驟、及貼合步驟等各種步驟,上述TFT形成步驟係於玻璃積層體100之玻璃基板20之第2主面20b上,使用抗蝕液,於藉由CVD(Chemical vapor deposition,化學氣相沈積)法及濺鍍法等通常之成膜法而形成之金屬膜及金屬氧化膜等進行圖案形成而形成薄膜電晶體(TFT);上述CF形成步驟係於另一玻璃積層體100之玻璃基板20之第2主面20b上,將抗蝕液用於圖案形成而形成彩色濾光片(CF);貼合步驟係將TFT形成步驟中所獲得之附TFT之積層體與CF形成步驟中所獲得之附CF之積層體進行積層。 In the case of manufacturing a TFT-LCD, for example, the manufacturing method includes various steps such as a TFT forming step, a CF forming step, and a bonding step. The TFT forming step is a second step of the glass substrate 20 of the glass laminate 100. A thin film is formed on the surface 20b by patterning a metal film, a metal oxide film, and the like formed by a common film forming method such as a CVD (Chemical Vapor Deposition) method and a sputtering method using a resist solution. Transistor (TFT); The above CF formation step is on the second main surface 20b of the glass substrate 20 of another glass laminate 100, and a resist is used for pattern formation to form a color filter (CF); The step is to laminate the laminated body with TFT obtained in the TFT formation step and the laminated body with CF obtained in the CF formation step.

於TFT形成步驟或CF形成步驟中,使用周知之光微影技術或蝕刻技術等而於玻璃基板20之第2主面20b形成TFT或CF。此時,可使用抗蝕液作為圖案形成用之塗佈液。 In the TFT formation step or the CF formation step, a TFT or CF is formed on the second main surface 20 b of the glass substrate 20 using a well-known photolithography technique or an etching technique or the like. In this case, a resist liquid can be used as a coating liquid for pattern formation.

再者,於形成TFT或CF前,亦可視需要而將玻璃基板20之第2主面20b洗淨。作為洗淨方法,可使用周知之乾式洗淨或濕式洗淨。 In addition, before forming the TFT or CF, the second main surface 20b of the glass substrate 20 may be cleaned if necessary. As a washing method, a well-known dry washing or wet washing can be used.

於貼合步驟中,使附TFT之積層體之薄膜電晶體形成面、與附CF之積層體之彩色濾光片形成面對向,並使用密封劑(例如,單元形成用紫外線硬化型密封劑)進行貼合。其後,向由附TFT之積層體與附CF之積層體所形成之單元內注入液晶材。作為注入液晶材之方法,例如有減壓注入法、滴加注入法。 In the bonding step, the thin-film transistor-forming surface of the multilayer body with TFT and the color filter of the multilayer body with CF are faced, and a sealant (for example, a UV-curable sealant for cell formation) is used. ). Thereafter, a liquid crystal material is injected into a cell formed by the laminated body with the TFT and the laminated body with the CF. Examples of the method for injecting the liquid crystal material include a reduced-pressure injection method and a dropwise injection method.

(分離步驟) (Separation step)

分離步驟係如圖6(B)所示般,以聚矽氧樹脂層16與玻璃基板20之界面為剝離面,自上述構件形成步驟中所獲得之附電子裝置用構件之積層體24分離為積層有電子裝置用構件22之玻璃基板20(電子裝置)、與附樹脂層之支持基板18,而獲得包含電子裝置用構件22及玻璃基板20之電子裝置26的步驟。 As shown in FIG. 6 (B), the separation step uses the interface between the polysiloxane resin layer 16 and the glass substrate 20 as a peeling surface, and separates from the laminated body 24 with a member for an electronic device obtained in the above-mentioned member forming step into A step of laminating a glass substrate 20 (electronic device) having a member 22 for electronic devices and a supporting substrate 18 with a resin layer to obtain an electronic device 26 including the member 22 for electronic devices and the glass substrate 20.

於剝離時之玻璃基板20上之電子裝置用構件22為必需之全部構成構件之形成之一部分的情形時,亦可於分離後,將剩餘之構成構件形成於玻璃基板20上。 In the case where the electronic device member 22 on the glass substrate 20 at the time of peeling is a part of all necessary constituent members, the remaining constituent members may be formed on the glass substrate 20 after separation.

將玻璃基板20與附樹脂層之支持基板18進行剝離之方法並無特別限定。具體而言,例如可向玻璃基板20與聚矽氧樹脂層16之界面插入銳利之刃具狀者,賦予剝離之起點後,吹送水與壓縮空氣之混合流體而進行剝離。較佳為以附電子裝置用構件之積層體24之支持基板10成為上側,電子裝置用構件22側成為下側之方式設置於壓盤上,將電子裝置用構件22側真空吸附於壓盤上(於兩面積層有支持基板之情形時依序進行),於該狀態下首先使刃具侵入玻璃基板20-聚矽氧樹脂層16界面。然後,其後利用複數個真空吸附墊吸附支持基板10側,自插入刃具處附近開始依序使真空吸附墊上升。藉此於聚矽氧樹脂層16與玻璃基板20之界面或聚矽氧樹脂層16之凝聚破損面形成空氣層,該空氣層擴展至界面或凝聚破損面之整面,而可容易地剝離支持基板10。 The method of peeling the glass substrate 20 and the support substrate 18 with a resin layer is not specifically limited. Specifically, for example, a sharp blade can be inserted into the interface between the glass substrate 20 and the silicone resin layer 16 to give a starting point for peeling, and then blow off a mixed fluid of water and compressed air. Preferably, the supporting substrate 10 of the laminated body 24 with the member for the electronic device is set on the upper side, and the side of the member for the electronic device 22 is set on the lower plate, and the side of the member 22 for the electronic device is vacuum-adsorbed on the platen. (Sequentially when the two-area layer has a supporting substrate), in this state, the cutting tool is first made to penetrate the interface of the glass substrate 20-polysiloxane layer 16. Then, the support substrate 10 side is adsorbed by a plurality of vacuum adsorption pads, and the vacuum adsorption pads are sequentially raised from the vicinity of the position where the cutting tool is inserted. Thereby, an air layer is formed at the interface between the silicone resin layer 16 and the glass substrate 20 or the condensation damage surface of the silicone resin layer 16, and the air layer extends to the entire surface of the interface or the condensation damage surface, and can be easily peeled and supported. Substrate 10.

又,支持基板10可與新的玻璃基板進行積層而製造本發明之玻璃積層體100。 The support substrate 10 can be laminated with a new glass substrate to produce the glass laminate 100 of the present invention.

再者,於自附電子裝置用構件之積層體24分離電子裝置26時,可藉由控制利用離子化器之吹送或濕度,而更為抑制聚矽氧樹脂層16之碎片靜電吸附於電子裝置26之情況。 Furthermore, when the electronic device 26 is separated from the laminated body 24 with the components for the electronic device, by controlling the blowing or humidity using the ionizer, it is possible to further suppress the electrostatic adsorption of the fragments of the silicone resin layer 16 on the electronic device. 26 case.

上述之電子裝置26之製造方法較佳用於如行動電話或PDA(Personal Digital Assistant,個人數位助理)之移動終端所使用之 小型顯示裝置之製造。顯示裝置主要有LCD或OLED,作為LCD,包括TN(Twisted Nematic,扭轉向列)型、STN(Super Twisted Nematic,超扭轉向列)型、FE(Ferroelectric,鐵電)型、TFT(Thin-film transistor,薄膜電晶體)型、MIM(Metal-Insulator-Metal,金屬-絕緣層-金屬)型、IPS(In-Plane Switching,橫向電場效應)型、VA(Vertical Aligned,垂直配向)型等。基本上於被動驅動型、主動驅動型中之任一種顯示裝置之情形時亦可應用。 The manufacturing method of the electronic device 26 described above is preferably applied to a mobile terminal such as a mobile phone or a PDA (Personal Digital Assistant). Manufacturing of small display devices. Display devices mainly include LCDs or OLEDs. As LCDs, they include TN (Twisted Nematic), STN (Super Twisted Nematic), FE (Ferroelectric), and TFT (Thin-film). A transistor (thin film transistor) type, a MIM (Metal-Insulator-Metal) type, an IPS (In-Plane Switching) type, a VA (Vertical Aligned) type, and the like. Basically, it can also be applied in the case of any one of a passive driving type and an active driving type display device.

作為利用上述方法製造之電子裝置26,可列舉:具有玻璃基板與顯示裝置用構件之顯示裝置用面板、具有玻璃基板與太陽電池用構件之太陽電池、具有玻璃基板與薄膜2次電池用構件之薄膜2次電池、具有玻璃基板與電子裝置用構件之電子零件等。作為顯示裝置用面板,包括液晶面板、有機EL面板、電漿顯示器面板、場發射面板等。 Examples of the electronic device 26 manufactured by the above method include a panel for a display device having a glass substrate and a member for a display device, a solar cell having a member for a glass substrate and a solar cell, and a member for a secondary battery having a glass substrate and a thin film. Thin-film secondary batteries, electronic components including glass substrates, and components for electronic devices. The display device panel includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

[實施例] [Example]

以下,藉由實施例等而對本發明具體地進行說明,但本發明並不受該等例限定。 Hereinafter, the present invention will be specifically described using examples and the like, but the present invention is not limited to these examples.

於以下之實施例及比較例中,使用由無鹼硼矽酸玻璃構成之玻璃板(長度880mm、寬度680mm、板厚0.2mm,線膨脹係數38×10-7/℃,旭硝子公司製造,商品名「AN100」)作為玻璃基板。又,作為支持基板,使用相同之由無鹼硼矽酸玻璃構成之玻璃板(長度920mm、寬度730mm、板厚0.5mm,線膨脹係數38×10-7/℃,旭硝子公司製造,商品名「AN100」)。 In the following examples and comparative examples, a glass plate (length 880 mm, width 680 mm, plate thickness 0.2 mm, linear expansion coefficient 38 × 10 -7 / ° C) made of alkali-free borosilicate glass was used. "AN100") as a glass substrate. And, as a supporting substrate, formed of the same alkali-free glass, boron silicate glass plate (length 920mm, width 730mm, thickness 0.5mm, a linear expansion coefficient 38 × 10 -7 / ℃, Asahi Glass Co., trade name " AN100 ").

<實施例1> <Example 1>

首先,利用鹼性水溶液將支持基板之表面洗淨,之後利用純水進行洗淨而潔淨化。 First, the surface of the support substrate is cleaned with an alkaline aqueous solution, and then cleaned with pure water.

繼而,利用模具塗佈機(塗佈速度:40mm/s,吐出量:8ml), 於支持基板之第1主面上塗佈下述之溶液S,將包含未硬化之交聯性有機聚矽氧烷之層(硬化性聚矽氧組合物層)設置於支持基板上,而獲得附硬化性層之支持基板(塗佈量20g/m2)。 Next, using a die coater (coating speed: 40 mm / s, discharge amount: 8 ml), the following solution S was coated on the first main surface of the support substrate to contain uncured cross-linked organic polysilicon An oxyalkane layer (curable polysiloxane composition layer) is provided on a support substrate, and a support substrate with a curable layer (a coating amount of 20 g / m 2 ) is obtained.

(溶液S) (Solution S)

將作為成分(A)之直鏈狀乙烯基甲基聚矽氧烷(Azmax公司製造,商品名「VDT-127」,25℃下之黏度:700-800cP(厘泊),有機聚矽氧烷1mol中之乙烯基之mol%:0.325)、作為成分(B)之直鏈狀甲基氫化聚矽氧烷(Azmax公司製造,商品名「HMS-301」,25℃下之黏度:25-35cP(厘泊),1分子內之鍵結於矽原子之氫原子之數量:8個)以全部乙烯基與鍵結於矽原子之全部氫原子的莫耳比(氫原子/乙烯基)成為0.9之方式進行混合,相對於該矽氧烷混合物100重量份,混合作為成分(C)之下述式(1)所示之具有乙炔系不飽和基之矽化合物(沸點:120℃)1質量份。 As a component (A), a linear vinyl methyl polysiloxane (manufactured by Azmax, trade name "VDT-127", viscosity at 25 ° C: 700-800 cP (centipoise), organic polysiloxane Mol% of vinyl group in 1 mol: 0.325), linear methyl hydride polysiloxane as component (B) (manufactured by Azmax, trade name "HMS-301", viscosity at 25 ° C: 25-35 cP (Centipoise), the number of hydrogen atoms bonded to silicon atoms in one molecule: 8) The molar ratio of all vinyl groups to all hydrogen atoms bonded to silicon atoms (hydrogen atom / vinyl group) becomes 0.9 The mixture was mixed in such a manner that 1 part by mass of a silicon compound having an acetylene-based unsaturated group (boiling point: 120 ° C.) represented by the following formula (1) as a component (C) was mixed with 100 parts by weight of the siloxane mixture. .

HC≡C-C(CH3)2-O-Si(CH3)3 式(1) HC≡CC (CH 3 ) 2 -O-Si (CH 3 ) 3 Formula (1)

繼而,相對於成分(A)與成分(B)與成分(C)之合計量,以鉑換算計鉑金屬濃度成為100ppm之方式添加鉑系觸媒(Shin-Etsu Silicones股份有限公司製造,商品名「CAT-PL-56」)而獲得有機聚矽氧烷組合物之混合液。進而,相對於所獲得之混合液100重量份,添加IP solvent 2028(初餾點:200℃,出光興產製造)150重量份而獲得混合溶液。 Next, a platinum-based catalyst (made by Shin-Etsu Silicones Co., Ltd., trade name) is added so that the platinum metal concentration becomes 100 ppm based on the total amount of the component (A), the component (B), and the component (C). "CAT-PL-56") to obtain a mixed solution of an organic polysiloxane composition. Furthermore, 150 parts by weight of IP solvent 2028 (initial boiling point: 200 ° C, manufactured by Idemitsu Kosan Co., Ltd.) was added to 100 parts by weight of the obtained mixed solution to obtain a mixed solution.

繼而,於設置於加熱處理裝置內之底部之複數個支持銷之頂端載置上述附硬化性層之支持基板。再者,支持銷之頂端係與附硬化性層之支持基板中之支持基板之第2主面側(與有硬化性聚矽氧組合物層之側相反側)的表面接觸,且於支持基板之第2主面側存在未與支持銷接觸之區域。 Then, the support substrate with a hardenable layer is placed on the top of a plurality of support pins provided at the bottom of the heat treatment device. In addition, the top end of the support pin is in contact with the surface on the second main surface side of the support substrate (the side opposite to the side with the curable polysiloxane composition layer) of the support substrate with a hardening layer, and is on the support substrate. There is a region not in contact with the support pin on the second main surface side.

於加熱處理裝置內,於附硬化性層之支持基板之硬化性聚矽氧組合物層之上部配置加熱板,藉由該加熱板,於200℃下對附硬化性 層之支持基板加熱(預烘烤加熱)3分鐘。 In the heat treatment device, a heating plate is arranged on the upper part of the hardening polysilicone composition layer of the supporting substrate with a hardening layer, and the hardening is performed at 200 ° C with the heating plate. The support substrate of the layer was heated (pre-baking heating) for 3 minutes.

繼而,針對上述加熱處理後之附硬化性層之支持基板,進而於250℃下實施1450秒鐘之加熱處理(後烘烤處理),而於支持基板之第1主面形成厚度8μm之聚矽氧樹脂層。 Next, for the support substrate with a hardening layer after the above-mentioned heat treatment, a heating treatment (post-baking treatment) was performed at 250 ° C. for 1450 seconds, and a polysilicon with a thickness of 8 μm was formed on the first main surface of the support substrate. Oxygen resin layer.

其後,於室溫下,藉由大氣壓加壓而將玻璃基板與支持基板上之聚矽氧樹脂層面進行貼合而獲得玻璃積層體A。 Thereafter, the glass substrate and the polysiloxane resin layer on the support substrate were bonded by atmospheric pressure at room temperature to obtain a glass laminate A.

於所獲得之玻璃積層體A中,支持基板與玻璃基板係於與聚矽氧樹脂層之間不產生氣泡之情況下進行密接,沒有變形缺陷,平滑性亦良好。再者,於玻璃積層體A中,聚矽氧樹脂層與支持基板之層之界面之剝離強度大於玻璃基板之層與聚矽氧樹脂層之界面的剝離強度。 In the obtained glass laminated body A, the support substrate and the glass substrate were adhered to each other without generating bubbles between them and the silicone resin layer, without deformation defects, and smoothness was also good. Furthermore, in the glass laminate A, the peel strength at the interface between the silicone resin layer and the layer supporting the substrate is greater than the peel strength at the interface between the glass substrate layer and the silicone layer.

繼而,針對所獲得之玻璃積層體A中之支持基板之第2主面,實施電暈處理(電力1kW,處理速度4m/min)。 Then, the second main surface of the support substrate in the obtained glass laminate A was subjected to a corona treatment (electric power: 1 kW, processing speed: 4 m / min).

對玻璃積層體A中之支持基板之第2主面之電暈處理前後的水接觸角進行測定,結果為電暈處理前為70度,電暈處理後為5度。自該等測定結果確認如下情況,即藉由電暈處理,從而附著於支持基板之第2主面側之聚矽氧樹脂被去除。 The water contact angle before and after the corona treatment of the second main surface of the supporting substrate in the glass laminate A was measured, and it was 70 degrees before the corona treatment and 5 degrees after the corona treatment. From these measurement results, it was confirmed that the silicone resin adhered to the second main surface side of the support substrate was removed by corona treatment.

(剝離評價) (Peel evaluation)

以實施過電暈處理之玻璃積層體A中之支持基板與胺基甲酸酯製之台墊接觸之方式將該玻璃積層體A載置於台墊上。繼而,將玻璃積層體A以100g/cm2壓接於台墊120秒鐘。壓接後,一面向支持基板與台墊之間吹送空氣與水,一面進行兩者之剝離,結果可剝離。 The glass laminate A was placed on a table mat in such a manner that a supporting substrate in the glass laminate A subjected to corona treatment was brought into contact with a urethane-made table mat. Then, the glass laminated body A was crimped to the table mat at 100 g / cm 2 for 120 seconds. After the crimping, air and water are blown between the support substrate and the pad, and the two are peeled off as a result.

再者,即便於將電暈處理中之處理速度變更為1m/min、6m/min之情形時,亦可獲得與上述相同之結果。 Furthermore, even when the processing speed in the corona treatment is changed to 1 m / min and 6 m / min, the same results as described above can be obtained.

<比較例1> <Comparative example 1>

不實施電暈處理,除此以外,依據與上述實施例1相同之程序而獲得玻璃積層體B。 Except that no corona treatment was performed, a glass laminated body B was obtained according to the same procedure as in Example 1 described above.

使用玻璃積層體B代替玻璃積層體A而進行上述(剝離評價)時,無法剝離玻璃積層體B。 When the above-mentioned (peel evaluation) is performed using the glass laminate B instead of the glass laminate A, the glass laminate B cannot be peeled.

<實施例2> <Example 2>

於本例中,使用實施例1中所獲得之實施過電暈處理之玻璃積層體A而製造OLED。 In this example, the corona-treated glass laminate A obtained in Example 1 was used to manufacture an OLED.

首先,於玻璃積層體A之玻璃基板之第2主面上,藉由電漿CVD法而依序將氮化矽、氧化矽、非晶矽成膜。繼而,藉由離子摻雜裝置而將低濃度之硼注入非晶矽層,於氮氣氛圍下進行加熱處理而進行脫氫處理。繼而,藉由雷射退火裝置而進行非晶矽層之結晶化處理。繼而,藉由使用光微影法之蝕刻及離子摻雜裝置,將低濃度之磷注入非晶矽層而形成N型及P型之TFT區域。繼而,於玻璃基板之第2主面側,藉由電漿CVD法將氧化矽膜成膜而形成閘極絕緣膜後,藉由濺鍍法而將鉬成膜,藉由使用光微影法之蝕刻而形成閘極電極。繼而,藉由光微影法與離子摻雜裝置,將高濃度之硼與磷注入N型、P型各自之所需區域而形成源極區域及汲極區域。繼而,於玻璃基板之第2主面側,以利用電漿CVD法之氧化矽之成膜形成層間絕緣膜,且藉由濺鍍法將鋁成膜,及藉由使用光微影法之蝕刻而形成TFT電極。繼而,於氫環境下,進行加熱處理而進行氫化處理後,以利用電漿CVD法之氮化矽之成膜形成鈍化層。繼而,於玻璃基板之第2主面側塗佈紫外線硬化性樹脂,藉由光微影法而形成平坦化層及接觸孔。繼而,藉由濺鍍法將氧化銦錫成膜,藉由使用光微影法之蝕刻而形成像素電極。 First, on the second main surface of the glass substrate of the glass laminate A, silicon nitride, silicon oxide, and amorphous silicon were sequentially formed into a film by a plasma CVD method. Then, a low-concentration boron is implanted into the amorphous silicon layer by an ion doping device, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment. Then, the amorphous silicon layer is crystallized by a laser annealing apparatus. Then, by using a photolithography etching and ion doping device, a low concentration of phosphorus is implanted into the amorphous silicon layer to form N-type and P-type TFT regions. Next, on the second main surface side of the glass substrate, a silicon oxide film is formed by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by a sputtering method, and a photolithography method is used. The gate electrode is formed by etching. Then, a photolithography method and an ion doping device are used to inject a high concentration of boron and phosphorus into each of the N-type and P-type required regions to form a source region and a drain region. Next, on the second main surface side of the glass substrate, an interlayer insulating film is formed by the formation of silicon oxide using a plasma CVD method, and aluminum is formed by a sputtering method, and etching by a photolithography method is used. A TFT electrode is formed. Then, in a hydrogen environment, heat treatment and hydrogenation treatment are performed, and then a passivation layer is formed by forming a silicon nitride film by a plasma CVD method. Next, an ultraviolet curable resin was applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole were formed by a photolithography method. Then, indium tin oxide was formed into a film by a sputtering method, and a pixel electrode was formed by etching using a photolithography method.

繼而,於玻璃基板之第2主面側,藉由蒸鍍法,依序將作為電洞注入層之4,4',4"-三(3-甲基苯基苯基胺基)三苯胺、作為電洞傳輸層之雙[(N-萘基)-N-苯基]聯苯胺、作為發光層之於8-羥喹啉鋁錯合物(Alq3)中混合有2,6-雙[4-[N-(4-甲氧基苯基)-N-苯基]胺基苯乙烯基]萘-1,5-二腈(BSN-BCN)40體積%者、及作為電子傳輸層之Alq3成膜。繼 而,藉由濺鍍法將鋁成膜,藉由使用光微影法之蝕刻形成對向電極。繼而,於玻璃基板之第2主面側,隔著紫外線硬化型之接著層而貼合另一片玻璃基板而進行密封。藉由上述程序而於玻璃基板上形成有機EL構造體。玻璃基板上具有有機EL構造體之玻璃積層體A(以下,稱為面板A)為本發明之附電子裝置用構件之積層體。 Next, on the second main surface side of the glass substrate, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was sequentially injected as a hole injection layer by a vapor deposition method. , Bis [(N-naphthyl) -N-phenyl] benzidine as a hole transport layer, and 2,6-bis as a light emitting layer in 8-hydroxyquinoline aluminum complex (Alq 3 ) [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-1,5-dinitrile (BSN-BCN) at 40% by volume, and as an electron transport layer Alq 3 was formed into a film. Then, aluminum was formed into a film by a sputtering method, and a counter electrode was formed by etching using a photolithography method. Then, on the second main surface side of the glass substrate, an ultraviolet curing type was interposed therebetween. Next, another glass substrate is laminated and sealed. The organic EL structure is formed on the glass substrate by the above procedure. The glass laminate A (hereinafter, referred to as a panel A) having the organic EL structure on the glass substrate is The laminated body with the member for electronic devices of this invention.

繼而,使面板A之密封體側真空吸附於壓盤後,向面板A之角隅部之玻璃基板與樹脂層之界面插入厚度0.1mm之不鏽鋼製刃具,而向玻璃基板與樹脂層之界面賦予剝離之起點。然後,利用真空吸附墊吸附面板A之支持基板第1主面後,使吸附墊上升。此處,刃具之插入係與自離子化器(KEYENCE公司製造)將除電性流體向上述玻璃基板與樹脂層之界面進行吹送一起進行。繼而,自離子化器繼續向所形成之空隙吹送除電性流體,並且將水注入剝離鋒面,同時提昇真空吸附墊。其結果為,於壓盤上僅殘留形成有有機EL構造體之玻璃基板,可將附樹脂層之支持基板剝離。 Next, after vacuum-sealing the sealing body side of the panel A to the platen, a 0.1 mm thick stainless steel cutting tool was inserted into the interface between the glass substrate and the resin layer at the corner of the panel A, and the interface between the glass substrate and the resin layer was applied. The beginning of the divestiture. Then, the first main surface of the support substrate of the panel A is adsorbed by the vacuum adsorption pad, and then the adsorption pad is raised. Here, the cutting tool is inserted together with a self-ionizer (manufactured by KEYENCE) to blow a static-eliminating fluid toward the interface between the glass substrate and the resin layer. Then, the self-ionizer continued to blow the static-eliminating fluid into the formed gap, and injected water into the peeling front, while lifting the vacuum adsorption pad. As a result, only the glass substrate on which the organic EL structure was formed remained on the platen, and the supporting substrate with a resin layer could be peeled off.

繼而,使用雷射裁刀或刻劃-斷裂法將被分離之玻璃基板進行切割,分割為複數個單元後,將形成有有機EL構造體之玻璃基板與對向基板組合,實施模組形成步驟而製作OLED。以上述方式獲得之OLED於特性上沒有問題。 Next, the separated glass substrate is cut using a laser cutter or a scribe-break method, and after being divided into a plurality of units, the glass substrate on which the organic EL structure is formed is combined with a counter substrate, and a module forming step is performed. And make OLED. The OLED obtained in the above manner has no problem in characteristics.

已詳細且參照特定之實施態樣對本發明進行了說明,但對從業者而言很明確,可不脫離本發明之精神及範圍而添加各種變更或修正。 Although the present invention has been described in detail and with reference to specific embodiments, it is clear to practitioners that various changes or modifications can be added without departing from the spirit and scope of the present invention.

本申請案係基於2013年12月17日提出申請之日本專利申請2013-260453者,且將其內容作為參照併入本文中。 This application is based on Japanese Patent Application No. 2013-260453 filed on Dec. 17, 2013, and the contents are incorporated herein by reference.

Claims (9)

一種玻璃積層體之製造方法,其係依序具有支持基板、聚矽氧樹脂層及玻璃基板之玻璃積層體之製造方法,且其包含:加熱步驟,其係對包含具有第1主面及第2主面之支持基板以及配置於上述支持基板之上述第1主面上之硬化性聚矽氧組合物層的附硬化性層之支持基板自上述支持基板之上述第2主面側利用複數個支持銷進行支持,對上述附硬化性層之支持基板實施加熱處理而形成聚矽氧樹脂層;積層步驟,其係於上述加熱步驟後,於上述聚矽氧樹脂層上積層玻璃基板;及表面處理步驟,其係於上述積層步驟後,或於上述加熱步驟後且上述積層步驟前,至少對上述支持基板之上述第2主面實施選自由電暈處理、電漿處理、及UV臭氧處理所組成之群中之至少1種處理。A manufacturing method of a glass laminated body is a manufacturing method of a glass laminated body having a supporting substrate, a polysiloxane resin layer, and a glass substrate in this order, and includes a heating step, which includes a first main surface and a first A support substrate of 2 main surfaces and a support substrate with a hardening layer of a curable polysiloxane composition layer disposed on the first main surface of the support substrate use a plurality of support substrates from the second main surface side of the support substrate. The support pin supports and heat-processes the above-mentioned support substrate with a hardening layer to form a polysiloxane resin layer; a lamination step is a step of laminating a glass substrate on the polysiloxane resin layer after the above-mentioned heating step; and a surface The processing step is after the above lamination step, or after the heating step and before the lamination step, at least the second main surface of the support substrate is selected from the group consisting of corona treatment, plasma treatment, and UV ozone treatment. At least one treatment in the group. 如請求項1之玻璃積層體之製造方法,其中上述硬化性聚矽氧組合物層至少包含具有烯基之有機烯基聚矽氧烷、及具有鍵結於矽原子之氫原子之有機氫聚矽氧烷。The method for manufacturing a glass laminate according to claim 1, wherein the hardening polysiloxane composition layer includes at least an organic alkenyl polysiloxane having an alkenyl group and an organic hydrogen polymer having a hydrogen atom bonded to a silicon atom. Siloxane. 如請求項1之玻璃積層體之製造方法,其中上述加熱步驟依序包含於第1溫度下實施加熱處理之第1加熱步驟、及於較上述第1溫度高之第2溫度下實施加熱處理之第2加熱步驟。For example, the method for manufacturing a glass laminate according to claim 1, wherein the heating step includes a first heating step in which a heating treatment is performed at a first temperature, and a heating treatment in a second temperature which is higher than the first temperature. The second heating step. 如請求項2之玻璃積層體之製造方法,其中上述加熱步驟依序包含於第1溫度下實施加熱處理之第1加熱步驟、及於較上述第1溫度高之第2溫度下實施加熱處理之第2加熱步驟。For example, the method for manufacturing a glass laminate according to claim 2, wherein the heating step includes a first heating step in which a heating treatment is performed at a first temperature, and a heating treatment in a second temperature which is higher than the first temperature. The second heating step. 如請求項3之玻璃積層體之製造方法,其中上述附硬化性層之支持基板係藉由將包含硬化性聚矽氧與溶劑之硬化性聚矽氧組合物塗佈於上述支持基板之上述第1主面上而形成,且上述第1溫度滿足上述溶劑之初餾點一30℃≦第1溫度≦上述溶劑之初餾點+30℃。For example, the method for manufacturing a glass laminated body according to claim 3, wherein the support substrate with a hardening layer is formed by applying a hardening polysiloxane composition containing a hardening polysiloxane and a solvent to the first support substrate. 1 is formed on the main surface, and the first temperature satisfies the initial boiling point of the solvent—30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C. 如請求項4之玻璃積層體之製造方法,其中上述附硬化性層之支持基板係藉由將包含硬化性聚矽氧與溶劑之硬化性聚矽氧組合物塗佈於上述支持基板之上述第1主面上而形成,且上述第1溫度滿足上述溶劑之初餾點一30℃≦第1溫度≦上述溶劑之初餾點+30℃。The method for manufacturing a glass laminated body according to claim 4, wherein the support substrate with a hardening layer is formed by applying a hardening polysiloxane composition containing a hardening polysiloxane and a solvent to the above-mentioned first support substrate. 1 is formed on the main surface, and the first temperature satisfies the initial boiling point of the solvent—30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C. 如請求項1至6中任一項之玻璃積層體之製造方法,其中於上述積層步驟後實施表面處理步驟。The method for manufacturing a glass laminate according to any one of claims 1 to 6, wherein a surface treatment step is performed after the above-mentioned lamination step. 如請求項7之玻璃積層體之製造方法,其中於上述表面處理步驟中,使複數對之包含隔著上述積層步驟中所獲得之玻璃積層體被搬送之搬送路徑相對向之高壓電極與接地電極的電極對沿著上述玻璃積層體之搬送方向進行排列,將鄰接之上述電極對中之一者之高壓電極配置於隔著上述搬送路徑之一側,將另一者之高壓電極配置於隔著上述搬送路徑之另一側,且一面將上述玻璃積層體沿著上述搬送路徑進行搬送,一面向上述高壓電極施加高頻電壓,而對上述玻璃積層體實施電暈處理。For example, the method for manufacturing a glass laminated body according to claim 7, wherein in the above-mentioned surface treatment step, a plurality of pairs including the high-voltage electrode and the ground electrode which are opposed to each other through the conveying path of the glass laminated body obtained through the above-mentioned laminating step. The electrode pairs are arranged along the conveying direction of the glass laminate, and the high-voltage electrode of one of the adjacent electrode pairs is disposed on one side across the conveying path, and the other high-voltage electrode is disposed on the opposite side. The other side of the conveying path, while carrying the glass laminate along the conveying path, applies high-frequency voltage to the high-voltage electrode, and performs corona treatment on the glass laminate. 一種電子裝置之製造方法,其包含:構件形成步驟,其係於藉由如請求項1至8中任一項之製造方法製造之玻璃積層體之上述玻璃基板的表面上形成電子裝置用構件,而獲得附電子裝置用構件之積層體;及分離步驟,其係自上述附電子裝置用構件之積層體去除具有上述聚矽氧樹脂層及上述支持基板之附樹脂層之支持基板,而獲得具有上述玻璃基板與上述電子裝置用構件之電子裝置。An electronic device manufacturing method including a member forming step of forming a member for an electronic device on a surface of the above-mentioned glass substrate of a glass laminated body manufactured by the manufacturing method according to any one of claims 1 to 8, And obtaining a laminated body with a member for an electronic device; and a separation step of removing the supporting substrate having the polysiloxane resin layer and the resinous layer with the supporting substrate from the laminated body with an electronic device member, and obtaining An electronic device of the glass substrate and the member for an electronic device.
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