WO2015016113A1

WO2015016113A1 - Electronic device manufacturing method

Info

Publication number: WO2015016113A1
Application number: PCT/JP2014/069461
Authority: WO
Inventors: 純一 ▲角▼田; 研一江畑; 祥孝松山
Original assignee: 旭硝子株式会社
Priority date: 2013-07-31
Filing date: 2014-07-23
Publication date: 2015-02-05
Also published as: KR20160039192A; JPWO2015016113A1; TW201518083A; CN105432147B; CN105432147A

Abstract

This electronic device manufacturing method has a step for obtaining an electronic device by separating a silicone resin layer-laminated supporting base material and the electronic device from an electronic device member-laminated laminated body by having, as a peeling surface, an interface between a silicone resin layer and a glass substrate, said electronic device member-laminated laminated body having a supporting base material, the silicone resin layer, the glass substrate, and an electronic device member laminated therein in this order. In the electronic device manufacturing method, the silicone resin-laminated supporting base material and the electronic device are separated from each other by supplying an organic solvent having a solubility parameter of more than 10 or a mixed solution of the organic solvent and water to a peeling line, i.e., a boundary line, on the peeling interface between the silicone resin layer and the glass substrate.

Description

Manufacturing method of electronic device

The present invention relates to an electronic device manufacturing method, and more particularly, to an electronic device manufacturing method including a separation step in which a predetermined organic solvent is supplied to a separation line between a silicone resin layer and a glass substrate to perform separation (peeling). .

In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and the glass substrates used in these devices have been made thinner. Progressing. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the device manufacturing process.
Therefore, conventionally, a method of forming a device member (for example, a thin film transistor) on a glass substrate thicker than the final thickness and then thinning the glass substrate by chemical etching is widely used.
However, in this method, for example, when the thickness of one glass substrate is reduced from 0.7 mm to 0.2 mm or 0.1 mm, most of the original glass substrate material is scraped off with an etching solution. Therefore, it is not preferable from the viewpoint of productivity and use efficiency of raw materials. In addition, in the method of thinning a glass substrate by the above chemical etching, if a fine scratch exists on the surface of the glass substrate, a fine recess (etch pit) is formed from the scratch by the etching process, resulting in an optical defect. There was a case.

Recently, in order to cope with the above problems, after preparing a glass laminate in which a thin glass substrate and a reinforcing plate are laminated and forming a member for an electronic device such as a display device on the thin glass substrate of the glass laminate, A method for separating a support plate from a thin glass substrate has been proposed (see, for example, Patent Document 1). The reinforcing plate has a support plate and a silicone resin layer fixed on the support plate, and the silicone resin layer and the thin glass substrate are in close contact with each other in a peelable manner. The reinforcing plate separated from the thin glass substrate is peeled off from the interface between the silicone resin layer of the glass laminate and the thin glass substrate, and can be reused as a glass laminate by being laminated with a new thin glass substrate.

International Publication No. 2007/018028

In recent years, with the increase in functionality and complexity of electronic device members formed on glass substrates of glass laminates, the temperature at which electronic device members are formed is further increased and exposed to such high temperatures. In many cases, it takes a long time.
The glass laminate described in Patent Document 1 causes no particular problem in the treatment at 300 ° C. for 1 hour in the atmosphere. However, according to studies by the present inventors, referring to Patent Document 1, when the glass laminate is treated at 350 ° C. for 1 hour, the glass substrate is peeled from the silicone resin layer surface. Since the glass substrate is not peeled off from the resin layer surface, a part of the glass substrate is destroyed or a part of the resin of the resin layer remains on the glass substrate. As a result, the electronic device is separated after forming the electronic device member. May not be successful, leading to reduced productivity of electronic devices.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for manufacturing an electronic device in which peeling between a silicone resin layer and a glass substrate easily proceeds even after high-temperature heat treatment conditions. And

The present inventor has examined the problems of the prior art, and it is easy to peel off by supplying an organic solvent having a predetermined property to the peeling line that is the boundary line of the peeling interface between the silicone resin layer and the glass substrate. The present invention has been completed.

That is, in order to achieve the above object, the first aspect of the present invention is a laminate with an electronic device member having a support base, a silicone resin layer, a glass substrate, and an electronic device member in this order. From the interface including the silicone resin layer and the glass substrate as a release surface, a support substrate with a silicone resin layer including the support substrate and the silicone resin layer, and an electron including the glass substrate and the electronic device member. A method of manufacturing an electronic device comprising a step of separating the device and obtaining the electronic device, wherein a solubility parameter is greater than 10 at a peeling line that is a boundary line of a peeling interface between the silicone resin layer and the glass substrate. An organic solvent or a mixed solution of the organic solvent and water is supplied to separate the support substrate with the silicone resin layer from the electronic device. It is a method of manufacturing an electronic device.
In the first embodiment, the organic solvent preferably contains an alcohol solvent that may have a halogen atom or an aprotic polar solvent.
In the first embodiment, the organic solvent is an alcohol solvent having 1 to 6 carbon atoms, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), It is preferable to include at least one selected from the group consisting of sulfolane and acetonitrile.
In the first aspect, the silicone resin in the silicone resin layer is preferably a reaction cured product of an organoalkenylpolysiloxane and an organohydrogenpolysiloxane.
The silicone resin is a cured product of an addition reaction type silicone, the addition reaction type silicone is a curable silicone resin composition including the following (a) and (b), and the silicone resin layer is It is preferably formed by curing a curable silicone resin composition on the surface of the support substrate: (a) a linear organopolysiloxane having at least two alkenyl groups per molecule, and (b) a silicon atom. Linear organopolysiloxane having at least 3 bonded hydrogen atoms per molecule, and at least one hydrogen atom bonded to a silicon atom is present on the silicon atom at the molecular end .

According to the present invention, it is possible to provide an electronic device manufacturing method in which peeling between the silicone resin layer and the glass substrate easily proceeds even after high-temperature heat treatment conditions.

FIG. 1A to FIG. 1C are schematic cross-sectional views sequentially showing the procedure of the separation step of the electronic device manufacturing method of the present invention. 2A and 2B are a perspective cross-sectional view and a top view, respectively, in the state of FIG. 1B. FIG. 3A and FIG. 3B are schematic cross-sectional views illustrating a configuration example of an electronic device. 4 (A) to 4 (C) are schematic cross-sectional views sequentially showing the procedure of each step of the method of manufacturing the laminate with the electronic device member. FIG. 5 is a schematic diagram of an apparatus for measuring peel strength.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not deviated from the scope of the present invention. Various modifications and substitutions can be made.

As a feature of the method for producing an electronic device of the present invention, an organic solvent exhibiting a predetermined solubility parameter (SP value) on a peeling line that is a boundary line of a peeling interface between a silicone resin layer and a glass substrate, or the above organic solvent And a mixed solution of water and water is supplied. By supplying the organic solvent or the mixed solution, the organic solvent enters the surface layer of the silicone resin layer on the glass substrate side, and decreases the interfacial adhesive force between the silicone resin layer and the glass substrate. It is presumed that exfoliation proceeds with easier.

The manufacturing method of the electronic device of the present invention includes a support base, a silicone resin layer, a glass substrate, and a laminate with an electronic device member having an electronic device member in this order, and a silicone resin layer and a glass substrate. Step of separating the support substrate with a silicone resin layer including the support substrate and the silicone resin layer and the electronic device including the glass substrate and the electronic device member to obtain an electronic device (separation step) ) At least.
FIG. 1A to FIG. 1C are schematic cross-sectional views sequentially showing the procedure of the separation step of the electronic device manufacturing method of the present invention. Hereinafter, the procedure of the separation step will be described in detail with reference to FIGS. 1 (A) to 1 (C).

First, with a member for an electronic device having a supporting substrate, a silicone resin layer disposed on the supporting substrate, a glass substrate disposed on the silicone resin layer, and an electronic device member disposed on the glass substrate Prepare a laminate. FIG. 1A is a schematic cross-sectional view of an example of a laminated body with a member for electronic devices according to the present invention.
As shown to FIG. 1 (A), the laminated body 10 with a member for electronic devices has the support base material 12, the silicone resin layer 14, the glass substrate 16, and the member 18 for electronic devices in this order. The silicone resin layer 14 has one surface fixed to the layer of the support substrate 12 and the other surface in contact with the first main surface of the glass substrate 16. The interface is preferably in close contact with the peelable surface.
The two-layer part consisting of the layer of the support substrate 12 and the silicone resin layer 14 reinforces the glass substrate 16 in a member forming step described later for manufacturing a member for an electronic device such as a liquid crystal panel. The two-layer portion composed of the layer of the support base 12 and the silicone resin layer 14 is also referred to as a support base 20 with a silicone resin layer.
In addition, the two-layer portion including the glass substrate 16 and the electronic device member 18 is also referred to as an electronic device 22.
In addition, each member which comprises the laminated body with a member for electronic devices, and its manufacturing procedure are demonstrated collectively in a back | latter stage.

First, the procedure for separating the support substrate with the silicone resin layer and the electronic device from the laminate with the electronic device member using the interface between the silicone resin layer and the glass substrate as the release surface will be described.
First, when separating a support base material with a silicone resin layer and an electronic device from a laminated body with a member for electronic devices, it is preferable to provide a trigger for peeling at the interface between the silicone resin layer and the glass substrate. For example, a sharp blade-like object is inserted into the interface between the glass substrate 16 and the silicone resin layer 14 in FIG.
Next, as shown in FIG. 1B, the support base material 20 with the silicone resin layer and the electronic device 22 are separated. At that time, an organic solvent having a solubility parameter of more than 10 or a mixed solution of the organic solvent and water (generically referred to as a solution) on a peeling line that is a boundary line of the peeling interface between the silicone resin layer 14 and the glass substrate 16. 24) is supplied.
2A and 2B show a perspective sectional view and a top view of the state of FIG. 1B, and a peeling line X (peeling boundary line) is shown. The peeling line X is a line indicating a boundary between a portion where the silicone resin layer 14 and the glass substrate 16 are not peeled and a portion where the silicone resin layer 14 and the glass substrate 16 are peeled. As shown in FIGS. 2A and 2B, in the case of peeling while lifting one end side of the electronic device 22, the peeling line X extends from one end side of the electronic device to the other end side (see FIG. 2B). Move from right to left)

As an organic solvent supplied to the peeling line, an organic solvent having a solubility parameter (SP value: cal / cm ³ ) of more than 10 is used. Especially, the solubility parameter of the organic solvent is preferably 11 or more in that the peeling between the silicone resin layer and the glass substrate proceeds more favorably. The upper limit is not particularly limited, but is usually preferably 23 or less from the viewpoint of wettability.
Only one organic solvent may be used, or two or more organic solvents may be used in combination.
The solubility parameter (δ) means that when the heat of evaporation per mole of the organic solvent is ΔH (cal / mol) and the molar volume is V (cm ³ · mol), δ = (ΔH / V) ^{1 / The} value defined by ² .
Further, the contact angle of the organic solvent with respect to the silicone resin layer described later is not particularly limited, but is preferably 90 ° or less from the viewpoint that the peeling between the silicone resin layer and the glass substrate proceeds better.
The contact angle was measured by using PCA-1 manufactured by Kyowa Interface Science Co., Ltd. with a drop volume of 1 μl, dropping 5 points per sample surface at 23 ° C., and contact angle 60 seconds after dropping. Was measured. The average value of the three contact angles excluding one of the maximum value and the minimum value of the five contact angles is obtained as the contact angle.

Examples of the solution supplied to the peeling line include a mixed solution of an organic solvent having a solubility parameter exceeding 10 and water. The definition of the organic solvent is as described above.
The content of the organic solvent in the mixed solution is not particularly limited, but is preferably 10% by mass or more, and 20% by mass with respect to the total amount of the mixed solution in that the peeling between the silicone resin layer and the glass substrate proceeds better. The above is more preferable. The upper limit is not particularly limited.

As a preferred embodiment of the organic solvent, an alcoholic solvent which may have a halogen atom, which satisfies the above-mentioned solubility parameter, or aprotic in that the peeling between the silicone resin layer and the glass substrate proceeds better. Examples include polar solvents.
The alcohol solvent is preferably an alcohol solvent having 1 to 6 carbon atoms, more preferably an alcohol solvent having 1 to 3 carbon atoms, from the viewpoint that peeling between the silicone resin layer and the glass substrate proceeds better. . Specific examples include ethanol, propanol, butanol, pentanol, and hexanol. The alcohol solvent may be linear, branched or cyclic.
The alcohol solvent may contain a halogen atom. That is, an alcohol solvent in which a hydrogen atom is substituted with a halogen atom may be used. Examples of the halogen atom include a fluorine atom, a bromine atom, and an iodine atom.
Examples of the aprotic polar solvent include dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), sulfolane, and acetonitrile.

The supply method of the organic solvent or the mixed solution is not particularly limited, and a method of supplying the organic solvent or the mixed solution directly to the peeling line using a syringe or the like, a method of spraying the organic solvent or the mixed solution on the peeling line by spraying, etc. Can be mentioned.
Also, once the organic solvent or mixed solution is supplied to the peeling line, the organic solvent or mixed solution also moves along the peeling line due to capillary action when the peeling line moves along with the peeling between the silicone resin layer and the glass substrate. For this reason, the peeling between the silicone resin layer and the glass substrate tends to proceed continuously. Further, during the peeling, an organic solvent or a mixed solution may be supplied continuously to the peeling line.
Note that the supply amount of the organic solvent or the mixed solution is not particularly limited, but may be an amount that covers the peeling line.

The method for separating the support substrate 20 with the silicone resin layer from the electronic device 22 is not particularly limited, and a known method can be used.
For example, the electronic device member-attached laminate 10 is placed on a surface plate so that the support base 12 is on the upper side and the electronic device member 18 side is on the lower side, and the electronic device member 18 side is vacuum-adsorbed on the surface plate. In this state, the blade is first allowed to enter the interface between the silicone resin layer 14 and the glass substrate 16. Then, the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted.

By performing the said process, as shown to FIG.1 (C), the laminated body 10 with a member for electronic devices can be isolate | separated into the support base material 20 with a silicone resin layer, and the electronic device 22. FIG.
In addition, the new glass substrate 16 and the member 18 for electronic devices are laminated | stacked on the support base material 20 with a silicone resin layer, and can be reused as the glass laminated body 10 with a member for electronic devices.
Moreover, as the electronic device 22 (laminated body including the glass substrate 16 and the electronic device member 18) manufactured by the above method, a display panel having a glass substrate and a display device member, a glass substrate and a solar cell member. It can be used as a solar cell having a glass substrate, a thin film secondary battery having a glass substrate and a member for a thin film secondary battery, an electronic component having a glass substrate and a member for an electronic device, and the like. Examples of the display device panel include a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.
As a more specific example of the electronic device, when a TFT-LCD described in a member forming process described later is manufactured, a liquid crystal panel as shown in FIG. 3A can be obtained. A liquid crystal panel 80 shown in FIG. 3A includes a TFT substrate 82, a CF substrate 84, a liquid crystal layer 86, and the like. The TFT substrate 82 is formed by patterning TFT elements (thin film transistors) 83 on the glass substrate 16. The CF substrate 84 is formed by patterning color filter elements 85 on the glass substrate 16. The TFT substrate 82 and the CF substrate 84 also correspond to the electronic device.
Another specific example of the electronic device is electronic paper illustrated in FIG. In FIG. 3B, the electronic paper 90 includes, for example, a glass substrate 16, a TFT layer 92, a layer 94 containing an electrical engineering medium (for example, microcapsule), a transparent electrode 96, and a front plate 98. The electronic paper element 91 is constituted by the TFT layer 92, the layer 94 of the electrical engineering medium, the transparent electrode 96, and the like. The electronic paper element may be any of a microcapsule type, an in-plane type, a twist ball type, a particle movement type, an electronic jet type, and a polymer network type.

Hereinafter, each structure (support base material 12, silicone resin layer 14, glass substrate 16, electronic device member 18) of the laminated body 10 with a member for electronic devices used above, and the laminated body with a member for electronic devices Ten manufacturing methods will be described.

The interface between the support substrate 12 and the silicone resin layer 14 has a peel strength (x), and a stress in the peeling direction exceeding the peel strength (x) is applied to the interface between the support substrate 12 and the silicone resin layer 14. And the interface of the support base material 12 and the silicone resin layer 14 peels. The interface between the silicone resin layer 14 and the glass substrate 16 has a peel strength (y). When a stress in the peeling direction exceeding the peel strength (y) is applied to the interface between the silicone resin layer 14 and the glass substrate 16, the silicone resin The interface between the 14 layers and the glass substrate 16 peels off.
In the laminated body 10 with a member for electronic devices, it is usually preferable that the peel strength (x) is higher than the peel strength (y). If it is this aspect, when the stress of the direction which peels the support base material 12 and the glass substrate 16 will be applied to the laminated body 10 with a member for electronic devices, the glass laminated body 10 with a member for electronic devices of this invention will be silicone. It peels at the interface of the resin layer 14 and the glass substrate 16, and it isolate | separates easily with the electronic device 22 and the support base material 20 with a silicone resin layer.

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 14 to the support base 12 can be increased, and a relatively higher adhesion to the glass substrate 16 can be maintained after the heat treatment. .
In order to increase the adhesion of the silicone resin layer 14 to the support substrate 12, for example, it is preferable to form a silicone resin layer 14 by crosslinking and curing a crosslinkable organopolysiloxane on the support substrate 12. The silicone resin layer 14 bonded to the support substrate 12 with a high bonding force can be formed by the adhesive force at the time of crosslinking and curing.
On the other hand, the bond strength of the cured product of the crosslinkable organopolysiloxane after the crosslink curing to the glass substrate 16 is usually lower than the bond strength generated at the time of the crosslink curing. Therefore, it is preferable to crosslink and cure the crosslinkable organopolysiloxane on the support substrate 12 to form the silicone resin layer 14 and then laminate the glass substrate 16 on the surface of the silicone resin layer 14.

[Supporting substrate]
The support base material 12 supports and reinforces the glass substrate 16, and the glass substrate 16 is deformed and scratched when the electronic device member is manufactured in a member forming step (step of manufacturing an electronic device member) described later. Prevent damage.
As the support substrate 12, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used. Usually, since the member forming process described later involves heat treatment, the support base 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16 and is formed of the same material as the glass substrate 16. Is more preferable, and the support substrate 12 is preferably a glass plate. In particular, the support base 12 is preferably a glass plate made of the same glass material as the glass substrate 16.

The thickness of the support base 12 may be thicker or thinner than the glass substrate 16. Preferably, the thickness of the support base 12 is selected based on the thickness of the glass substrate 16 and the thickness of the silicone resin layer 14. For example, when the current member forming process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the glass substrate 16 and the thickness of the silicone resin layer 14 is 0.1 mm, The thickness of the support base 12 is set to 0.4 mm. In general, the thickness of the support base 12 is preferably 0.2 to 5.0 mm.

When the support substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons such as being easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.

The difference in average linear expansion coefficient between the support base 12 and the glass substrate 16 at 25 to 300 ° C. is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably 300 × 10 ⁻⁷ / ° C. or less. More preferably, it is 200 × 10 ⁻⁷ / ° C. or less. If the difference is too large, the support base 12 and the glass substrate 16 may be peeled off at the time of heating and cooling in the member forming step described later. When the material of the support base material 12 is the same as the material of the glass substrate 16, it can suppress that such a problem arises.

[Silicone resin layer]
The silicone resin layer 14 prevents misalignment of the glass substrate 16 until the operation of separating the support base material 20 with the silicone resin layer and the electronic device 22 is performed, and the glass substrate 16 and the like are damaged by the separation operation. To prevent. The surface 14a of the silicone resin layer 14 that is in contact with the glass substrate 16 is in close contact with the first main surface 16a of the glass substrate 16 in a peelable manner. The silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the peeling strength (y) at the interface is the peeling at the interface between the silicone resin layer 14 and the support base 12. The strength is preferably lower than (x).
That is, when separating the glass substrate 16 and the support base material 12, the glass substrate 16 is peeled off at the interface between the first main surface 16 a of the glass substrate 16 and the silicone resin layer 14, and the support base material 12 and the silicone resin layer 14 are separated. It is preferable that peeling at the interface is difficult. In this preferred embodiment, the silicone resin layer 14 is in close contact with the first main surface 16a of the glass substrate 16, but has a surface characteristic that allows the glass substrate 16 to be easily peeled off. That is, the silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a certain amount of bonding force to prevent the glass substrate 16 from being displaced, and at the same time, when the glass substrate 16 is peeled off. The glass substrate 16 is bonded with a bonding force that can be easily peeled without breaking the glass substrate 16. The property that the surface of the silicone resin layer 14 can be easily peeled is called peelability. On the other hand, the 1st main surface of the support base material 12 and the silicone resin layer 14 are couple | bonded by the bonding force which cannot be peeled relatively.
The bonding force at the interface between the silicone resin layer 14 and the glass substrate 16 may change before and after forming the electronic device member on the surface of the glass substrate 16 (second main surface 16b) (that is, peel strength). (X) and peel strength (y) may be changed). However, even after the electronic device member is formed, the peel strength (y) is preferably lower than the peel strength (x).

It is preferable that the silicone resin layer 14 and the layer of the glass substrate 16 are bonded to each other with a bonding force resulting from weak adhesive force or van der Waals force. When the glass substrate 16 is laminated on the surface after the silicone resin layer 14 is formed, if the silicone resin of the silicone resin layer 14 is sufficiently cross-linked so as not to exhibit an adhesive force, the binding force due to van der Waals force It is thought that it is combined with. However, the silicone resin of the silicone resin layer 14 often has a certain weak adhesive force. Even when the adhesion is extremely low, when forming the electronic device member, the silicone resin of the silicone resin layer 14 is adhered to the surface of the glass substrate 16 by a heating operation or the like. The bonding force between the layers of the substrate 16 is considered to increase.
In some cases, the surface of the silicone resin layer 14 before lamination or the first main surface 16a of the glass substrate 16 before lamination can be laminated by performing a treatment for weakening the bonding force between them. By performing non-adhesive treatment or the like on the surface to be laminated and then laminating, the bonding strength at the interface between the silicone resin layer 14 and the glass substrate 16 can be weakened, and the peel strength (y) can be lowered.

The silicone resin layer 14 is preferably bonded to the surface of the support substrate 12 with a strong bonding force such as an adhesive force or an adhesive force. For example, as described above, by crosslinking and curing the crosslinkable organopolysiloxane on the surface of the support substrate 12, a silicone resin as a crosslinked product can be adhered to the surface of the support substrate 12 and high bonding strength can be obtained. . Moreover, the process (for example, process using a coupling agent) which produces strong bond strength between the support base material 12 surface and the silicone resin layer 14 is given, and between the support base material 12 surface and the silicone resin layer 14 The binding power of can be increased.
The fact that the silicone resin layer 14 and the layer of the supporting substrate 12 are bonded with a high bonding force means that the peel strength (x) at the interface between them is high.

The thickness of the silicone resin layer 14 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. When the thickness of the silicone resin layer 14 is within such a range, even if air bubbles or foreign matter may be present between the silicone resin layer 14 and the glass substrate 16, the occurrence of distortion defects in the glass substrate 16 is suppressed. can do. In addition, if the thickness of the silicone resin layer 14 is too thick, it takes time and materials to form it, which is not economical and the heat resistance may decrease. Moreover, when the thickness of the silicone resin layer 14 is too thin, the adhesiveness of the silicone resin layer 14 and the glass substrate 16 may fall.
The silicone resin layer 14 may be composed of two or more layers. In this case, “the thickness of the silicone resin layer 14” means the total thickness of all the layers.
Moreover, when the silicone resin layer 14 consists of two or more layers, resin which forms each layer may consist of a different crosslinked silicone resin.

The silicone resin contained in the silicone resin layer 14 is a crosslinked product of a crosslinkable organopolysiloxane, and the silicone resin preferably forms a three-dimensional network structure.
The type of the crosslinkable organopolysiloxane is not particularly limited, and the structure is not particularly limited as long as it is cross-linked and cured through a predetermined cross-linking reaction to obtain a cross-linked product (cured product) constituting the silicone resin. What is necessary is just to have sex. The form of crosslinking is not particularly limited, and a known form can be appropriately employed depending on the kind of the crosslinkable group contained in the crosslinkable organopolysiloxane. Examples thereof include a hydrosilylation reaction, a condensation reaction, a heat treatment, a high energy ray treatment, or a radical reaction using a radical polymerization initiator.
More specifically, when the crosslinkable organopolysiloxane has a radical reactive group such as an alkenyl group or an alkynyl group, the cured product (crosslinked silicone resin) is crosslinked by a reaction between the radical reactive groups via the radical reaction. )
Moreover, when crosslinkable organopolysiloxane has a silanol group, it crosslinks by the condensation reaction of silanol groups, and it becomes a hardened | cured material.
In addition, the crosslinkable organopolysiloxane has an organopolysiloxane having an alkenyl group (such as a vinyl group) bonded to a silicon atom (ie, an organoalkenylpolysiloxane) and a hydrogen atom bonded to a silicon atom (hydrosilyl group). In the case of containing the organopolysiloxane having (that is, organohydrogenpolysiloxane), it is crosslinked by a hydrosilylation reaction in the presence of a hydrosilylation catalyst (for example, a platinum-based catalyst) to form a cured product.

Of these, the crosslinkable organopolysiloxane is an organopolysiloxane having alkenyl groups at both ends and / or side chains (hereinafter referred to as organopolysiloxane as appropriate) because the silicone resin layer 14 can be easily formed and is excellent in the peelability of the glass substrate. An embodiment including polysiloxane A) and organopolysiloxane having hydrosilyl groups at both ends and / or side chains (hereinafter also referred to as organopolysiloxane B as appropriate) is preferable.
The alkenyl group is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, and a hexynyl group. Among them, the heat resistance is excellent. A vinyl group is preferred.
Examples of the group other than the alkenyl group contained in the organopolysiloxane A and the group other than the hydrosilyl group contained in the organopolysiloxane B include an alkyl group (particularly an alkyl group having 4 or less carbon atoms).

The position of the alkenyl group in the organopolysiloxane A is not particularly limited. However, when the organopolysiloxane A is linear, the alkenyl group may be present in any one of the M unit and D unit shown below. And D units may be present. From the viewpoint of curing speed, it is preferably present at least in M units, and preferably present in both two M units.
The M unit and D unit are examples of basic structural units of organopolysiloxane. The M unit is a monofunctional siloxane unit in which three organic groups are bonded. The D unit is bonded to two organic groups. Bifunctional siloxane unit. In the siloxane unit, the siloxane bond is a bond in which two silicon atoms are bonded through one oxygen atom, so that the oxygen atom per silicon atom in the siloxane bond is regarded as ½, Expressed as O _1/2 .

The number of alkenyl groups in organopolysiloxane A is not particularly limited, but is preferably 1 to 3 and more preferably 2 per molecule.
The position of the hydrosilyl group in the organopolysiloxane B is not particularly limited. However, when the organopolysiloxane A is linear, the hydrosilyl group may be present in either the M unit or the D unit. It may be present in both D units. It is preferable that it exists in at least D unit from the point of a cure rate.
The number of hydrosilyl groups in the organopolysiloxane B is not particularly limited, but it is preferably at least 3 per molecule, and more preferably 3.

The mixing ratio of organopolysiloxane A and organopolysiloxane B is not particularly limited, but the molar ratio of hydrogen atoms bonded to silicon atoms in organopolysiloxane B and all alkenyl groups in organopolysiloxane A (hydrogen atoms / The alkenyl group is preferably adjusted to 0.7 to 1.05. In particular, it is preferable to adjust the mixing ratio so as to be 0.8 to 1.0.

As the hydrosilylation catalyst, a platinum group metal catalyst is preferably used. Examples of the platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and it is particularly preferable to use as a platinum-based catalyst from the viewpoint of economy and reactivity. As the platinum group metal catalyst, known catalysts can be used. Specifically, platinum fine powder, platinum black, chloroplatinic acid such as chloroplatinic acid, chloroplatinic acid, platinum tetrachloride, alcohol compounds of chloroplatinic acid, aldehyde compounds, platinum olefin complexes, alkenyls Examples thereof include siloxane complexes and carbonyl complexes.
The amount of the hydrosilylation catalyst used is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total mass of organopolysiloxane A and organopolysiloxane B.

The number average molecular weight of the crosslinkable organopolysiloxane is not particularly limited, but it is excellent in handleability, excellent in film formability, and is more resistant to decomposition of the silicone resin under high temperature processing conditions. The weight average molecular weight in terms of polystyrene as measured by chromatography is preferably 1,000 to 5,000,000, and more preferably 2,000 to 3,000,000.
The viscosity of the crosslinkable organopolysiloxane is preferably 10 to 5000 mPa · s, more preferably 15 to 3000 mPa · s.

In addition, as a commercially available product name or model number of the crosslinkable organopolysiloxane, KNS-320A and KS-847 (both manufactured by Shin-Etsu Silicone Co., Ltd.) are used as the crosslinkable organopolysiloxane having no aromatic group. ), TPR6700 (made by Momentive Performance Materials Japan GK), vinyl silicone “8500” (made by Arakawa Chemical Industries) and methylhydrogenpolysiloxane “12031” (made by Arakawa Chemical Industries), vinyl A combination of silicone “11364” (Arakawa Chemical Industries) and methylhydrogenpolysiloxane “12031” (Arakawa Chemical Industries), vinyl silicone “11365” (Arakawa Chemical Industries) and methylhydrogenpolysiloxane “ 12031 "(Arakawa Chemical Industries Such as a combination of a Ltd.) and the like. As the silicone resin, addition reaction type silicone is preferable. This is because the curing reaction is easy, the degree of peelability is good when the silicone resin layer is formed, and the heat resistance is also high. The addition reaction type silicone is preferably a curable silicone resin composition containing the following linear organopolysiloxane (a) and the following linear organopolysiloxane (b) (linear organopolysiloxane (a): alkenyl. A linear organopolysiloxane having at least two groups per molecule, a linear organopolysiloxane (b): a linear organopolysiloxane having at least three hydrogen atoms bonded to silicon atoms per molecule, and A linear organopolysiloxane in which at least one hydrogen atom bonded to a silicon atom is present on the silicon atom at the molecular end.)
The silicone resin layer 14 is more preferably a cured silicone resin layer formed by curing the curable silicone resin composition on the surface of the support substrate 12.

[Glass substrate]
As for the glass substrate 16, the 1st main surface 16a touches the silicone resin layer 14, and the member for electronic devices is provided in the 2nd main surface 16b on the opposite side to the silicone resin layer 14 side.
The glass substrate 16 may be of a general type, and examples thereof include a glass substrate for a display device such as an LCD or an OLED. The glass substrate 16 is excellent in chemical resistance and moisture permeability and has a low heat shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.

If the linear expansion coefficient of the glass substrate 16 is large, the member forming process described later often involves a heat treatment, and various inconveniences are likely to occur. For example, when a TFT is formed on the glass substrate 16, if the glass substrate 16 on which the TFT is formed is cooled under heating, the TFT may be displaced excessively due to thermal contraction of the glass substrate 16.

The glass substrate 16 is obtained by melting a glass raw material and molding the molten glass into a plate shape. Such a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a full call method, a rubber method, or the like is used. The glass substrate 16 having a particularly small thickness can be obtained by heating a glass once formed into a plate shape to a moldable temperature and then stretching it by means of stretching or the like to make it thin (redraw method).

The type of glass of the glass substrate 16 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses mainly composed of silicon oxide are preferable. As the oxide-based glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.

As the glass of the glass substrate 16, glass suitable for the type of electronic device member and the manufacturing process thereof is employed. For example, a glass substrate for a liquid crystal panel is made of glass (non-alkali glass) that does not substantially contain an alkali metal component because the elution of an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) Ingredients are included). Thus, the glass of the glass substrate 16 is appropriately selected based on the type of device to be applied and its manufacturing process.

The thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.15 mm or less, and even more preferably 0.10 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 16. It is. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 16. In the case of 0.15 mm or less, the glass substrate 16 can be rolled up.
Further, the thickness of the glass substrate 16 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 16 and easy handling of the glass substrate 16.

The glass substrate 16 may be composed of two or more layers. In this case, the material forming each layer may be the same material or a different material. In this case, “the thickness of the glass substrate 16” means the total thickness of all the layers.

[Electronic device components (functional elements)]
The electronic device member 18 is a member formed on the glass substrate 16 and constituting at least a part of the electronic device. More specifically, as the electronic device member 18, a member used for an electronic component such as a display panel, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on the surface (for example, Display member, solar cell member, thin film secondary battery member, electronic component circuit).

For example, as a member for a solar cell, a silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
Further, as a member for a thin film secondary battery, in the lithium ion type, a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, a resin as a sealing layer, etc. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
In addition, as a circuit for an electronic component, in a CCD or CMOS, a metal of a conductive part, a silicon oxide or a silicon nitride of an insulating part, and the like, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board And various members corresponding to a rigid flexible printed circuit board.

[Method for producing laminate with electronic device member]
Although the manufacturing method of the laminated body 10 with a member for electronic devices is not specifically limited, in order to obtain a laminated body whose peel strength (x) is higher than the peel strength (y), a predetermined crosslinkable organo on the surface of the support substrate 12 is obtained. It is preferable to include a step of forming a silicone resin layer 14 by crosslinking and curing polysiloxane. That is, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate 12, and the crosslinkable organopolysiloxane is crosslinked on the surface of the support substrate 12 to form a silicone resin layer 14 (crosslinked silicone resin). Next, the glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14, and the electronic device member 18 is further formed on the glass substrate 16 to manufacture the laminated body 10 with the electronic device member.
When the crosslinkable organopolysiloxane is cured on the surface of the support substrate 12, it is considered that the crosslinkable organopolysiloxane adheres due to the interaction with the surface of the support substrate 12 during the curing reaction, and the peel strength between the silicone resin and the surface of the support substrate 12 increases. . Therefore, even if the glass substrate 16 and the support base 12 are made of the same material, a difference can be provided in the peel strength between the silicone resin layer 14 and the both.
Hereinafter, a step of forming a silicone resin layer 14 by forming a layer containing a crosslinkable organopolysiloxane on the surface of the support substrate 12 and crosslinking the crosslinkable organopolysiloxane on the surface of the support substrate 12 is a resin layer forming step. The step of laminating the glass substrate 16 on the silicone resin surface of the silicone resin layer 14 is referred to as a laminating step, and the step of forming the electronic device member 18 on the glass substrate 16 is referred to as a member forming step. .

(Resin layer forming process)
In the resin layer forming step, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate 12, and the crosslinkable organopolysiloxane is crosslinked on the surface of the support substrate 12 to form the silicone resin layer 14.
In order to form a layer containing a crosslinkable organopolysiloxane on the support substrate 12, a coating composition in which the crosslinkable organopolysiloxane is dissolved in a solvent is used, and this composition is formed on the support substrate 12. It is preferable to form a solution layer by coating, and then remove the solvent to form a layer containing a crosslinkable organopolysiloxane. The thickness of the layer containing the crosslinkable organopolysiloxane can be controlled by adjusting the concentration of the crosslinkable organopolysiloxane in the composition.
The solvent is not particularly limited as long as it can easily dissolve the crosslinkable organopolysiloxane in a working environment and can be easily volatilized and removed. Specific examples include butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF, chloroform and the like.

The method for applying the composition containing the crosslinkable organopolysiloxane on the surface of the support substrate 12 is not particularly limited, and a known method can be used. Examples thereof include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating.
Then, if necessary, a drying process for removing the solvent may be performed. The method for the drying treatment is not particularly limited, and examples thereof include a method of removing the solvent under reduced pressure conditions and a method of heating at a temperature at which the curing of the crosslinkable organopolysiloxane does not proceed.

Next, the crosslinkable organopolysiloxane on the support substrate 12 is crosslinked to form the silicone resin layer 14. More specifically, as shown in FIG. 4A, in this step, a silicone resin layer 14 is formed on at least one surface of the support base 12.
As described above, the curing (crosslinking) method is appropriately selected according to the crosslinking type of the crosslinkable organopolysiloxane, and examples thereof include heat treatment and exposure treatment. In particular, when the crosslinkable organopolysiloxane is crosslinked by a hydrosilylation reaction, a condensation reaction, or a radical reaction, a silicone resin having excellent adhesion and heat resistance to the glass substrate 16 can be obtained. It is preferable to manufacture.
Hereinafter, the aspect of thermosetting is explained in full detail.

The temperature condition for thermally curing the crosslinkable organopolysiloxane improves the heat resistance of the silicone resin layer 14 and is preferably 150 to 300 ° C, more preferably 180 to 250 ° C. The heating time is usually preferably 10 to 120 minutes, more preferably 30 to 60 minutes.

The crosslinkable organopolysiloxane may be cured by precuring (precuring) and then by postcuring (main curing). By performing the pre-cure, the silicone resin layer 14 having better heat resistance can be obtained. Precuring is preferably performed following the removal of the solvent. In that case, there is no particular distinction between the step of removing the solvent from the layer to form a layer containing a crosslinkable organopolysiloxane and the step of performing precuring.

The formation of the silicone resin layer 14 is not limited to the above method.
For example, in the case of using a support base material 12 having a higher adhesion to the silicone resin surface than the glass substrate 16, a crosslinkable organopolysiloxane is cured on some peelable surface to produce a silicone resin film, This film can be interposed between the glass substrate 16 and the support base 12 and laminated simultaneously.
Moreover, when the adhesiveness by hardening of crosslinkable organopolysiloxane is low enough with respect to the glass substrate 16, and the adhesiveness is high enough with respect to the support base material 12, it bridge | crosslinks between the glass substrate 16 and the support base material 12. The silicone resin layer 14 can be formed by curing the functional organopolysiloxane.
Furthermore, even when the support base 12 is made of the same glass material as that of the glass substrate 16, it is possible to increase the peel strength with respect to the silicone resin layer 14 by performing a process for improving the adhesion of the support base 12 surface. For example, a chemical method (primer treatment) that improves the fixing force chemically such as a silane coupling agent, a physical method that increases surface active groups such as a flame (flame) treatment, or a surface such as a sandblast treatment Examples of such a mechanical processing method increase the catch by increasing the roughness of the material.

(Lamination process)
In the laminating step, the glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14 obtained in the resin layer forming step, and the layer of the supporting base 12, the silicone resin layer 14, and the glass substrate 16 are laminated. This is a step of obtaining a glass laminate provided in this order. More specifically, as shown in FIG. 4B, a glass substrate having a surface 14a opposite to the support base 12 side of the silicone resin layer 14, and a first main surface 16a and a second main surface 16b. The silicone resin layer 14 and the glass substrate 16 are laminated by using the first principal surface 16a of 16 as a lamination surface to obtain a glass laminate 26.

The method in particular of laminating | stacking the glass substrate 16 on the silicone resin layer 14 is not restrict | limited, A well-known method is employable.
For example, a method of stacking the glass substrate 16 on the surface of the silicone resin layer 14 under a normal pressure environment can be mentioned. If necessary, after the glass substrate 16 is overlaid on the surface of the silicone resin layer 14, the glass substrate 16 may be pressure-bonded to the silicone resin layer 14 using a roll or a press. Air bubbles mixed between the silicone resin layer 14 and the glass substrate 16 can be removed relatively easily by pressure bonding using a roll or a press, which is preferable.

It is more preferable to perform pressure bonding by a vacuum laminating method or a vacuum pressing method because it can suppress mixing of bubbles and ensure good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are not likely to lead to a distortion defect of the glass substrate 16.

When laminating the glass substrate 16, it is preferable that the surface of the glass substrate 16 in contact with the silicone resin layer 14 is sufficiently washed and laminated in an environment with a high cleanliness. The higher the degree of cleanliness, the better the flatness of the glass substrate 16, which is preferable.

In addition, after laminating | stacking the glass substrate 16, you may perform a pre-annealing process (heat processing) as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the silicone resin layer 14 can be improved, and an appropriate peel strength (y) can be obtained. Misalignment of members is less likely to occur, and the productivity of electronic devices is improved.
The conditions for the pre-annealing treatment are appropriately selected according to the type of the silicone resin layer 14 to be used, but the peel strength (y) between the glass substrate 16 and the silicone resin layer 14 is more appropriate. In view of this, it is preferable to perform heat treatment at 300 ° C. or higher (preferably 300 to 400 ° C.) for 5 minutes or longer (preferably 5 to 30 minutes).

(Member formation process)
A member formation process is a process of forming the member for electronic devices on the glass substrate 16 in the glass laminated body 26 obtained in the said lamination process. More specifically, as shown in FIG. 4C, the electronic device member 18 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 to obtain the laminated body 10 with the electronic device member. .

The procedure of this step is not particularly limited, and for the electronic device, on the surface of the second main surface 16b of the glass substrate 16 of the glass laminate 26 by a conventionally known method according to the type of the constituent member of the electronic device member. The member 18 is formed.
The electronic device member 18 is not all of the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter referred to as “all members”), but a part of all members (hereinafter referred to as “parts”). May be referred to as a member. The glass substrate with a partial member peeled from the silicone resin layer 14 can be used as a glass substrate with an all member (corresponding to an electronic device described later) in the subsequent steps.
Moreover, the other electronic device member may be formed in the peeling surface (1st main surface 16a) in the glass substrate with all the members peeled from the silicone resin layer 14. FIG. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the support substrate 12 from the laminate with all members. Furthermore, it is also possible to assemble using two laminates with all members, and then peel off the two support bases 12 from the laminate with all members to produce a glass substrate with a member having two glass substrates. it can.

For example, taking the case of manufacturing an OLED as an example, an organic EL structure is formed on the surface of the glass substrate 16 opposite to the silicone resin layer 14 (corresponding to the second main surface 16b of the glass substrate 16). For this purpose, a transparent electrode is formed, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and a sealing plate is used for sealing. Various layer formation and processing such as stopping are performed. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.

Further, for example, when manufacturing a TFT-LCD, a resist film is used on the second main surface 16b of the glass substrate 16 of the glass laminate 26 by a general film forming method such as a CVD method or a sputtering method. A pattern is formed on the formed metal film and metal oxide film to form a thin film transistor (TFT), and a resist solution is patterned on the second main surface 16b of the glass substrate 16 of another glass laminate 26. Various processes such as a CF forming step for forming a color filter (CF) to be used for forming, a laminating step for laminating a laminated body with TFT obtained in the TFT forming step and a laminated body with CF obtained in the CF forming step, etc. Process.

In the TFT formation process and the CF formation process, the TFT and the CF are formed on the second main surface 16b of the glass substrate 16 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist solution is used as a coating solution for pattern formation.
In addition, before forming TFT and CF, you may wash | clean the 2nd main surface 16b of the glass substrate 16 as needed. As a cleaning method, known dry cleaning or wet cleaning can be used.

In the laminating step, the thin film transistor forming surface of the laminated body with TFT and the color filter forming surface of the laminated body with CF are opposed to each other, and are bonded using a sealant (for example, an ultraviolet curable sealant for cell formation). Thereafter, a liquid crystal material is injected into a cell formed by the laminate with TFT and the laminate with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.

Hereinafter, the present invention will be specifically described with reference to examples and the like, but the present invention is not limited to these examples.

<Example 1>
A support glass substrate (Asahi Glass Co., Ltd., AN100) having a length of 400 mm, a width of 300 mm, a thickness of 0.7 mm, and a linear expansion coefficient of 38 × 10 ⁻⁷ / ° C. is cleaned with pure water, UV cleaning, etc. Solvent-free addition reaction type release paper silicone (KNS-320A manufactured by Shin-Etsu Silicone Co., Ltd., mixture of organoalkenylpolysiloxane and organohydrogenpolysiloxane) and platinum catalyst (manufactured by Shin-Etsu Silicone Co., Ltd.) (CAT-PL-56) 2 parts by weight of the mixture was applied with a spin coater (coating amount 10 g / m ² ), and heated and cured in the air at 180 ° C. for 30 minutes to form a silicone resin layer having a thickness of 16 μm. Obtained.
Clean the surface of the thin glass substrate (AN100) with a length of 400 mm, width of 300 mm, thickness of 0.7 mm, and linear expansion coefficient of 38 × 10 ⁻⁷ / ° C. with pure water cleaning, UV cleaning, etc. Then, the silicone resin layer forming surface of the supporting glass substrate and the thin glass substrate were bonded together by a vacuum press at room temperature to obtain a glass laminate A having a silicone resin layer.

Next, the glass laminate A was heat-treated at 350 ° C. for 60 minutes in the atmosphere.
Then, a stainless steel cutting tool having a thickness of 0.1 mm was inserted into the interface between the thin glass substrate and the silicone resin layer at one corner of the four portions of the glass laminate A to form a notch for peeling. Next, a vacuum suction pad is adsorbed on the surface of each of the thin glass substrate and the supporting glass substrate that is not on the separation surface side, and a syringe is used for the separation line that is the boundary line between the silicone resin layer and the thin glass substrate. While supplying methanol (solubility parameter: 14.5 cal / cm ³ ), when an external force was applied in a direction in which the thin glass substrate and the supporting glass substrate were separated, the thin glass substrate was separated without being damaged.

(Measurement of peel strength)
A peel test was performed using the jig described in paragraph 0050 of Japanese Patent No. 5200538. The jig used is shown in FIG. In FIG. 5, the glass laminate A includes a supporting glass substrate 40, a silicone resin layer 30, and a thin glass substrate 50.
The glass laminate A is cut into a size of 50 mm in length and 50 mm in width, and a polycarbonate of 50 mm in length, 50 mm in width, and 5 mm in thickness on the glass (supporting glass substrate 40 and thin glass substrate 50) on both sides of the glass laminate A. 60 were bonded together with an adhesive for epoxy two-component glass. Further, polycarbonates 70 each having a length of 50 mm, a width of 50 mm, and a thickness of 5 mm were further vertically bonded to the surfaces of both the bonded polycarbonates 60. As shown in FIG. 5, the place where the polycarbonate 70 is bonded is the position where the vertical direction is the end of the polycarbonate 60 and the horizontal direction is parallel to the side of the polycarbonate 60.
The glass laminate A bonded with the

polycarbonates

60 and 70 was placed so that the supporting glass substrate was on the lower side. The polycarbonate 70 affixed to the thin glass substrate side was fixed with a jig, and the polycarbonate 70 affixed to the support glass substrate side was pulled vertically downward at a speed of 300 mm / min. As a result, 0.34 kg / cm ² was applied. Sometimes the supporting glass substrate peeled off.

<Example 2>
The thin glass substrate was peeled according to the same procedure as in Example 1 except that ethanol (solubility parameter: 12.7 cal / cm ³ ) was used instead of methanol (solubility parameter: 14.5 cal / cm ³ ). As a result, the thin glass substrate was separated without breaking. Table 1 shows the measurement results of the peel strength.

<Example 3>
Instead of, ethanol (solubility parameter: 12.7cal / cm ^3): methanol (14.5cal / cm ³ Solubility Parameter) mixed solution of water (ethanol: water (mass ratio) = 1: 1) was used Except for the above, the thin glass substrate was peeled according to the same procedure as in Example 1, and the thin glass substrate was separated without being damaged. Table 1 shows the measurement results of the peel strength.

<Example 4>
Instead of methanol (solubility parameter: 14.5 cal / cm ³ ), a mixed solution of ethanol and 1-propanol (content: ethanol 90 mass%, 1-propanol 10 mass%. Solubility parameter: ethanol 12.7 cal / cm ³⁾ Except for using 1-propanol 12.0 cal / cm ³ ), the thin glass substrate was peeled according to the same procedure as in Example 1, and the thin glass substrate was separated without being damaged. Table 1 shows the measurement results of the peel strength.

<Example 5>
The thin glass substrate was peeled according to the same procedure as in Example 1 except that 1-propanol (solubility parameter: 12.0 cal / cm ³ ) was used instead of methanol (solubility parameter: 14.5 cal / cm ³ ). As a result, the thin glass substrate was separated without being damaged. Table 1 shows the measurement results of the peel strength.

<Example 6>
Methanol (solubility parameter: 14.5cal / cm ³⁾ in place of isopropanol (solubility parameter: 11.5cal / cm ³⁾ except for using, in accordance with the procedure as in Example 1, subjected to a peeling of the thin glass substrate As a result, the thin glass substrate was separated without breaking. Table 1 shows the measurement results of the peel strength.

<Example 7>
The thin glass substrate was peeled according to the same procedure as in Example 1 except that 1-butanol (solubility parameter: 11.4 cal / cm ³ ) was used instead of methanol (solubility parameter: 14.5 cal / cm ³ ). As a result, the thin glass substrate was separated without being damaged. Table 1 shows the measurement results of the peel strength.

<Example 8>
The thin glass substrate was peeled according to the same procedure as in Example 1 except that 1-hexanol (solubility parameter: 10.7 cal / cm ³ ) was used instead of methanol (solubility parameter: 14.5 cal / cm ³ ). As a result, the thin glass substrate was separated without being damaged. Table 1 shows the measurement results of the peel strength.

<Example 9>
The thin glass substrate was peeled according to the same procedure as in Example 1 except that dimethyl sulfoxide (solubility parameter: 12.0 cal / cm ³ ) was used instead of methanol (solubility parameter: 14.5 cal / cm ³ ). As a result, the thin glass substrate was separated without breaking. Table 1 shows the measurement results of the peel strength.

<Example 10>
The thin glass substrate was peeled according to the same procedure as in Example 1 except that dimethylformamide (solubility parameter: 12.1 cal / cm ³ ) was used instead of methanol (solubility parameter: 14.5 cal / cm ³ ). As a result, the thin glass substrate was separated without breaking. Table 1 shows the measurement results of the peel strength.

<Example 11>
A thin glass substrate was prepared in the same manner as in Example 1 except that N-methylpyrrolidone (solubility parameter: 11.3 cal / cm ³ ) was used instead of methanol (solubility parameter: 14.5 cal / cm ³ ). As a result of peeling, the thin glass substrate was separated without being damaged. Table 1 shows the measurement results of the peel strength.

<Comparative Example 1>
The thin glass substrate was peeled off according to the same procedure as in Example 1 except that methanol (solubility parameter: 14.5 cal / cm ³ ) was not supplied. Damage to the substrate was observed. The results of peel strength are shown in Table 1.

<Comparative example 2>
The thin glass substrate was peeled according to the same procedure as in Example 1 except that heptane (solubility parameter: 7.4 cal / cm ³ ) was used instead of methanol (solubility parameter: 14.5 cal / cm ³ ). As a result, the thin glass substrate was hardly peeled off, and the thin glass substrate was damaged. The results of peel strength are shown in Table 1.

In Table 1, the “Glass peeling” column is indicated by “◯” when the peeling of the thin glass proceeds without any problem, and “X” when the breakage or peeling of the thin glass is difficult to proceed.
In Table 1, the “SP value” column of Example 3 shows the SP value of ethanol, and the “SP value” column of Example 4 shows the SP value of ethanol and 1-propanol.

As shown in Table 1, when an organic solvent exhibiting a predetermined SP value or a mixed solution of the organic solvent and water is used, the peel strength decreases, and the thin glass substrate is damaged during the peeling. I couldn't.
On the other hand, in Comparative Example 1 in which the above organic solvent or mixed solution was not used and in Comparative Example 2 in which an organic solvent having an SP value outside the predetermined range was used, the peel strength was large, and a thin glass substrate was used for peeling. Damage was seen.

<Example 12>
In this example, an OLED was manufactured using the glass laminate A obtained in Example 1.
More specifically, molybdenum was deposited on the thin glass substrate of the glass laminate A by a sputtering method, and a gate electrode was formed by etching using a photolithography method. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are further formed in this order on the second main surface side of the peelable glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. A gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by film formation and etching using a photolithography method. Next, after forming a passivation layer by forming a silicon nitride film on the second main surface side of the peelable glass substrate by a plasma CVD method, an indium tin oxide film is formed by a sputtering method. A pixel electrode was formed by etching using.
Subsequently, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer was further deposited on the surface of the obtained laminate on the side of the thin glass substrate by vapor deposition. The layer is bis [(N-naphthyl) -N-phenyl] benzidine, and the light-emitting layer is 8-quinolinol aluminum complex (Alq ₃ ) with 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl. Aminostyryl] A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN), and Alq ₃ as an electron transport layer were formed in this order. An aluminum film was formed on the substrate side surface by sputtering, and a counter electrode was formed by etching using a photolithography method. A glass substrate A2 having an organic EL structure on a thin glass substrate, obtained by the above procedure, was sealed on the surface with another glass substrate bonded via an ultraviolet curable adhesive layer. It corresponds to the laminated body with the member for electronic devices.
In the above manufacturing process, the heat treatment at 350 ° C. for 1 hour was the treatment at the highest temperature.

Except that the glass laminate A2 was used in place of the glass laminate A1, the silicone resin layer and the thin glass substrate were separated according to the same procedure as in Example 1, and the same degree of separation as in Example 1 was performed. Separation of both proceeded with strength, and an electronic device including a thin glass substrate and an electronic device member could be obtained.

Further, even when the procedures of Examples 2 to 11 were carried out instead of the procedure of Example 1, the silicone resin layer and the thin glass substrate were peeled off at the same degree as those of Examples 2 to 11, respectively. The electronic device including the thin glass substrate and the electronic device member could be obtained.

On the other hand, when the procedures of Comparative Examples 1 and 2 are carried out instead of the procedure of Example 1, the thin glass substrate is damaged when the silicone resin layer is peeled off from the thin glass substrate, and the desired electronic device Could not get.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope and spirit of the invention.
This application is based on Japanese Patent Application No. 2013-159724 filed on July 31, 2013, the contents of which are incorporated herein by reference.

DESCRIPTION OF SYMBOLS 10 Laminated body with member for electronic devices 12

Support base material

14,30 Silicone resin layer 14a 1st main surface of silicone resin layer 16 Glass substrate 16a 1st main surface of glass substrate 16b 2nd main surface of glass substrate 18 For electronic devices Member 20 Support substrate with silicone resin layer 22 Electronic device 24 Solution 26 Glass laminate 40 Support glass substrate 50

Thin glass substrate

60, 70 Polycarbonate 80 Liquid crystal panel 82 TFT substrate 83 TFT element 84 CF substrate 85 Color filter element 90 Electronic paper 91 Electronic paper elements 92 TFT layers 94 Layers of electrical engineering media 96 Transparent electrodes

Claims

From a laminate with an electronic device member having a support base material, a silicone resin layer, a glass substrate, and an electronic device member in this order, the interface between the silicone resin layer and the glass substrate as a release surface, Manufacturing of an electronic device having a step of obtaining the electronic device by separating the supporting substrate with a silicone resin layer including the supporting substrate and the silicone resin layer, and the electronic device including the glass substrate and the electronic device member. A method,
An organic solvent having a solubility parameter of more than 10 or a mixed solution of the organic solvent and water is supplied to a peeling line which is a boundary line of a peeling interface between the silicone resin layer and the glass substrate, and the silicone resin layer The manufacturing method of an electronic device which performs isolation | separation with a support substrate with an attachment, and the said electronic device.
The method for producing an electronic device according to claim 1, wherein the organic solvent includes an alcohol solvent that may have a halogen atom or an aprotic polar solvent.
The organic solvent is an alcohol solvent having 1 to 6 carbon atoms, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), sulfolane, and acetonitrile. The manufacturing method of the electronic device of Claim 1 or 2 containing at least 1 sort (s) selected from the group which consists of these.
The method for producing an electronic device according to any one of claims 1 to 3, wherein the silicone resin in the silicone resin layer is a reaction cured product of an organoalkenylpolysiloxane and an organohydrogenpolysiloxane.
The silicone resin is a cured product of addition reaction type silicone,
The addition reaction type silicone is a curable silicone resin composition containing the following (a) and (b):
The said silicone resin layer is a manufacturing method of the electronic device of Claim 4 formed by hardening the said curable silicone resin composition on the surface of the said support base material:
(A) a linear organopolysiloxane having at least two alkenyl groups per molecule;
(B) a linear organopolysiloxane having at least three hydrogen atoms bonded to a silicon atom per molecule, and at least one of the hydrogen atoms bonded to the silicon atom is present on the silicon atom at the molecular end. Linear organopolysiloxane.