TWI596006B - A glass laminate, a method of manufacturing the same, and a supporting substrate of an agglomerated silicone resin layer - Google Patents

Description

Glass laminate, method of manufacturing the same, and support substrate for agglomerating epoxy resin layer Field of invention

The present invention relates to a glass laminate and a method for producing the same, and more particularly to a glass laminate having a polyoxyalkylene resin layer exhibiting a predetermined modulus of elasticity and a method for producing the same.

Further, the present invention relates to a support substrate for agglomerating a silicone resin layer, and more particularly to a support substrate having an agglomerated epoxy resin layer which is laminated on the surface of the glass substrate in a peelable manner, and a method for producing the same.

Background of the invention

In recent years, thinner and lighter devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCDs), and organic EL panels (OLEDs) are being used, and thinning of glass substrates for these devices is also underway. in. If the strength of the glass substrate is insufficient due to thinning, the handleability of the glass substrate is lowered in the manufacturing process of the device.

Therefore, in the past, the following method has been widely used: after forming a device member (for example, a thin film transistor) on a glass substrate having a thickness larger than the final thickness, the glass substrate is thinned by a chemical etching treatment.

However, in this method, for example, the thickness of one glass substrate is When 0.7 mm is thinned to 0.2 mm or 0.1 mm, most of the material of the original glass substrate is scraped off with an etching solution, which is not preferable from the viewpoints of productivity, raw material use efficiency, and the like. Further, in the method of thinning the glass substrate by chemical etching, when there is a fine flaw on the surface of the glass substrate, fine pits (etching spots) may be formed starting from the scratch by the etching process. And become the case of optical defects.

Recently, in order to cope with the above-mentioned problems, there has been proposed a method of 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 a thin glass substrate of a glass laminate, and then supporting the support plate. The thin glass substrate is separated (for example, Patent Document 1). The reinforcing plate has a support plate and a polyoxymethylene resin layer fixed to the support plate, and the polyoxymethylene resin layer and the thin glass substrate are in close contact with each other in a peelable manner. The interface between the polyoxymethylene resin layer of the glass laminate and the thin glass substrate is peeled off, and the reinforcing plate separated from the thin glass substrate can be laminated with a new thin glass substrate to be reused as a glass laminate.

Advanced technical literature Patent literature

Patent Document 1: International Publication No. 2007/018028

Summary of invention

In the glass laminate described in Patent Document 1, a higher heat resistance is required in recent years. Forming an electronic device with high functionality and complexity of components for electronic devices formed on a glass substrate of a glass laminate The temperature at which the member is used becomes higher and the temperature is required to be exposed to the high temperature for a long time. Moreover, since the glass substrate to be used has also been made thinner, workability becomes difficult.

The glass laminate system described in Patent Document 1 can withstand treatment at 300 ° C for 1 hour in the atmosphere. However, in the case of the inventors of the present invention, in the case where the glass laminate using a thick thin glass substrate is subjected to treatment at 360 ° C for 1 hour, the glass substrate is subjected to polyfluorination. When the surface of the resin layer is peeled off, the glass substrate is not peeled off from the surface of the resin layer and a part thereof is broken, or a part of the resin of the resin layer remains on the glass substrate, resulting in low productivity of the electronic device.

The present invention has been made in view of the above problems, and an object of the invention is to provide a glass laminate which can suppress peeling strength between a glass substrate and a polyoxymethylene resin layer even after high-temperature heat treatment, and a method for producing the same. Ascending, the glass substrate can be easily peeled off.

Further, it is an object of the present invention to provide a support substrate for producing an agglomerated epoxy resin layer of the glass laminate.

The present inventors have completed the present invention as a result of efforts to develop the above problems.

That is, the first aspect of the present invention is a glass laminate having a support substrate, a polyoxyxene resin layer, and a glass substrate in this order, and the peel strength of the interface between the support substrate and the polyoxyxene resin layer is greater than that of the polyfluorene. The peeling strength of the interface between the oxygen resin layer and the glass substrate, and the polyoxynoxy resin of the polyoxyxylene resin layer is a crosslinked product of the crosslinkable organic polyoxyalkylene, and the polyfluorene measured by the nanoindentation method The modulus of elasticity of the oxygen resin layer is 0.5 to 2.5 MPa.

In the first aspect, the crosslinked product of the crosslinkable organopolyoxane is a crosslinked product obtained by reacting an organic polyoxyalkylene having an alkenyl group with an organopolysiloxane having a hydroquinone group. It is appropriate.

In the first aspect, the molar ratio of the alkenyl group to the hydroquinone group (alkenyl molar number/hydroquinone molar number) is preferably 1/1 to 1/0.8.

In the first aspect, the polyoxyphthalocene resin layer preferably contains a polyoxygenated oil.

In the first aspect, the thickness of the polyoxyxene resin layer is preferably 2 to 100 μm.

In the first aspect, it is preferred to support the substrate-based glass plate.

A second aspect of the present invention is a method for producing a glass laminate according to a first aspect, which comprises forming a layer containing a crosslinkable organopolysiloxane on one side of a support substrate, and on a support substrate surface The crosslinkable organopolyoxane is crosslinked to form a polyoxyxene resin layer, followed by a glass substrate on the surface area of the polyoxyxene resin layer.

A third aspect of the present invention is a support substrate for agglomerating an epoxy resin layer, which has a support substrate and a polyoxyxene resin layer provided on the surface of the support substrate, and a polyoxyxylene resin layer The resin is a crosslinked product of a crosslinkable organopolyoxane, and the elastic modulus of the polyoxyxylene resin layer measured by a nanoindentation method is 0.5 to 2.5 MPa. .

According to the present invention, it is possible to provide a glass laminate and a method for producing the same, which can suppress the increase in the peeling strength of the glass substrate and the polyoxymethylene resin layer even after the high-temperature heat treatment, and can easily peel off the glass substrate.

Further, according to the present invention, it is also possible to provide a support substrate for use in the production of the agglomerated epoxy resin layer of the glass laminate.

10‧‧‧glass laminate

12‧‧‧Support substrate

14‧‧‧Polyoxy resin layer

14a‧‧‧1st main surface of polyoxyl resin layer

16‧‧‧ glass substrate

16a‧‧‧1st main surface of the glass substrate

16b‧‧‧2nd main surface of the glass substrate

18‧‧‧Support substrate with polyoxyl resin layer

20‧‧‧Members for electronic devices

22‧‧‧Laminated body of components for electronic devices

24‧‧‧ Glass substrate with attached components

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a glass laminate of the present invention.

2(A) to 2(D) are schematic cross-sectional views showing an embodiment of a method of manufacturing a glass substrate of an attached member of the present invention in order of steps.

Form for implementing the invention

In the following, the present invention is not limited to the following embodiments, and various modifications and changes can be made to the following embodiments without departing from the scope of the invention.

The glass laminate of the present invention has a support substrate, a polyoxymethylene resin layer, and a glass substrate in this order. That is, a polyoxyxylene resin layer is interposed between the support substrate and the glass substrate, so that one side of the polyoxyxene resin layer is in contact with the support substrate, and the other side is in contact with the glass substrate.

One of the characteristics of the glass laminate of the present invention is such that the elastic modulus of the polyoxynated resin layer measured by the nanoindentation method is within a predetermined range. In particular, the elastic modulus of the polyoxynated resin layer formed on the support substrate is within a predetermined range. The polyoxyxene resin layer having an elastic modulus within a predetermined range is softer than a conventional polyoxyxene resin layer. When such a soft polyoxyalkylene resin layer is used, the glass substrate disposed on the polyoxyalkylene resin layer is adhered to a certain extent to prevent the positional deviation, and the glass substrate can be easily peeled off. Although it is not clear to obtain detailed reasons for the above characteristics, it is presumed as follows. First, when the glass substrate is laminated on the polyoxyalkylene resin layer, since the polyoxyxylene resin layer is soft, it deforms along the shape of the surface of the glass substrate, and there is no possibility between the polyoxyalkylene resin layer and the glass substrate. A void or the like occurs, and the polyoxymethylene resin layer and the glass substrate can be in close contact with each other. Further, when the glass substrate is peeled off from the polyoxyxene resin layer after the high-temperature heat treatment, since the polyoxynitride resin layer is easily deformed, local stress can be prevented from being locally applied to the glass substrate, and as a result, the glass substrate can be easily peeled off.

Fig. 1 is a schematic cross-sectional view showing an example of a glass laminate of the present invention.

As shown in Fig. 1, the glass laminate 10 is a laminate of the support substrate 12, the glass substrate 16, and the polyoxyn resin layer 14 present between them. The polyoxyxene resin layer 14 is in contact with the support substrate 12 on one side, and the other surface thereof is in contact with the first main surface 16a of the glass substrate 16. In other words, the polyoxyxene resin layer 14 is in contact with the first main surface 16a of the glass substrate 16.

The two-layer portion composed of the support base material 12 and the polyoxyxene resin layer 14 is used to reinforce the glass substrate 16 in the member forming step of manufacturing a member for an electronic device such as a liquid crystal panel. Further, the two-layer portion composed of the support base material 12 and the polyoxynoxy resin layer 14 which are previously manufactured for the production of the glass laminate 10 is referred to as a support base material 18 for agglomerating the epoxy resin layer.

This glass laminate 10 is used until the member forming step described later. In other words, the glass laminate 10 is formed by forming a member for an electronic device such as a liquid crystal display device on the surface of the second main surface 16b of the glass substrate 16. After that, the glass laminate in which the member for electronic device is formed is separated into the support substrate 18 of the agglomerated epoxy resin layer and the glass of the member for electronic device. The substrate, while the support substrate 18 of the agglomerated epoxy resin layer does not become part of the electronic device. Therefore, the new glass substrate 16 can be laminated on the support substrate 18 of the agglomerated epoxy resin layer and reused as a new glass laminate 10.

The interface between the support substrate 12 and the polyoxyxene resin layer 14 has a peel strength (x), and if a stress exceeding the peel strength (x) is applied to the interface between the support substrate 12 and the polyoxyxyl resin layer 14, The interface between the support substrate 12 and the polyoxyxene resin layer 14 is peeled off. The interface between the polyoxyxene resin layer 14 and the glass substrate 16 has a peeling strength (y), and if a stress exceeding the peeling strength (y) in the pulling direction is applied to the interface between the polyoxynoxy resin layer 14 and the glass substrate 16, the poly The interface between the silicone resin layer 14 and the glass substrate 16 is peeled off.

In the glass laminate 10 (also referred to as a laminate of a member for an electronic device to be described later), the peel strength (x) is greater than (higher than) the peel strength (y). Therefore, when the stress in the direction in which the support substrate 12 and the glass substrate 16 are pulled apart is applied to the glass laminate 10, the glass laminate 10 of the present invention is peeled off at the interface between the polyimide layer 14 and the glass substrate 16. The support substrate 18 is separated into a glass substrate 16 and an agglomerated epoxy resin layer.

In other words, the polyoxyxene resin layer 14 is fixed to the support substrate 12 to form the support substrate 18 of the agglomerated epoxy resin layer, and the glass substrate 16 is adhered to the polyoxynitride resin layer 14 in a peelable manner.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means increasing the adhesion of the silicone resin layer 14 to the support substrate 12, and maintaining relatively high adhesion to the glass substrate 16 after the heat treatment.

In order to improve the adhesion of the polyoxyxene resin layer 14 to the support substrate 12, such as Generally, it is preferable that the crosslinkable organopolysiloxane is cross-linked and hardened on the support substrate 12 to form the polyoxyxene resin layer 14. By the adhesive force at the time of cross-linking hardening, the polyoxyalkylene resin layer 14 in which the support substrate 12 is bonded with high bonding force can be formed.

On the other hand, it is common that the cross-linking of the cross-linking organopolyoxane hardened material after crosslinking hardening has a lower binding force to the glass substrate 16 than the above-described cross-linking hardening. Therefore, the crosslinkable organopolyoxane is cross-linked and hardened on the support substrate 12 to form the polyoxyxene resin layer 14, and then the glass substrate 16 is laminated on the surface of the polyoxynoxy resin layer 14 to produce the glass laminate 10. , is suitable.

The glass laminate according to the first aspect of the present invention has a support substrate, a polyoxynitride resin layer, and a glass substrate in this order, and the peel strength of the interface between the support substrate and the polyoxyxylene resin layer is larger than that of the polyoxynoxy resin. The peel strength of the interface between the layer and the glass substrate, and the polyoxynoxy resin of the polyoxyxene resin layer is a crosslinked product of a crosslinkable organopolyoxyalkylene, and the polyoxyalkylene resin layer is measured by a nanoindentation method. The modulus of elasticity is 0.5 to 2.5 MPa.

In the following, the respective layers (the support substrate 12, the glass substrate 16, and the polyoxyalkylene resin layer 14) constituting the glass laminate 10 will be described in detail, and then the glass substrate of the glass laminate and the member for an electronic device will be described in detail. Production method.

[Support substrate]

The support substrate 12 is reinforced by supporting the glass substrate 16 and prevents deformation, damage, breakage, etc. of the glass substrate 16 when the electronic device member is manufactured in the member forming step (the step of manufacturing the electronic device member) to be described later. .

As the support base material 12, a metal plate such as a glass plate, a plastic plate, or a SUS plate can be used. In general, the member forming step is accompanied by a heat treatment, so that the support substrate 12 is preferably formed of a material having a small difference in the average linear expansion coefficient of the glass substrate 16, and is preferably formed of the same material as the glass substrate 16, and The support substrate 12 is preferably a glass plate. In particular, the support substrate 12 is preferably a glass plate composed of the same glass material as the glass substrate 16.

The thickness of the support substrate 12 can be thicker or thinner than the glass substrate 16. The thickness of the support substrate 12 is preferably selected in accordance with the thickness of the glass substrate 16, the thickness of the polyoxynitride resin layer 14, and the thickness of the glass laminate 10. For example, the current member forming step is designed to handle a substrate having a thickness of 0.5 mm, and when the thickness of the glass substrate 16 and the thickness of the polyoxyxene resin layer 14 are 0.1 mm in total, the thickness of the support substrate 12 is 0.4. Mm. The thickness of the support substrate 12 is generally 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 from the viewpoints of easy handling and difficulty in cracking. Further, after the member for an electronic device is formed, it is necessary to appropriately bend the rigidity without being broken at the time of peeling. Therefore, the thickness of the glass plate is preferably 1.0 mm or less.

The difference between the average linear expansion coefficient of the support substrate 12 and the glass substrate 16 at 25 to 300 ° C is preferably 500 × 10 ^-7 / ° C or less, preferably 300 × 10 ^-7 / ° C or less, more preferably 200 × 10 ^-7 / °C or less. If the difference in the average linear expansion coefficient is too large, the glass laminate 10 may be largely recurved during heating and cooling in the member forming step, and the support substrate 12 and the glass substrate 16 may be peeled off. When the material of the support substrate 12 and the material of the glass substrate 16 are the same, such problems can be suppressed, so the support substrate is preferably a glass plate.

[glass substrate]

In the glass substrate 16, the first main surface 16a is in contact with the polyoxynitride resin layer 14, and the electronic device member is provided on the second main surface 16b on the side opposite to the polyoxynitride resin layer 14 side.

The type of the glass substrate 16 can be generally used, 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. The average linear expansion coefficient specified in JIS R 3102 (1995 Revision) was used as an index of the heat shrinkage rate.

When the average linear expansion coefficient of the glass substrate 16 is high, since the member forming step is often accompanied by heat treatment, various defects 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 under heating is cooled, the positional shift of the TFT may become excessive 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 forming method may be a general method, and for example, a floating glass plate method, a melting method, a slit down method, a vertical lead method, a Lubbers process, or the like may be used. Further, in particular, the glass substrate 16 having a small thickness can be formed by a method of reshaping (redraw process) in which a glass temporarily formed into a plate shape is heated to a temperature at which it can be formed, and stretched by stretching or the like. Thinning.

The glass of the glass substrate 16 is not particularly limited, and is preferably an alkali-free borosilicate glass, a borosilicate glass, a soda lime glass, or a high cerium oxide glass. Other oxide-based glass containing cerium oxide as a main component. The oxide-based glass is preferably glass having a cerium oxide content of 40 to 90% by mass in terms of oxide.

As the glass of the glass substrate 16, a glass suitable for a type such as a member for an electronic device, a manufacturing step thereof, or the like is used. For example, a glass substrate for a liquid crystal panel is formed of glass (alkali-free glass) which does not substantially contain an alkali metal component because it is easily affected by elution of an alkali metal component (but usually contains an alkaline earth metal component). As such, the glass of the glass substrate 16 is suitably selected based on the type of device to be applied and the manufacturing steps thereof.

The thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.20 mm or less, more preferably 0.15 mm or less, and particularly preferably 0.10 mm or less from the viewpoint of reduction in thickness and/or weight reduction of the glass substrate 16. When it is 0.3 mm or less, it is possible to impart good flexibility to the glass substrate 16. When it is 0.15 mm or less, the glass substrate 16 can be wound up in a roll shape.

Moreover, the thickness of the glass substrate 16 is preferably 0.03 mm or more from the viewpoint of easy production of the glass substrate 16, easy operation of the glass substrate 16, and the like.

Further, 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. Moreover, in this case, "the thickness of the glass substrate 16" means the total thickness of all layers.

[Polyoxygenated resin layer]

The polyoxyxene resin layer is substantially composed of a polyfluorene oxide resin, and the polyfluorene oxide resin is a crosslinked product of a crosslinkable organopolyoxyalkylene oxide, and the polyoxynoxy resin layer is measured by a nanoindentation method. The modulus of elasticity is 0.5 to 2.5 MPa. The peel strength of the interface between the support substrate and the polyoxyxene resin layer is greater than that of the polysiloxane resin layer and the glass Peel strength of the interface of the glass substrate.

The polyoxyxene resin layer 14 prevents the positional shift of the glass substrate 16 until the operation of separating the glass substrate 16 from the support substrate 12, and prevents the glass substrate 16 and the like from being damaged by the separation operation. The surface of the polyoxyxene resin layer 14 that is in contact with the glass substrate 16 (the first main surface of the polyoxyxene resin layer) 14a is detachably adhered to the first main surface 16a of the glass substrate 16. On the other hand, the polyoxyxene resin layer 14 is fixed to the support substrate 12. Therefore, the polyoxyxene resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the peel strength (y) of the interface is between the polyoxynitride resin layer 14 and the support substrate 12. The interface peel strength (x) is lower.

In other words, when the glass substrate 16 is separated from the support substrate 12, the interface between the first main surface 16a of the glass substrate 16 and the polyoxy-oxygen resin layer 14 is peeled off, and the support substrate 12 and the polyoxy-oxygen resin layer 14 are separated. The interface is not easy to peel off. Therefore, although the polyoxyxene resin layer 14 is in close contact with the first main surface 16a of the glass substrate 16, it has surface characteristics which can easily peel the glass substrate 16. In other words, the polyoxyxene resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a certain degree of bonding force to prevent the positional shift of the glass substrate 16, and the like, while peeling off the glass substrate 16 The glass substrate 16 is not damaged, and the bonding force to the extent that it can be easily peeled off is combined. In the present invention, the property of the surface of the polyoxyxylene resin layer 14 which can be easily peeled off is referred to as peelability. On the other hand, the first main surface of the support substrate 12 and the polyoxynitride resin layer 14 are bonded by a bonding force which is relatively difficult to peel off.

Further, the bonding force between the polyoxy-oxygen resin layer 14 and the interface of the glass substrate 16 can be formed on the surface (second main surface 16b) of the glass substrate 16 of the glass laminate 10. The front and rear members of the electronic device are changed (that is, the peel strength (x) or the peel strength (y) may vary). However, even after forming the member for an electronic device, the peel strength (y) is lower than the peel strength (x).

The polyoxyxene resin layer 14 and the glass substrate 16 are considered to be bonded by a bonding force derived from a weak adhesion force or a van der Waals force. When the polyoxyxene resin layer 14 is formed and the glass substrate 16 is formed on the surface layer thereof, if the polyoxyxylene resin of the polyoxyxylene resin layer 14 is sufficiently crosslinked to the extent that the adhesion is not exhibited, the salt is derived from The combination of Van der Waals force is combined. However, many of the polyoxynoxy resins of the polyoxyxene resin layer 14 have a certain degree of weak adhesion. In the case where the member for an electronic device is formed on the laminated body after the production of the glass laminate 10, for example, when the adhesiveness is extremely low, the polyoxynoxy resin of the polyoxyxene resin layer 14 is still affected by the heating operation or the like. It adheres to the surface of the glass substrate 16, and the bonding force between the polyoxy-resin layer 14 and the glass substrate 16 rises.

In some cases, it is also possible to perform a process of weakening the bonding force between the surface of the polyoxynoxy resin layer 14 before lamination or the first main surface 16a of the glass substrate 16 before lamination. By laminating after the non-adhesive treatment or the like on the buildup layer, the bonding strength between the polyimide resin layer 14 and the glass substrate 16 can be weakened, and the peel strength (y) can be lowered.

Further, the polyoxyxene resin layer 14 is bonded to the surface of the support substrate 12 by a strong bonding force such as an adhesive force or an adhesive force. For example, as described above, the cross-linking organopolysiloxane can be cross-linked and hardened on the surface of the support substrate 12, whereby the polyoxyxylene resin as a cross-linking material is adhered to the surface of the support substrate 12, thereby obtaining high. Binding force. Further, a treatment (for example, treatment using a coupling agent) for causing a strong bonding force between the surface of the support substrate 12 and the polyoxyalkylene resin layer 14 can be applied. The bonding force between the surface of the support substrate 12 and the polyoxyalkylene resin layer 14 is increased.

The polyoxyxene resin layer 14 is bonded to the support substrate 12 with a high bonding force, meaning that the interface peel strength (x) of both is high.

The elastic modulus of the polyoxyxene resin layer 14 measured by the nanoindentation method is 0.5 to 2.5 MPa. Among them, from the viewpoint of better peelability of the glass substrate 16, it is preferably 0.5 to 2.0 MPa, and preferably 0.5 to 1.2 MPa.

When the elastic modulus of the polyoxyxene resin layer 14 is less than 0.5 MPa and the polyoxyxylene resin layer 14 is broken and exceeds 2.5 MPa, the glass substrate 16 and the polyoxynoxy resin layer 14 are hardly peeled off. Further, the elastic modulus is an average value obtained by arithmetically averaging the elastic modulus measured at any five or more points on the surface of the polyoxynphthene resin layer 14.

In order to make the elastic modulus measured by the nanoindentation method in the above range, as described later, the polyfluorene oxide layer may be contained in the polyfluorene oxide resin layer by using a specific polyoxynitride resin layer as the polyoxynitride resin layer. The oil, the method of forming the polyoxyxene resin layer, and the like are controlled.

In the present invention, the elastic modulus measuring method using the nanoindentation method is obtained by combining JKR (Johnson-Kendall-Roberts) analysis and force test using an atomic force microscope to obtain an elastic modulus (Young's rate). In this manner, the cantilever is moved vertically to the sample surface, and the load is measured at the position of the cantilever. The sample which is very hard to the elastic constant of the cantilever does not undergo deformation of the sample, but the soft sample is deformed depending on the load, and the relationship between the load and the amount of deformation of the sample is obtained by using this point. In the range where the indentation is small and the sample is soft, the JKR analysis is optimized.

The details of the above method for determining the modulus of elasticity are revealed in the theory of polymer. Collection Vol.69, No. 7, 435~442. In addition, the measurement procedure of the elastic modulus is described in detail in the section of the embodiment to be described later.

The thickness of the polyoxyxene resin layer 14 is not particularly limited, but is preferably 2 to 100 μm, more preferably 3 to 50 μm, and still more preferably 7 to 20 μm. When the thickness of the polyoxyxene resin layer 14 is in such a range, the occurrence of warpage defects of the glass substrate 16 can be suppressed even if bubbles or foreign matter or the like is interposed between the polyoxynoxy resin layer 14 and the glass substrate 16. Further, when the thickness of the polyoxyxene resin layer 14 is too thick, it takes time and material to form it, which is not economical, and heat resistance may be lowered. Further, if the thickness of the polyoxyxene resin layer 14 is too small, the adhesion between the polyoxymethylene resin layer 14 and the glass substrate 16 may be lowered.

Further, the polyoxyxene resin layer 14 may be composed of two or more layers. At this time, "the thickness of the polyoxyxene resin layer 14" means the total thickness of all the layers.

Further, when the polyoxyxene resin layer 14 is composed of two or more layers, the resin forming each layer may be a different crosslinked polyfluorene oxide resin.

The polyfluorene oxide resin contained in the polyoxyxene resin layer 14 is a crosslinked product of a crosslinkable organopolyoxane, and usually forms a three-dimensional network structure.

The type of the cross-linkable organopolysiloxane is not particularly limited, and as long as it is crosslinked and hardened by a predetermined crosslinking reaction to form a crosslinked product (hardened product) constituting the polyoxynoxy resin, the structure is not particularly limited. It has a predetermined crosslinkability. The form of crosslinking is not particularly limited, and a suitable conventional form can be employed depending on the kind of the crosslinkable group contained in the crosslinkable organopolysiloxane. For example, a hydroquinonelation reaction, a condensation reaction, or a radical reaction by a heat treatment, a high energy ray treatment or a radical polymerization initiator may be mentioned.

More specifically, the crosslinkable organopolyoxane has an alkenyl group or an alkynyl group. When a radical reactive group is used, it is crosslinked by the reaction of the radical reactive groups by the above-mentioned radical reaction to become a cured product (crosslinked polyoxyl resin).

Further, when the crosslinkable organopolysiloxane has a sterol group, it is crosslinked by a condensation reaction of sterol groups to form a cured product.

Further, when the crosslinkable organopolyoxane contains an organic polyoxyalkylene (ie, an organic alkenyl polyoxyalkylene) having an alkenyl group (vinyl group or the like) bonded to a ruthenium atom, and having an anthracene When an atomically bonded hydrogen atom (hydroquinone) of an organopolyoxyalkylene (ie, an organohydrogenpolyoxyalkylene) is in the presence of a hydroquinone catalyst (for example, a platinum-based catalyst), It is crosslinked by a hydroquinone reaction to become a cured product.

Among them, from the viewpoint that the polyether oxide resin layer 14 and the glass substrate 16 are easily formed, the crosslinkable organopolysiloxane is preferably in the form of the following organic polyoxane: at both ends and/or Or an organopolysiloxane having an alkenyl group (hereinafter also referred to as an organic polyoxosiloxane A as appropriate), and an organopolyoxyalkylene having a hydroquinone at both terminals and/or a side chain (hereinafter also suitably referred to as It is an organic polyoxane B).

Further, 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, a hexenyl group, and the like, and from the viewpoint of good heat resistance. It is preferred to use vinyl.

Further, examples of the group other than the alkenyl group contained in the organopolyoxyalkylene A and the hydroquinone group contained in the organopolyoxyalkylene B include an alkyl group (especially an alkyl group having 4 or less carbon atoms). base).

The position of the alkenyl group in the organopolyoxane A is not particularly limited. When the organopolyoxyalkylene A is linear, the alkenyl group may be present in any of the M unit and the D unit shown below, or may be present in both the M unit and the D unit. From the viewpoint of the hardening speed, it is preferably present in at least the M unit, and is preferably present in both of the M units.

In addition, the M unit and the D unit are examples of the basic structural unit of the organopolyoxyalkylene, the M unit is bonded with three organic monofunctional oxirane units; the D unit is bonded with two organic groups. Bifunctional oxirane unit. In the oxoxane unit, since the oxime is bonded to the bond of two ruthenium atoms through one oxygen atom, the oxygen atom of each ruthenium atom bonded by the siloxane is regarded as 1/2. The formula in the formula is O _1/2 .

The number of alkenyl groups in the organopolyoxane A is not particularly limited, but it is preferably 1 to 3 in one molecule, and preferably 2 in two.

A suitable structure of the organopolyoxane A is linear or cyclic, and has two or more alkenyl groups in one molecule, and the alkenyl group has one or more on both sides of two M units.

The position of the hydroquinone group in the organopolyoxane B is not particularly limited. When the organopolyoxane A is linear, the hydroquinone group may be present in any of the M unit and the D unit, or may be present in Both M units and D units. From the standpoint of the hardening speed, it is preferred to exist at least in the D unit.

The number of hydroquinone groups in the organic polyoxetane B is not particularly limited, and is preferably 1 minute. There are at least 3 in the sub, and 3 are preferred.

A suitable structure of the organic polyoxyalkylene B is preferably a hydrofluorenyl group having two or more hydroquinone groups in one molecule when the organopolyoxane A is linear or cyclic. More than 30%.

The mixing ratio of the organopolyoxane A to the organopolyoxane B is not particularly limited, but the organic polyfluorene oxide can be adjusted so that the elastic modulus of the obtained polyoxynoxy resin layer by the nanoindentation method is within a specific range. The mixing ratio of the alkane A to the organopolyoxane B. From the viewpoint of good releasability of the glass substrate, the molar ratio of all alkenyl groups in the organopolyoxane A to hydroquinone groups (hydrogen atoms bonded to the ruthenium atoms) in the organopolyoxane B ( The alkenyl molar number/hydroquinone molar number is preferably adjusted to 1/1 to 1/0.8. Among them, it is preferable to adjust the mixing ratio to be 1/1 to 1/0.9.

As the crosslinkable organopolyoxane, the organopolyoxane A is preferably linear or cyclic in terms of a suitable structure and mixing ratio, and has two or more alkenyl groups in one molecule. In the case where one or more of the two M units are present on each side, the organopolyoxane B is preferably one or more hydroquinone groups in one molecule, and the molar content of the hydroquinone group is 30% or more; The molar ratio of all alkenyl groups in the oxoxane A to the hydroquinone group (hydrogen atom bonded to the ruthenium atom) in the organopolyoxane B (alkenyl mole number / hydroquinone molar number) Should be adjusted to 1/1~1/0.8.

As the hydroquinone catalyst, a platinum group metal catalyst is preferably used. The platinum group-based catalyst may, for example, be a catalyst such as a platinum-based, palladium-based or ruthenium-based catalyst, and in particular, a platinum-based catalyst is suitable from the viewpoint of economy and reactivity. As the platinum group metal catalyst, a conventional one can be used. Specifically, platinum micro Powder, platinum black, chlorinated first platinum acid and chlorinated second platinum acid such as chloroplatinic acid, platinum tetrachloride, chloroplatinic acid alcohol compound or aldehyde compound, or platinum olefin complex, alkenyl hydrazine Oxylkane complex, carbonyl complex, and the like.

The amount of use of the hydroquinone-based catalyst is preferably 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the total mass of the organopolyoxane A and the organopolyoxyalkylene B. . The platinum component is preferably 2 to 400 ppm, and preferably 2 to 300 ppm, based on 100 masses of the total mass of the organopolyoxane A and the organopolyoxane B.

The weight average molecular weight of the cross-linkable organopolysiloxane is not particularly limited, but it is good in handleability and good film formability, and more suppresses the decomposition of the polyoxyl resin under high-temperature treatment conditions, and GPC (condensation) The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably from 1,000 to 5,000,000, preferably from 2,000 to 3,000,000.

The viscosity of the cross-linkable organopolysiloxane is preferably from 10 to 5,000 mPa s, preferably from 15 to 3,000 mPa s. Also in the present specification, the viscosity is a value measured at 25 ° C especially when not specified.

The curable polyanthracene resin composition of the present invention is preferably used in combination with an activity inhibitor (also referred to as a reaction inhibitor, a retarder, etc.) having an activity of inhibiting catalyst activity for the purpose of adjusting the activity of the catalyst and the catalyst. ). Examples of the activity inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, hydrazine compounds, and organic chlorine compounds. Specific examples of the acetylene-based compound include 1-acetyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 4-ethyl-1-octyn-3-ol, and the like. . Further, as needed, various cerium oxide, calcium carbonate, and oxygen may be contained within a range that does not impair the effects of the present invention. Inorganic fillers such as iron. Further, a metal compound such as a metal oxide may be contained as a heat resistance improving agent.

Further, an organic solvent such as hexane, heptane, octane, toluene or xylene or a dispersion medium such as water is a component which does not constitute a cured polyfluorene oxide resin, but may be used for coating a curable polyoxyxene resin composition. For the purpose of improving workability and the like, the curable polyoxyxene resin composition of the present invention is used in combination.

In the polyoxyxene resin layer 14, a polyoxygenated oil may be included. By including polyoxyxylene oil in the polyoxyxene resin layer, the elastic modulus of the polyoxyxene resin layer measured by the nanoindentation method can be controlled to a predetermined value. Unlike the above-mentioned crosslinkable organopolyoxane, the polyoxygenated oil does not react to the crosslinkable organopolyoxane, and is a non-crosslinkable (non-reactive) organic polyfluorene which does not have crosslinkability. Oxytomane.

The type of the polyoxygenated oil is not particularly limited, and examples thereof include straight-chain polyfluorene oxides such as dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene, and diphenyl polyoxyalkylene. A modified polyoxygenated oil such as a polyether group or a halogen group is introduced into the side chain or the terminal of the helium oxide oil.

In addition, a specific commercially available product name or model of the polyoxygenated oil may be, for example, KTSF433 (made by Momentive Advanced Materials Japan Group) in the case of a polyoxyphthalic acid having an aromatic group (for example, phenyl group); KF-50 , KF-53, KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.); SH550 (manufactured by Toray Dow Corning Co., Ltd.).

In the case of a polyphthalic acid oil having no aromatic group, SH200 (manufactured by Toray Dow Corning Co., Ltd.), KNS-330 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

The viscosity of the polyoxygenated oil is not particularly limited, but is preferable from the viewpoint that the surface of the polyimide resin layer 14 is easily bleed out, the peeling property of the glass substrate 16 is further improved, and the transparency of the peeled glass substrate 16 is further improved. It is preferably 100~6000mm ² /s, preferably 100~3000mm ² /s, and more preferably 125~1000mm ² /s.

The content of the polyoxygenated oil in the polyoxyxene resin layer 14 is not particularly limited, but the peeling property from the glass substrate 16 is good, and the transparency of the peeled glass substrate is further improved, with respect to the polyoxyxene resin 100. The mass fraction is preferably 6 to 20 parts by mass, 6 to 15 parts by mass, and more preferably 8 to 15 parts by mass.

[Glass laminate and its manufacturing method]

The glass laminate 10 of the present invention is a laminate of the support substrate 12, the glass substrate 16, and the polyoxyalkylene resin layer 14 present between them, as described above.

The method for producing the glass laminate 10 of the present invention is not particularly limited, and a conventional method can be employed. For example, a method of supporting the substrate 18 on which the agglomerated epoxy resin layer of the polyoxyxylene resin layer 14 is fixed on the support substrate 12 and laminating the glass substrate 16 on the polyoxynitride layer 14 is preferable. Among them, in order to obtain a laminate having a peel strength (x) larger than the peel strength (y), it is preferred to form a polyoxyxyl resin layer 14 by crosslinking and hardening a predetermined crosslinkable organopolysiloxane on the surface of the support substrate 12. Methods. That is, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate 12, and the crosslinkable organopolyoxane is crosslinked on the surface of the support substrate 12 to form a polyoxyxene resin layer 14. (Crosslinked polyoxynoxy resin), followed by a method of producing a glass laminate 10 on the polycrystalline epoxy resin layer of the polyoxyxylene resin layer 14 on the glass substrate 16. Further, by subjecting the predetermined crosslinkable organopolyoxane to cross-linking and hardening on the surface of the support substrate 12, the elastic modulus by the nanoindentation method can be controlled to a predetermined range.

When the surface of the support substrate 12 is hardened by the cross-linking organopolysiloxane, the interaction between the polyoxyxene resin and the surface of the support substrate 12 is followed by the interaction with the surface of the support substrate 12 during the hardening reaction. It will become higher. Therefore, even if the glass substrate 16 and the support substrate 12 are made of the same material, the difference in peel strength between the polyoxymethylene resin layer 14 and the two can be made.

Hereinafter, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate 12, and a crosslinkable organopolysiloxane is crosslinked on the surface of the support substrate 12 to form a polyoxyxene resin layer 14. The step of forming the resin layer forming step; the step of forming the glass layered body 10 on the polyoxyxylene resin-area glass substrate 16 of the polyoxynoxy resin layer 14 is referred to as a lamination step, and the procedure of each step is detailed. Said.

(Resin layer forming step)

In the resin layer forming step, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate 12, and a crosslinkable organopolyoxane is crosslinked on the surface of the support substrate 12 to form a crosslinkable layer. Polyoxygenated resin layer 14.

In order to form a layer containing a crosslinkable organopolyoxane on the support substrate 12, it is preferred to use a coating composition obtained by dissolving a crosslinkable organopolysiloxane in a solvent, and coating the composition. A solution layer is formed on the support substrate 12, and the solvent is removed to form a layer containing a crosslinkable organopolyoxane. The thickness of the layer containing the crosslinkable organopolysiloxane can be controlled by adjusting the concentration of the crosslinkable organopolyoxane in the composition or the like.

The solvent is not particularly limited as long as it is a solvent which can easily dissolve the crosslinkable organopolysiloxane in an operating environment and is easily volatilized and removed. Specifically, for example, butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF, chloroform, and the like.

A method of applying a composition containing a crosslinkable organopolysiloxane on the surface of the support substrate 12 is not particularly limited, and a conventional method can be used. For example, 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, a gravure printing method, and the like can be mentioned.

Thereafter, a drying treatment may be performed to remove the solvent, as needed. The method of the drying treatment is not particularly limited, and examples thereof include a method of removing a solvent under reduced pressure, and a method of heating at a temperature at which the crosslinkable organopolysiloxane is not cured.

Next, the crosslinkable organopolyoxane on the support substrate 12 is crosslinked to form the polyoxynoxy resin layer 14. More specifically, as shown in FIG. 2(A), a polyoxynitride resin layer 14 is formed on at least one surface of the support substrate 12 in this step.

As a method of hardening (crosslinking), as described above, an appropriate optimum method can be selected in view of the crosslinking form of the crosslinkable organopolyoxane, and examples thereof include heat treatment or exposure treatment. In the case where the crosslinkable organopolysiloxane is crosslinked by a hydroquinonelation reaction, a condensation reaction or a radical reaction, a polyoxyxene resin having good adhesion to the glass substrate 16 and heat resistance can be obtained. From the viewpoint, the polyoxynoxy resin layer 14 is preferably produced by thermosetting.

Hereinafter, the heat hardening state will be described in detail.

The temperature condition for thermally curing the crosslinkable organopolysiloxane is to improve the heat resistance of the polyoxynated resin layer 14 and to control the peel strength (y) of the glass substrate 16 and the laminate to be within the range as described above. There is no particular limitation, but 150 to 300 ° C is preferred, and 180 to 250 ° C is preferred. Again, heating time Usually 10 to 120 is appropriate, 30 to 60 is preferred. If the temperature of the heat curing is too low, the flatness such as heat resistance or the silicone resin layer 14 may be lowered; on the other hand, if the temperature is too high, the peel strength (y) may become too low, which may cause The adhesion between the glass substrate 16 and the polyoxyn resin layer 14 is weak.

Further, the crosslinkable organopolysiloxane can be post-cured (formally hardened) and then cured after pre-curing (pre-curing). By performing pre-curing, a polyoxynitride resin layer 14 having better heat resistance can be obtained. The pre-curing is preferably carried out by removing the solvent. In this case, the step of removing the solvent from the layer to form a layer containing the crosslinkable organopolysiloxane and the polyoxygenated oil is not particularly distinguished from the step of performing the pre-curing.

(layering step)

In the laminating step, the glass substrate 16 is laminated on the surface of the polyoxyxylene resin layer of the polyoxyxylene resin layer 14 obtained in the resin layer forming step, and the support substrate 12, the polyoxyxylene resin layer 14 and the glass substrate 16 are sequentially obtained. The step of the glass laminate 10. More specifically, as shown in FIG. 2(B), the surface of the polyoxyxylene resin layer 14 on the side opposite to the side of the support substrate 12 (the first main surface of the polyoxyalkylene resin layer) 14a, and the first main The first main surface 16a of the glass substrate 16 of the surface 16a and the second main surface 16b serves as an integrated layer, and the polyoxynoxy resin layer 14 and the glass substrate 16 are laminated to obtain a glass laminate 10.

The method of laminating the glass substrate 16 on the polyoxynoxy resin layer 14 is not particularly limited, and a known method can be employed.

For example, a method of laminating the glass substrate 16 on the surface of the polyoxyxene resin layer 14 under a normal pressure environment can be mentioned. In addition, if the glass substrate 16 is overlapped on the surface of the polyoxyxene resin layer 14 as needed, the glass substrate may be formed using a roll or a press member. 16 is pressed against the polyoxyxene resin layer 14. It is preferable that the bubbles mixed between the polyoxynoxy resin layer 14 and the glass substrate 16 are relatively easily removed by pressing by a roll or a press.

When the pressure is laminated by a vacuum lamination method or a vacuum calendering method, it is preferable to suppress the incorporation of air bubbles and ensure good adhesion. The pressing under vacuum also has the advantage that even if fine bubbles remain, the bubbles are not allowed to grow due to heating, and the distortion of the glass substrate 16 is not easily involved.

When the glass substrate 16 is laminated, it is preferable to sufficiently wash the surface of the glass substrate 16 which is in contact with the polyoxynoxy resin layer 14, and to laminate it in an environment having high cleanliness. The higher the degree of cleanliness, the better the flatness of the glass substrate 16 is, and therefore it is preferable.

Further, after the glass substrate 16 is laminated, a pre-annealing treatment (heat treatment) may be performed as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the polyoxynitride resin layer 14 can be improved to achieve an appropriate peel strength (y), and the position of the electronic device member at the member forming step described later. Offsets and the like are less likely to occur, and the productivity of an electronic device is improved.

The conditions of the pre-annealing treatment are selected according to the kind of the polyoxynoxy resin layer 14 to be used, and the peeling strength (y) between the glass substrate 16 and the polyoxyxene resin layer 14 is more suitable. From the viewpoint of the viewpoint, it is preferable to carry out heat treatment for 5 minutes or more (5 to 30 minutes is preferable) at 300 ° C or higher (300 to 400 ° C is preferable).

Further, the formation of the polyoxyxene resin layer 14 is not limited to the above method.

For example, when a support substrate 12 having a surface adhesiveness to a surface of the polysiloxane resin is used, which is made of a material of the glass substrate 16, the cross-linkable organopolysiloxane can be cured on any peelable surface to produce a polyoxyn resin film. The film is interposed between the glass substrate 16 and the support substrate 12 while being laminated.

Further, when the adhesion obtained by the curing of the crosslinkable organopolysiloxane is sufficiently low for the glass substrate 16, and the adhesion is sufficiently high for the support substrate 12, it may be between the glass substrate 16 and the support substrate 12. The crosslinkable organopolysiloxane is hardened to form a polyoxyxene resin layer 14.

Further, even when the support substrate 12 is made of the same glass material as the glass substrate 16, the treatment for improving the surface adhesion of the support substrate 12 can be applied to improve the peel strength to the polyoxymethylene resin layer 14. For example, it can be exemplified by a chemical method (primer treatment) which is a chemically enhanced fixing force of a decane coupling agent, a physical method of increasing a surface active group such as a flame (flame) treatment, and a method of increasing the surface roughness by sandblasting. A mechanical treatment method that increases the grip force.

(glass laminate)

The glass laminate 10 of the present invention can be used for various applications, and examples thereof include the use of an electronic component such as a panel for a display device to be described later, a PV, a secondary battery, and a semiconductor wafer having a circuit formed thereon. Further, in this use, the glass laminate 10 is often exposed to high temperature conditions (for example, 360 ° C or higher) (for example, 1 hour or longer).

Here, the panel for a display device includes an LCD, an OLED, an electronic paper, a plasma display panel, a field small panel, a quantum dot LED panel, a MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

[Glass substrate with attached member and method of manufacturing the same]

In the present invention, a glass substrate (a glass substrate with a member for an electronic device) including a member for a glass substrate and a member for an electronic device is produced by using the laminate.

The method for producing the glass substrate of the member is not particularly limited. However, from the viewpoint of good productivity of the electronic device, it is preferable to form a member for an electronic device on the glass substrate in the glass laminate to produce an electron. The laminated body of the member for a device is used as a peeling surface of the glass substrate side interface of the polyoxyxylene resin layer, and is separated from the laminated body of the member for electronic device to be a support substrate of the glass substrate and the agglomerated epoxy resin layer of the attached member. .

In the following, the step of forming the laminate for the electronic device member on the glass substrate in the glass laminate is described as a member forming step, and the laminate from the electronic device member is The step of separating the glass substrate side of the polyoxyxylene resin layer into a release surface and separating the glass substrate of the attached member and the support substrate of the agglomerated epoxy resin layer is referred to as a separation step.

Hereinafter, the materials and procedures used in each step will be described in detail.

(component forming step)

The member forming step is a step of forming a member for an electronic device on the glass substrate 16 in the glass laminate 10 obtained in the above laminating step. More specifically, as shown in FIG. 2(C), the electronic device member 20 is formed on the second main surface 16b (exposed surface) of the glass substrate 16, and the laminated body 22 of the member for electronic device is obtained.

First, the component 20 for an electronic device used in this step will be described in detail. The procedure of the steps will be detailed later.

(Mechanical components (functional components))

The electronic device member 20 is a member formed on the glass substrate 16 in the glass laminate 10 and constituting at least a part of the electronic device. More specifically, examples of the electronic device member 20 include a member for a display device panel, a solar cell, a thin film secondary battery, or an electronic component such as a semiconductor wafer on which a circuit is formed (for example, for a display device). Member, member for solar cell, member for film secondary battery, circuit for electronic component).

For example, as a member for a solar cell, a transparent electrode such as a tin oxide of a positive electrode, a ruthenium layer represented by a p layer/i layer/n layer, and a metal of a negative electrode may be mentioned as the ruthenium type; Various components such as a compound type, a dye-sensitized type, and a quantum dot type.

In addition, examples of the lithium ion type include 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 collector layer, a resin as a sealing layer, and the like. In other respects, various members such as a nickel-hydrogen type, a polymer type, a ceramic electrolyte type, and the like can be cited.

Further, as a circuit for an electronic component, for example, a CCD or a CMOS may be, for example, a metal of a conductive portion, a tantalum oxide or a tantalum nitride of an insulating portion, and the like, and other aspects may be cited as corresponding to a pressure sensor. Various sensors such as a sensor or a rigid printed circuit board, a flexible printed circuit board, and a rigid flexible printed circuit board.

(procedure of steps)

The method for manufacturing the laminated body 22 of the member for electronic device described above is not particularly In the meantime, the electronic device member 20 is formed on the surface of the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a conventional method depending on the type of the structural member of the electronic device member.

In addition, the electronic device member 20 is not necessarily all of the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter referred to as "all members"), and may be one part of the entire member (hereinafter referred to as "partial" member"). The glass substrate with a part of the member which has been peeled off from the polyoxygenated resin layer 14 can be formed into a glass substrate (corresponding to an electronic device to be described later) to which all the members are attached in the subsequent steps.

Moreover, the glass substrate with all the members peeled off from the polyoxynoxy resin layer 14 can form another member for electronic devices on the peeling surface (first main surface 16a). Further, a laminate having all the members may be assembled, and then the support substrate 12 may be peeled off from the laminate including all the members to produce an electronic device. Furthermore, it is also possible to assemble by using two laminated bodies with all the members, and then peeling off the two supporting base materials 12 from the laminated body with all the members, and manufacturing the glass substrate of the member with two glass substrates.

For example, in the case where the OLED is manufactured, an organic EL is formed on the surface of the glass substrate 16 of the glass laminate 10 on the side opposite to the side of the polyoxynitride layer 14 (corresponding to the second main surface 16b of the glass substrate 16). The structure is formed, and various layers are formed or processed, for example, a transparent electrode is formed, and a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and the like are deposited on the surface on which the transparent electrode is formed to form a back electrode. Use a sealing plate to seal etc. Specific examples of the formation or treatment of these layers include a film formation treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate.

Further, for example, in the production of a TFT-LCD, there are various steps such as a step of forming a TFT, using a photoresist on the second main surface 16b of the glass substrate 16 of the glass laminate 10, and using a CVD method. A metal film and a metal oxide film formed by a general film formation method such as a sputtering method are patterned to form a thin film transistor (TFT), and a CF forming step is performed on the second main glass substrate 16 of the other glass laminate 10. On the surface 16b, a photoresist is used to form a pattern to form a color filter (CF); and a bonding step, a TFT laminated body obtained in the TFT forming step, and a CF laminated body obtained in the CF forming step Laminated.

In the TFT formation step or the CF formation step, TFT or CF is formed on the second main surface 16b of the glass substrate 16 by a well-known photolithography technique, etching technique, or the like. At this time, a photoresist liquid is used as a coating liquid for pattern formation.

Further, before forming the TFT or CF, the second main surface 16b of the glass substrate 16 can be cleaned as needed. As the cleaning method, a well-known dry cleaning method or a wet cleaning method can be used.

In the bonding step, the thin film transistor forming surface of the TFT laminated body is opposed to the color filter forming surface of the CF laminated body, and a sealing agent (for example, an ultraviolet curing type sealing for forming a cell groove) is used. Mixture) to make it fit. Thereafter, a liquid crystal material is injected into a cell cell formed by the TFT laminate and the CF laminate. The method of injecting the liquid crystal material is, for example, a vacuum injection method or a dropping injection method.

(separation step)

The separation step is as shown in FIG. 2(D), which is a step of collecting the polylayer from the laminate 22 of the member for an electronic device obtained by the above-described member forming step. The interface between the oxygen resin layer 14 and the glass substrate 16 serves as a peeling surface, and is separated into a glass substrate 16 (a glass substrate 24 with a member) on which the electronic device member 20 is laminated, and a support substrate 12, thereby obtaining a member 20 for electronic devices. And a glass substrate 24 attached to the glass substrate 16.

When the electronic device member 20 on the glass substrate 16 at the time of peeling is a part of the formation of all necessary structural members, the remaining structural members can be formed on the glass substrate 16 after separation.

The method of peeling the glass substrate 16 and the support substrate 12 is not specifically limited. Specifically, for example, a sharp cutting tool can be inserted at the interface between the glass substrate 16 and the resin layer 14 to provide a starting point of peeling, and then a mixed fluid of water and compressed air is sprayed and peeled off. It is preferable that the support base material 12 of the laminated body 22 with the electronic device member is placed on the upper side, the electronic device member 20 side is placed on the pressure plate, and the electronic device member 20 side is vacuum-adsorbed to the pressure. On the disk (in the case of the two-area support plate, sequentially), in this state, the cutter is first invaded to the interface of the glass substrate 16 - the resin layer 14. Then, the support substrate 12 side is adsorbed by a plurality of vacuum suction pads, and the vacuum adsorption pad is sequentially raised from the vicinity of the position where the cutter is inserted. Thus, an air layer is formed at the interface between the resin layer 14 and the glass substrate 16 or the agglomerated fracture surface of the resin layer 14, and the air layer spreads to the entire surface of the interface or the agglomerated fracture surface, and the support substrate 12 can be easily peeled off. .

Further, the support substrate 12 can be laminated with a new glass substrate to produce the glass laminate 10 of the present invention.

In addition, when the glass substrate 24 of the attached member is separated from the laminated body 22 of the member for electronic device, by using the ionizer to spray or control the humidity, It is possible to further suppress the electrostatic adsorption of the fragments of the polyoxynitride resin layer 14 on the glass substrate 24 of the attached member.

The method of manufacturing the glass substrate 24 of the above-described member is suitable for manufacturing a small display device for use in a mobile terminal such as a mobile phone or a PDA. The display device is mainly LCD or OLED, and the LCD includes TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type and the like. Basically, it can also be applied to any of the passive drive type and the active drive type.

The glass substrate 24 of the member to be manufactured by the above-mentioned method includes a panel for a display device having a member for a glass substrate and a display device, a solar cell having a member for a glass substrate and a solar cell, and a secondary battery having a glass substrate and a film. A film secondary battery of a member, an electronic component having a glass substrate and a member for an electronic device, and the like. The panel for a display device includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

The support substrate of the agglomerated epoxy resin layer according to the third aspect of the present invention is a support substrate and a polyoxyxene resin layer provided on the surface of the support substrate, and the polyoxyxene resin layer is aggregated. The epoxy resin is a crosslinked product of a crosslinkable organopolyoxane, and the elastic modulus of the polyoxyxene resin layer measured by a nanoindentation method is 0.5 to 2.5 MPa.

The support substrate of the agglomerated epoxy resin layer is formed on the surface of the same support substrate as that described in the first aspect, and the same polyoxyxylene resin layer as that of the first aspect is formed. The support substrate of such an agglomerated epoxy resin layer is obtained by, for example, forming a polyoxyxylene resin layer on the surface of the support substrate or peeling the glass substrate or the glass member from the laminate.

Example

Hereinafter, the present invention will be specifically described by way of Examples and the like, but the present invention is not limited by the Examples.

In the following Examples 1 to 9 and Comparative Examples 1 and 2, a glass plate composed of alkali-free borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.2 mm, average linear expansion coefficient 38 × 10 ^-7 / ° C, The brand name "AN100" manufactured by Asahi Glass Co., Ltd. is used as a glass substrate. In addition, a glass plate (240 mm long, 240 mm wide, 0.5 mm thick, average linear expansion coefficient 38×10 ^-7 /°C, trade name "AN100" manufactured by Asahi Glass Co., Ltd.) was used as the glass plate of the same alkali-free borosilicate glass. Support substrate.

<Example 1>

First, the support substrate having a thickness of 0.5 mm was washed with pure water, and then washed with UV to be cleaned.

Next, a base agent (ASA-V01) (100 parts by mass) of Arakawa Chemical Co., Ltd. and a hardener (ASA-X01) (13 parts by mass) manufactured by Arakawa Chemical Co., Ltd. were mixed. To 5 parts by mass of (ASA-V01), 5 parts by weight of a catalyst (ASA-C01) made by Arakawa Chemical Co., Ltd. was added. Further, heptane was added to prepare a solution X containing a crosslinkable organopolysiloxane. This solution X was applied onto the first main surface of the support substrate by a spin coating method (rotation number: 300 rpm, 15 seconds), and a layer containing the unhardened crosslinkable organopolysiloxane was set on the support group. On the material (coating amount 20g/m ² ).

Subsequently, it was heat-hardened in the atmosphere at 230 ° C for 10 minutes to form a polyoxyxylene resin layer having a thickness of 10 μm on the first main surface of the support substrate.

Then, the glass substrate and the polyoxyl resin layer of the support substrate were bonded together at room temperature by a vacuum press to obtain a glass laminate A.

In the obtained glass laminate A, the support substrate and the glass substrate were in close contact with the polyoxymethylene resin layer in a state where no bubbles were generated, and there was no skewed defect, and the smoothness was also good.

Next, the glass laminate A was heat-treated at 360 ° C for 60 minutes in a nitrogen atmosphere, and after cooling to room temperature, no separation of the support substrate of the glass laminate A from the glass substrate, or polyoxylization was observed. A change in appearance such as foaming or whitening of the resin layer.

Then, at a corner portion of one of the four portions of the glass laminate A, a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer of the support sheet to form a peeled portion, and at the same time The vacuum adsorption pad is adsorbed on the non-peeling surface of each of the glass substrate and the support plate, and an external force is applied to the direction in which the glass substrate and the support plate are separated from each other, and the glass substrate and the support substrate are separated without being damaged. Here, the insertion of the cutter is performed while the static-eliminating fluid is sprayed from the ionizer (manufactured by KEYENCE Co., Ltd.) to the interface. Specifically, the vacuum adsorption pad is pulled while continuously ejecting an electrostatic fluid from the ionizer toward the formed void.

Further, the polyoxyphthalocene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the peel strength (x) at the interface between the support substrate and the polyoxyxylene resin layer was larger than that of the polyoxymethylene resin layer and Peel strength (y) of the interface of the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 2.36 MPa.

The measurement conditions of the nanoindentation method are as follows.

Using TI-950 made by Omicron Nano Technology Japan Co., Ltd. Tribo Indenter performs various physical property values of the polyoxynated resin layer. That is, using a Conical 5um type triangular pyramid press as a pressure pin, pressurizing in a displacement speed fixed mode of 30 nm/sec and increasing the load, and after reaching a maximum load of 2 μN, the load is also pressed in a stepwise manner and the load is gradually increased. The measurement was carried out under a constant temperature condition of 25 ° C, and after the temperature of the measuring device and the sample was sufficiently stabilized, the modulus of elasticity at a press-in strength of 0.2 μN and a depth of 200 nm was measured, and the average value of five times was continuously measured as a measured value.

<Example 2>

Further, in the solution X containing the crosslinkable organopolyoxane, methyl phenyl polyphthalide oil (KF-50, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 100 mm ² /s) is further added, in addition to In the same manner as in Example 1, a glass laminate B was obtained.

In addition, the amount of the methylphenyl polyfluorene oxide used is 5 parts by mass based on 100 parts by mass of the polyoxyxylene resin.

In the obtained glass laminate B, the support substrate and the glass substrate were in close contact with the polyoxymethylene resin layer in a state where no bubbles were generated, and there was no skew defect, and the smoothness was also good.

Then, the glass laminate B was subjected to the same heat treatment as in Example 1. As a result, no separation of the support substrate of the glass laminate B and the glass substrate, or foaming or whitening of the polyoxyalkyl resin layer was observed. Variety.

Then, the glass laminate B was separated from the glass substrate in the same manner as in Example 1, and as a result, the glass substrate and the support substrate were separated without damage. Further, the polyoxyphthalocene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the support substrate and the polyoxymethylene resin layer were supported. The peel strength (x) of the interface is greater than the peel strength (y) of the interface between the polyoxynated resin layer and the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 2.29 MPa.

<Example 3>

The same method as in Example 2 was carried out, except that the amount of use of methyl phenyl polyfluorene oxide (KF-50, viscosity 100 mm ² /s, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 5 parts by mass to 15 parts by mass. A glass laminate C is obtained.

In the obtained glass laminate C, the support substrate and the glass substrate were in close contact with the polyoxymethylene resin layer in a state where no bubbles were generated, and there was no skew defect, and the smoothness was also good.

Then, the glass laminate C was subjected to the same heat treatment as in Example 1, and as a result, no separation of the support substrate and the glass substrate of the glass laminate C, or foaming or whitening of the polyoxyxene resin layer was observed. Variety.

Then, the glass laminate C was separated from the glass substrate in the same manner as in Example 1. As a result, the glass substrate and the support substrate were separated without damage. Further, the polyoxyphthalocene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the peel strength (x) at the interface between the support substrate and the polyoxyxylene resin layer was larger than that of the polyoxymethylene resin layer and Peel strength (y) of the interface of the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 2.09 MPa.

<Example 4>

The same method as in Example 2 was carried out except that the amount of use of methylphenyl polyfluorene oxide (KF-50, viscosity 100 mm ² /s, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 5 parts by mass to 20 parts by mass. A glass laminate D is obtained.

In the obtained glass laminate D, the support substrate and the glass substrate were in close contact with the polyoxyxene resin layer in a state where no bubbles were generated, and there was no skew defect, and the smoothness was also good.

Then, the glass laminate D was subjected to the same heat treatment as in Example 1, and as a result, no separation of the support substrate of the glass laminate D and the glass substrate, or foaming or whitening of the polyoxyalkylene layer was observed. Variety.

Then, the glass laminate D was separated from the glass substrate by the same method as in Example 1, and as a result, the glass substrate and the support substrate were separated without damage. Further, the polyoxyphthalocene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the peel strength (x) at the interface between the support substrate and the polyoxyxylene resin layer was larger than that of the polyoxymethylene resin layer and Peel strength (y) of the interface of the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 1.15 MPa.

<Example 5>

Methylphenyl polyfluorene oxide (SH200, viscosity 200mm ² /s, manufactured by Toray Dow Corning Co., Ltd.) was used instead of methyl phenyl polyphthalide oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm ² In the same manner as in Example 2, a glass laminate E was obtained.

In the obtained glass laminate E, the support substrate and the glass substrate were in close contact with the polyoxyxene resin layer in a state where no bubbles were generated, and there was no skew defect, and the smoothness was also good.

Then, the glass laminate E was subjected to the same heat treatment as in Example 1. As a result, no separation of the support substrate of the glass laminate E and the glass substrate, or foaming or whitening of the polyoxyalkylene layer was observed. Variety.

Then, the glass laminate E was separated from the glass substrate in the same manner as in Example 1. As a result, the glass substrate and the support substrate were separated without damage. Further, the polyoxyphthalocene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the peel strength (x) at the interface between the support substrate and the polyoxyxylene resin layer was larger than that of the polyoxymethylene resin layer and Peel strength (y) of the interface of the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 2.34 MPa.

<Example 6>

The same method as in Example 5 was carried out except that the amount of use of methylphenyl polyfluorene oxide (SH200, viscosity 200 mm ² /s, manufactured by Toray Dow Corning Co., Ltd., SH200, viscosity: 200 mm ² /s) was changed from 5 parts by mass to 10 parts by mass. A glass laminate F is obtained.

In the obtained glass laminate F, the support substrate and the glass substrate were in close contact with the polyoxymethylene resin layer in a state where no bubbles were generated, and there was no skew defect, and the smoothness was also good.

Then, the glass laminate F was subjected to the same heat treatment as in Example 1. As a result, no separation of the support substrate of the glass laminate F from the glass substrate or foaming or whitening of the polyoxyxene resin layer was observed. Variety.

Then, the glass laminate F was separated from the glass substrate in the same manner as in Example 1, and as a result, the glass substrate and the support substrate were separated without damage. In addition, the polyoxyl resin layer is combined with the support substrate from the glass From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the polyoxyxene resin layer was larger than the peel strength (y) at the interface between the polyoxymethylene resin layer and the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 2.31 MPa.

<Example 7>

The same method as in Example 5 was carried out except that the amount of use of methylphenyl polyfluorene oxide (SH200, viscosity 200 mm ² /s, manufactured by Toray Dow Corning Co., Ltd., SH200, viscosity: 200 mm ² /s) was changed from 5 parts by mass to 15 parts by mass. A glass laminate G is obtained.

In the obtained glass laminate G, the support substrate and the glass substrate were in close contact with the polyoxyxene resin layer in a state where no bubbles were generated, and there was no skew defect, and the smoothness was also good.

Then, the glass laminate G was subjected to the same heat treatment as in Example 1. As a result, no separation of the support substrate and the glass substrate of the glass laminate G, or foaming or whitening of the polyoxymethylene resin layer was observed. Variety.

Then, the glass laminate G was separated from the glass substrate in the same manner as in Example 1. As a result, the glass substrate and the support substrate were separated without damage. Further, the polyoxyphthalocene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the peel strength (x) at the interface between the support substrate and the polyoxyxylene resin layer was larger than that of the polyoxymethylene resin layer and Peel strength (y) of the interface of the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 2.09 MPa.

<Example 8>

A glass laminate H was obtained in the same manner as in Example 1 except that the following solution Y containing a crosslinkable organopolyoxane was used instead of the solution X containing a crosslinkable organopolysiloxane.

(solution Y containing crosslinkable organopolyoxane)

One vinyl group of dimethylpolyphosphonium (56 mPa ‧ ) (100 parts by mass), and methyl hydrogen hydride as a hardener (methyl: hydrogen (mo) Ear ratio) = 2:1, the molar content of the hydroquinone group was 33.3%, and 104 mPa s) (10 parts by mass) was mixed. The Karstedt catalyst was added in an amount of 3 ppm in terms of platinum relative to the resin component. 0.2 part by mass of 1-acetylyne-1-cyclohexanol was added as a retarder based on the resin component. Then, heptane was added to prepare a solution Y containing a crosslinkable organopolyoxane. The molar ratio of the vinyl group of the main agent to the hydroquinone of the hardener (alkenyl mole number / hydroquinone molar number) was formulated to be 1 mole: 0.8 mole.

In the obtained glass laminate H, the support substrate and the glass substrate were in close contact with the polyoxymethylene resin layer in a state where no bubbles were generated, and there was no skew defect, and the smoothness was also good.

Then, the glass laminate H was subjected to the same heat treatment as in Example 1, and as a result, no separation of the support substrate and the glass substrate of the glass laminate H or foaming or whitening of the polyoxyn resin layer was observed. Variety.

Then, the glass laminate H was separated from the glass substrate in the same manner as in Example 1. As a result, the glass substrate and the support substrate were separated without damage. Further, the polyoxyphthalocene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the peel strength (x) at the interface between the support substrate and the polyoxyxylene resin layer was larger than that of the polyoxymethylene resin layer and Glass substrate Peel strength (y) of the interface.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 0.65 MPa.

<Example 9>

A glass laminate I was obtained in the same manner as in Example 1 except that the following solution Z containing a crosslinkable organopolyoxane was used instead of the solution X containing a crosslinkable organopolysiloxane.

(solution Z containing crosslinkable organopolyoxane)

The main ingredient (A78) (100 parts by mass) of Arakawa Chemical Co., Ltd. and the hardener (ASA-X01) (15 parts by mass) manufactured by Arakawa Chemical Co., Ltd. were mixed. The Arakawa Chemical Co., Ltd. catalyst (ASA-C01) was added in an amount of 5 parts by weight based on 100 parts by mass of (A78). Further, heptane was added to prepare a solution Z containing a crosslinkable organopolyoxane.

In the obtained glass laminate I, the support substrate and the glass substrate were in close contact with the polyoxymethylene resin layer in a state where no bubbles were generated, and there was no skew defect, and the smoothness was also good.

Then, the glass laminate 1 was subjected to the same heat treatment as in Example 1. As a result, no separation of the support substrate of the glass laminate I and the glass substrate, or foaming or whitening of the polyoxyalkylene layer was observed. Variety.

Then, the glass laminate 1 was separated from the glass substrate in the same manner as in Example 1. As a result, the glass substrate and the support substrate were separated without damage. Further, the polyoxyphthalocene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the peel strength (x) at the interface between the support substrate and the polyoxyxylene resin layer was larger than that of the polyoxymethylene resin layer and Peel strength (y) of the interface of the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 1.10 MPa.

<Comparative Example 1>

A glass laminate J was obtained in the same manner as in Example 1 except that the following solution W containing a crosslinkable organopolysiloxane was used instead of the solution X containing a crosslinkable organopolyoxane.

(solution containing crosslinkable organopolyoxane W)

FX-T153Vi-5K (900 mPa‧ s) (100 parts by mass) manufactured by ADEKA Co., Ltd. and FX-T153H-5K (1240 mPa ‧ s) (10 parts by mass) manufactured by ADEKA Co., Ltd. were mixed. Further, dodecane was added to prepare a solution W containing a crosslinkable organopolyoxane. The molar ratio of alkenyl to hydroquinone is adjusted to be 1:1.

In the same manner as in Example 1, the obtained glass laminate J was separated from the support substrate and the glass substrate. As a result, the polysiloxane resin layer and the glass substrate were not easily peeled off, and the glass substrate was broken or the polyoxymethylene resin layer was broken. Most of them are attached to the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 0.23 MPa.

<Comparative Example 2>

A glass laminate K was obtained in the same manner as in Example 1 except that the following solution V containing a crosslinkable organopolysiloxane was used instead of the solution X containing a crosslinkable organopolysiloxane.

(solution V containing crosslinkable organopolyoxane)

Arakawa Chemical Co., Ltd. main agent (A41) (100 parts by mass), and Arakawa Chemical A company hardener (ASA-X01) (13 parts by mass) was mixed so that the molar ratio of the alkenyl group to the hydroquinone group was 1:1. The Arakawa Chemical Co., Ltd. catalyst (ASA-C01) was added in an amount of 5 parts by weight based on 100 parts by mass of (A41). Further, dodecane was added to prepare a solution V containing a crosslinkable organopolyoxane.

In the obtained glass laminate K, separation between the support substrate and the glass substrate was carried out in the same manner as in Example 1. As a result, the polyoxyxylene resin layer and the glass substrate were not easily peeled off, and the glass substrate was broken or the polyoxyalkylene resin layer was broken. Partially attached to the glass substrate.

Further, the modulus of elasticity of the polyoxyxylene resin layer on the support substrate after peeling of the glass substrate was measured by a nanoindentation method and found to be 3.15 MPa.

The results of the above examples and comparative examples are shown as follows.

In addition, in the table 1, the "peelability" is a case where the glass substrate and the polyoxymethylene resin layer are not broken, and the glass substrate can be peeled off from the glass laminate as "○"; when the glass substrate is peeled off, a glass substrate or a glass substrate is generated. The state of destruction of the polyoxymethylene resin layer is referred to as "x".

Further, the glass laminates A to K subjected to heat treatment at 360 ° C for 60 minutes were subjected to the following peeling test, and the peel strength (N/25 mm) of the glass substrate was measured.

The glass laminates A to K having a width of 25 mm and a length of 70 mm were prepared, and the glass substrate was peeled off using a universal testing machine Autograph AG-20/50kNXDplus (Shimadzu Corporation). In addition, the peeling speed was 30 mm/min. The spot where the load was detected was taken as 0, and the peeling strength at a position of 1.5 mm from the position was used as a measured value.

[Table 1]

As is apparent from the above Table 1, it was confirmed that when the elastic modulus of the polyoxyxene resin layer was within a specific range (0.5 to 2.5 MPa), the peeling property of the glass substrate was excellent.

On the other hand, in Comparative Example 1 in which the modulus of elasticity of the polyoxyxene resin layer was too low, and in Comparative Example 2 which was too high, the peeling property of the glass substrate was not good.

<Example 10>

In this example, an OLED was produced using the glass laminate A obtained in Example 1.

First, a film is formed on the second main surface of the glass substrate in the glass laminate A in the order of tantalum nitride, ruthenium oxide, and amorphous ruthenium by a plasma CVD method. Next, a low concentration of boron was injected into the amorphous germanium layer by an ion doping apparatus, and heat treatment was performed at 450 ° C for 60 minutes in a nitrogen atmosphere to carry out dehydrogenation treatment. Next, the crystallization of the amorphous germanium layer is performed by a laser annealing device. deal with. Next, N-type and P-type TFT regions are formed by implanting a low concentration of phosphorus into the amorphous germanium layer by using an etching and ion doping apparatus of photolithography. Next, a ruthenium oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by sputtering, and etching is performed by photolithography. A gate electrode is formed. Next, a source region and a drain region are formed by injecting a high concentration of boron and phosphorus into a region required for each of the N-type and the P-type by photolithography and an ion doping apparatus. Then, on the second main surface side of the glass substrate, an interlayer insulating film is formed by film formation of ruthenium oxide by a plasma CVD method, and aluminum is formed by sputtering and photolithography is used. The etching is performed to form a TFT electrode. Next, after performing hydrogenation treatment at 450 ° C for 60 minutes in a hydrogen atmosphere, the passivation layer was formed by film formation of tantalum nitride by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, indium tin oxide is formed into a film by sputtering, and a pixel electrode is formed by etching using photolithography.

Next, 4,4',4"-tris(3-methylphenylamino)triphenylamine was sequentially formed into a positive hole injection layer on the second main surface side of the glass substrate by a vapor deposition method. , the bis[(N-naphthyl)-N-phenyl]benzidine is formed into a positive pore transport layer, and 2,6-bis[4] is mixed in the 8-hydroxyquinoline aluminum complex (Alq ₃ ). -[N-(4-Methoxyphenyl)-N-phenyl]aminostyryl]-naphthyl-1,5-dicarbonitrile (BSN-BCN) 40% by volume The light-emitting layer is formed by forming Alq ₃ into an electron transport layer. Secondly, aluminum is formed into a film by sputtering, and a counter electrode is formed by etching using photolithography. Secondly, the second main layer of the glass substrate is formed. The surface side is bonded to another glass substrate via an ultraviolet curing type, and an organic EL structure is formed on the glass substrate in accordance with the above procedure. The glass laminate A having an organic EL structure on the glass substrate (hereinafter referred to as The panel A) is a laminate of the member for an electronic device of the present invention (a panel for a display device with a support substrate).

Next, after the sealing body side of the panel A is vacuum-adsorbed to the fixing plate, a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of the panel A to provide an interface between the glass substrate and the resin layer. The starting point of stripping. Then, after the surface of the support substrate of the panel A is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the cutter is performed while ejecting an electrostatic fluid from the ionizer (manufactured by KEYENCE Co., Ltd.) to the interface. Next, the vacuum adsorption pad is pulled while continuously ejecting the static-eliminating fluid from the ionizer toward the formed gap. As a result, only the glass substrate on which the organic EL structure is formed remains on the plate, and the support substrate with the resin layer can be peeled off.

Next, the peeled surface of the separated glass substrate was cleaned by the same method as in Example 1, and the separated glass substrate was cut using a laser cutter or a scribe-break method, and divided into After the plurality of cell grooves, the glass substrate on which the organic EL structure is formed is assembled with the counter substrate, and the module formation step is performed to fabricate the OLED. The OLED thus obtained has no problem in characteristics.

<Example 11>

In this example, an LCD was produced using the glass laminate A obtained in Example 1.

First, two glass laminates A are prepared, and the second main surface of the glass substrate in one of the glass laminates A1 is nitrided by plasma CVD. Film formation is carried out in the order of ruthenium, iridium oxide, and amorphous ruthenium. Next, a low concentration of boron was injected into the amorphous germanium layer by an ion doping apparatus, and heat treatment was performed at 450 ° C for 60 minutes in a nitrogen atmosphere to carry out dehydrogenation treatment. Next, the crystallization treatment of the amorphous germanium layer is performed by a laser annealing apparatus. Next, by using a photolithography etching and ion doping apparatus, a low concentration of phosphorus is implanted into the amorphous germanium layer to form N-type and P-type TFT regions. Next, a gate insulating film is formed by a plasma CVD method on the second main surface side of the glass substrate, and then molybdenum is formed by sputtering, and etching is performed by photolithography. A gate electrode is formed. Next, a high concentration of boron and phosphorus is implanted into a region required for each of the N-type and the P-type by photolithography and an ion doping apparatus to form a source region and a drain region. Then, on the second main surface side of the glass substrate, an interlayer insulating film is formed by film formation of ruthenium oxide by a plasma CVD method, and aluminum is formed by sputtering and photolithography is used. The etching is performed to form a TFT electrode. Next, after performing hydrogenation treatment at 450 ° C for 60 minutes in a hydrogen atmosphere, the passivation layer was formed by film formation of tantalum nitride by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, indium tin oxide is formed into a film by sputtering, and a pixel electrode is formed by etching using photolithography.

Next, another piece of the glass laminate A2 was heat-treated at 450 ° C for 60 minutes in an atmosphere. Next, chromium is formed on the second main surface of the glass substrate in the glass laminate A by sputtering, and a light shielding layer is formed by etching using photolithography. Next, a color resist is applied by a die coating method on the second main surface side of the glass substrate, and formed by photolithography and thermal hardening. Color filter layer. Next, indium tin oxide is formed into a film by a sputtering method to form a counter electrode. Next, the ultraviolet curable resin liquid was applied onto the second main surface side of the glass substrate by a die coating method, and a columnar spacer was formed by photolithography and thermal curing. Next, the polyimide resin solution was applied by a roll coating method to form an alignment layer by thermal hardening, and rubbing was performed.

Next, the sealing resin liquid is drawn into a frame shape by a dispenser method, and after the liquid crystal is dropped into the frame by a dispenser method, the glass laminated body A1 on which the pixel electrode is formed is used to laminate two glass layers. The second main surface side of the glass substrate of the body A is bonded to each other, and an LCD panel is obtained by ultraviolet curing and thermal curing.

Next, the second main surface of the glass laminate A1 is vacuum-adsorbed to the fixed plate, and a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of the glass laminate A2 to provide a glass substrate. The starting point of the peeling of the first main surface and the peeling surface of the resin layer. Here, the insertion of the cutter is performed while ejecting an electrostatic fluid from the ionizer (manufactured by KEYENCE Co., Ltd.) to the interface. Next, the vacuum adsorption pad is pulled while continuously ejecting the static-eliminating fluid from the ionizer toward the formed gap. Then, after adsorbing the second main surface of the support substrate of the glass laminate A2 by the vacuum adsorption pad, the adsorption pad is raised. As a result, only the empty cell cell of the LCD having the support substrate of the glass laminate A1 remains on the fixed plate, and the support substrate can be peeled off.

Then, the second main surface of the glass substrate on which the color filter is formed on the first main surface is vacuum-adsorbed to the fixed plate, and the stainless steel having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of the glass laminate A1. Tool, Further, the starting point of the peeling of the first main surface of the glass substrate and the peeling surface of the resin layer is provided. Then, after adsorbing the second main surface of the support substrate of the glass laminate A1 by the vacuum adsorption pad, the adsorption pad is raised. As a result, only the LCD cell groove remains on the plate, and the support substrate to which the resin layer is fixed can be peeled off. Thus, a cell groove of a plurality of LCDs composed of a glass substrate having a thickness of 0.1 mm was obtained.

Then, by the step of cutting, the cell slots of the plurality of LCDs are divided. The step of adhering the polarizing plate to each of the obtained LCD cell grooves is performed, and then the module forming step is performed to obtain the LCD. The LCD thus obtained has no problem in characteristics.

<Example 12>

In this example, an OLED was produced using the glass laminate A obtained in Example 1.

First, molybdenum is formed on the second main surface of the glass substrate in the glass laminate A by sputtering, and a gate electrode is formed by etching using photolithography. Next, a gate insulating film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then indium gallium zinc oxide is formed by sputtering, and is used by using a sputtering method. Etching by photolithography forms an oxide semiconductor layer. Next, a channel protective layer is formed by forming a film of tantalum nitride on the second main surface side of the glass substrate by a plasma CVD method, and then molybdenum is formed by sputtering, and photolithography is used. Etching forms a source electrode and a drain electrode. Next, heat treatment was carried out at 450 ° C for 60 minutes in the atmosphere. Next, a passivation layer is formed on the second main surface side of the glass substrate by a plasma CVD method to form a passivation layer, and then indium tin oxide is formed into a film by sputtering. The pixel electrode is formed by etching using photolithography.

Next, 4,4′,4′′-tris(3-methylphenylamino)triphenylamine is sequentially formed into a positive hole injection layer on the second main surface side of the glass substrate by a vapor deposition method. The bis[(N-naphthyl)-N-phenyl]benzidine is formed into a positive pore transport layer, and 2,6-bis[4-] is mixed in the 8-hydroxyquinoline aluminum complex (Alq ₃ ). [N-(4-Methoxyphenyl)-N-phenyl]aminostyryl]-naphthyl-1,5-dicarbonitrile (BSN-BCN) 40% by volume In the layer, Alq _{3 is} formed into an electron transport layer. Secondly, aluminum is formed into a film by sputtering, and a counter electrode is formed by etching using photolithography. Next, on the second main surface side of the glass substrate Sealing is performed by bonding another glass substrate to the adhesive layer of the ultraviolet curing type. The organic EL structure is formed on the glass substrate in accordance with the above procedure. The glass laminate A having the organic EL structure on the glass substrate (hereinafter referred to as panel A) A laminate for a member for an electronic device according to the present invention (a panel for a display device with a support substrate).

Next, after the sealing body side of the panel A is vacuum-adsorbed to the fixed plate, a stainless steel cutter having a thickness of 0.1 mm is 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 is inserted. Provide a starting point for stripping. Then, after adsorbing the surface of the support substrate of the panel A with a vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the cutter is performed while ejecting an electrostatic fluid from the ionizer (manufactured by KEYENCE Co., Ltd.) to the interface. Next, the vacuum adsorption pad is pulled while continuously ejecting the static-eliminating fluid from the ionizer toward the formed gap. As a result, only the glass substrate on which the organic EL structure is formed remains on the fixed plate, and the support substrate with the resin layer can be peeled off.

Next, the separated glass substrate was used in the same manner as in Example 1. The peeling surface is cleaned, and the separated glass substrate is cut into a plurality of cell grooves by a laser cutting or scribing-fracturing method, and the glass substrate and the opposite substrate on which the organic EL structure is formed are formed. The OLED is fabricated by performing a module forming step. The OLED thus obtained has no problem in characteristics.

The present application is based on Japanese Patent Application No. 2012-286768, filed on Dec.

10‧‧‧glass laminate

12‧‧‧Support substrate

14‧‧‧Polyoxy resin layer

14a‧‧‧1st main surface of polyoxyl resin layer

16‧‧‧ glass substrate

16a‧‧‧1st main surface of the glass substrate

16b‧‧‧2nd main surface of the glass substrate

18‧‧‧Support substrate with polyoxyl resin layer

Claims (13)

A glass laminate having a support substrate, a polyoxyxene resin layer and a glass substrate in sequence, and a peeling strength of an interface between the support substrate and the polyoxymethylene resin layer is greater than that of the polysilicon oxide resin layer and the glass substrate The peeling strength of the interface, the polyfluorene oxide resin of the polyfluorene oxide layer is a crosslinked product of a crosslinkable organopolyoxyalkylene, and is further measured by a nanoindentation method after being heated at 360 ° C for 60 minutes. The polyoxynoxy resin layer has an elastic modulus of 0.5 to 2.5 MPa. The glass laminate according to claim 1, wherein the crosslinked product of the crosslinkable organopolyoxane is obtained by reacting an organopolysiloxane having an alkenyl group with an organopolysiloxane having a hydroquinone group. Crosslinks. The glass laminate according to claim 2, wherein a mixed molar ratio (alkenyl mole number/hydroquinolyl mole number) of the aforementioned alkenyl group to the aforementioned hydroquinone group is from 1/1 to 1/0.8. The glass laminate according to claim 1, wherein the polysilicon oxide resin layer further comprises a polyoxygenated oil. The glass laminate according to claim 2, wherein the polysilicon oxide resin layer further comprises a polyoxygenated oil. The glass laminate according to claim 3, wherein the polysilicon oxide resin layer further comprises a polyoxygenated oil. The glass laminate according to claim 1, wherein the polysilicon oxide resin layer has a thickness of 2 to 100 μm. The glass laminate according to claim 2, wherein the polysilicon oxide resin layer has a thickness of 2 to 100 μm . The glass laminate according to claim 3, wherein the polysilicon oxide resin layer has a thickness of 2 to 100 μm . The glass laminate according to claim 4, wherein the polysilicon oxide resin layer has a thickness of 2 to 100 μm . The glass laminate according to any one of claims 1 to 10, wherein the aforementioned support substrate is a glass plate. A method for producing a glass laminate according to any one of claims 1 to 11, which is to form a layer containing a crosslinkable organopolysiloxane on one side of a support substrate, and to provide the foregoing on the surface of the support substrate The crosslinkable organopolyoxane is crosslinked to form a polyoxyxylene resin layer, followed by a glass substrate on the surface layer of the aforementioned polyoxynitride resin layer. A support substrate with an agglomerated epoxy resin layer, comprising a support substrate and a polyoxymethylene resin layer disposed on the surface of the support substrate, wherein the polyfluorene resin of the polyoxyxylene resin layer is a crosslinkable organic polyfluorene The crosslinked product of the oxyalkylene is further subjected to a heat treatment at 360 ° C for 60 minutes, and the elastic modulus of the polyfluorene oxide resin layer measured by a nanoindentation method is 0.5 to 2.5 MPa.