JP6252490B2 - GLASS LAMINATE, PROCESS FOR PRODUCING THE SAME, AND SUPPORT SUBSTRATE WITH SILICONE RESIN LAYER - Google Patents

Description

The present invention relates to a glass laminate and a method for producing the same, and more particularly to a glass laminate having a silicone resin layer exhibiting a predetermined elastic modulus and a method for producing the same.
The present invention also relates to a support base material with a silicone resin layer, and more particularly, to a support base material with a silicone resin layer on which a glass substrate is releasably laminated and a manufacturing method thereof.

  In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and the glass substrates used in these devices have been made thinner. Progressing. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the device manufacturing process.

Therefore, conventionally, a method of forming a device member (for example, a thin film transistor) on a glass substrate thicker than the final thickness and then thinning the glass substrate by chemical etching is widely used.
However, in this method, for example, when the thickness of one glass substrate is reduced from 0.7 mm to 0.2 mm or 0.1 mm, most of the original glass substrate material is scraped off with an etching solution. Therefore, it is not preferable from the viewpoint of productivity and use efficiency of raw materials. In addition, in the method of thinning a glass substrate by the above chemical etching, if a fine scratch exists on the surface of the glass substrate, a fine recess (etch pit) is formed from the scratch by the etching process, resulting in an optical defect. There was a case.

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

International Publication No. 2007/018028

In recent years, higher heat resistance has been required for the glass laminate described in Patent Document 1. As the electronic device members formed on the glass substrate of the glass laminate become more functional and complex, the temperature at which the electronic device members are formed becomes even higher, and the time exposed to the high temperatures also increases. It often takes a long time. Moreover, the glass substrate used is also made thinner, making it difficult to handle.
The glass laminate described in Patent Document 1 can withstand treatment at 300 ° C. for 1 hour in the air. However, according to studies by the present inventors, referring to Patent Document 1, when a glass laminate using a thinner glass substrate is treated at 360 ° C. for 1 hour, the glass substrate is When peeling from the surface of the silicone resin layer, the glass substrate is not peeled off from the surface of the resin layer, but part of it is destroyed, or part of the resin of the resin layer remains on the glass substrate, resulting in an electronic device. In some cases, the productivity of the product was reduced.

The present invention has been made in view of the above problems, and even after high-temperature heat treatment, the increase in peel strength between the glass substrate and the silicone resin layer is suppressed, and the glass substrate can be easily peeled off. It aims at providing a glass laminated body and its manufacturing method.
Another object of the present invention is to provide a support substrate with a silicone resin layer used in the production of the glass laminate.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the first aspect of the present invention includes a support base material, a silicone resin layer, and a glass substrate in this order, and the peel strength at the interface between the support base material and the silicone resin layer is between the silicone resin layer and the glass substrate. The glass laminate is larger than the peel strength at the interface, and the silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane, and the elastic modulus of the silicone resin layer measured by the nanoindentation method is 0. It is a glass laminated body which is 5-2.5 MPa.

In the first embodiment, the crosslinked product of the crosslinkable organopolysiloxane is preferably a crosslinked product obtained by reacting an organopolysiloxane having an alkenyl group and an organopolysiloxane having a hydrosilyl group.
In the first aspect, the mixing molar ratio of alkenyl group to hydrosilyl group (number of moles of alkenyl group / number of moles of hydrosilyl group) is preferably 1/1 to 1 / 0.8.
In the first aspect, the silicone resin layer preferably further contains silicone oil.
1st aspect WHEREIN: It is preferable that the thickness of a silicone resin layer is 2-100 micrometers.
1st aspect WHEREIN: It is preferable that a support base material is a glass plate.

  In the second aspect of the present invention, a layer containing a crosslinkable organopolysiloxane is formed on one side of a support substrate, and the silicone resin layer is formed by crosslinking the crosslinkable organopolysiloxane on the support substrate surface. It is a method for producing a glass laminate of the first embodiment in which a glass substrate is laminated on the surface of a silicone resin layer.

  According to a third aspect of the present invention, there is provided a support substrate with a silicone resin layer having a support substrate and a silicone resin layer provided on the support substrate surface, wherein the silicone resin of the silicone resin layer is crosslinkable. It is a cross-linked product of organopolysiloxane, and is a support substrate with a silicone resin layer, wherein the elastic modulus of the silicone resin layer measured by the nanoindentation method is 0.5 to 2.5 MPa.

ADVANTAGE OF THE INVENTION According to this invention, even after high temperature heat processing, the raise of the peeling strength of a glass substrate and a silicone resin layer is suppressed, and the glass laminated body which can peel a glass substrate easily, and its manufacturing method are provided. be able to.
Moreover, according to this invention, the support base material with a silicone resin layer used for manufacture of this glass laminated body can also be provided.

FIG. 1 is a schematic cross-sectional view of an embodiment of a glass laminate according to the present invention. Drawing 2 (A)-Drawing 2 (D) are typical sectional views showing one embodiment of a manufacturing method of a glass substrate with a member concerning the present invention in order of a process.

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

The glass laminated body of this invention is equipped with a support base material, a silicone resin layer, and a glass substrate in this order. That is, it has a silicone resin layer between a support base material and a glass substrate, therefore, one side of the silicone resin layer is in contact with the support base material, and the other side is in contact with the glass substrate.
One of the characteristic points of the glass laminate of the present invention is that the elastic modulus of the silicone resin layer measured by the nanoindentation method is within a predetermined range. In particular, the elastic modulus of the silicone resin layer formed on the support substrate is within a predetermined range. A silicone resin layer having an elastic modulus within a predetermined range is softer than a conventional silicone resin layer. When such a flexible silicone resin layer is used, the glass substrate can be peeled relatively easily while being in close contact with the glass substrate disposed on the silicone resin layer to a certain degree to prevent positional displacement. Although the detailed reason for obtaining the above characteristics is unknown, it is presumed as follows. First, when the glass substrate is laminated on the silicone resin layer, the silicone resin layer is soft so that it deforms to follow the shape of the glass substrate surface without causing a gap or the like between the silicone resin layer and the glass substrate. The silicone resin layer and the glass substrate adhere well. Further, when the glass substrate is peeled from the silicone resin layer after the high-temperature heat treatment, the silicone resin layer is easily deformed, so that it is possible to suppress stress from being locally applied to the glass substrate, and as a result, the glass substrate is easily peeled off. be able to.

FIG. 1 is a schematic cross-sectional view of an example of a glass laminate according to the present invention.
As shown in FIG. 1, the glass laminated body 10 is a laminated body in which the support base material 12, the glass substrate 16, and the silicone resin layer 14 exist among them. The silicone resin layer 14 has one surface in contact with the support base 12 and the other surface in contact with the first main surface 16 a of the glass substrate 16. In other words, the silicone resin layer 14 is in contact with the first major surface 16 a of the glass substrate 16.
The two-layer portion composed of the support base 12 and the silicone resin layer 14 reinforces the glass substrate 16 in a member forming process for manufacturing a member for an electronic device such as a liquid crystal panel. In addition, the two-layer part which consists of the support base material 12 manufactured in advance for manufacture of the glass laminated body 10 and the silicone resin layer 14 is called the support base material 18 with a silicone resin layer.

  This glass laminated body 10 is used until the member formation process mentioned later. That is, the glass laminate 10 is used until a member for an electronic device such as a liquid crystal display device is formed on the surface of the second main surface 16b of the glass substrate 16. Thereafter, the glass laminate on which the electronic device member is formed is separated into a supporting substrate 18 with a silicone resin layer and a glass substrate with an electronic device member, and the supporting substrate 18 with a silicone resin layer is a portion constituting an electronic device. It will not be. A new glass substrate 16 is laminated on the support base material 18 with the silicone resin layer, and can be reused as a new glass laminate 10.

The interface between the support substrate 12 and the silicone resin layer 14 has a peel strength (x), and when a stress in the peeling direction exceeding the peel strength (x) is applied to the interface between the support substrate 12 and the silicone resin layer 14, The interface between the support base 12 and the silicone resin layer 14 is peeled off. The interface between the silicone resin layer 14 and the glass substrate 16 has a peel strength (y). When a stress in the peeling direction exceeding the peel strength (y) is applied to the interface between the silicone resin layer 14 and the glass substrate 16, the silicone resin The interface between the layer 14 and the glass substrate 16 is peeled off.
In the glass laminate 10 (which also means a laminate with an electronic device member described later), the peel strength (x) is greater (higher) than the peel strength (y). Therefore, when a stress is applied to the glass laminate 10 in the direction of peeling the support base 12 and the glass substrate 16, the glass laminate 10 of the present invention peels off at the interface between the silicone resin layer 14 and the glass substrate 16. It separates into a glass substrate 16 and a support substrate 18 with a silicone resin layer.
That is, the silicone resin layer 14 is fixed on the support substrate 12 to form a support substrate 18 with a silicone resin layer, and the glass substrate 16 is in close contact with the silicone resin layer 14 so as to be peeled off.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the silicone resin layer 14 to the support base 12 can be increased, and a relatively higher adhesion to the glass substrate 16 can be maintained after the heat treatment. .
In order to increase the adhesion of the silicone resin layer 14 to the support substrate 12, it is preferable to form a silicone resin layer 14 by crosslinking and curing a crosslinkable organopolysiloxane on the support substrate 12, as will be described later. The silicone resin layer 14 bonded to the support substrate 12 with a high bonding force can be formed by the adhesive force at the time of crosslinking and curing.
On the other hand, the bond strength of the cured product of the crosslinkable organopolysiloxane after the crosslink curing to the glass substrate 16 is usually lower than the bond strength generated at the time of the crosslink curing. Therefore, the crosslinkable organopolysiloxane is crosslinked and cured on the support base 12 to form the silicone resin layer 14, and then the glass substrate 16 is laminated on the surface of the silicone resin layer 14 to produce the glass laminate 10. Is preferred.

  The glass laminate according to the first aspect of the present invention includes a support base, a silicone resin layer, and a glass substrate in this order, and the peel strength at the interface between the support base and the silicone resin layer is the silicone resin layer and the glass. The glass laminate is larger than the peel strength at the interface with the substrate, and the silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane, and the elasticity of the silicone resin layer measured by the nanoindentation method A glass laminate having a rate of 0.5 to 2.5 MPa.

  Below, each layer (support base material 12, glass substrate 16, silicone resin layer 14) which comprises the glass laminated body 10 is explained in full detail first, About the manufacturing method of a glass laminated body and the glass substrate with a member for electronic devices after that. Detailed description.

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

  The thickness of the support base 12 may be thicker or thinner than the glass substrate 16. Preferably, the thickness of the support base 12 is selected based on the thickness of the glass substrate 16, the thickness of the silicone resin layer 14, and the thickness of the glass laminate 10. For example, when the current member forming process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the glass substrate 16 and the thickness of the silicone resin layer 14 is 0.1 mm, The thickness of the support base 12 is set to 0.4 mm. In general, the thickness of the support base 12 is preferably 0.2 to 5.0 mm.

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

The difference in average linear expansion coefficient at 25 to 300 ° C. between the support base 12 and the glass substrate 16 is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably 300 × 10 ⁻⁷ / ° C. or less. More preferably, it is 200 × 10 ⁻⁷ / ° C. or less. If the difference in the average linear expansion coefficient is too large, the glass laminate 10 may be warped severely or the support base 12 and the glass substrate 16 may be peeled off during heating and cooling in the member forming process. When the material of the support base material 12 is the same as the material of the glass substrate 16, it is possible to suppress the occurrence of such a problem, and therefore the support base material is preferably a glass plate.

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

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

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

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

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

The thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.20 mm or less, and further preferably 0.15 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 16. Especially preferably, it is 0.10 mm or less. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 16. In the case of 0.15 mm or less, the glass substrate 16 can be rolled up.
Further, the thickness of the glass substrate 16 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 16 and easy handling of the glass substrate 16.

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

[Silicone resin layer]
The silicone resin layer is substantially composed of a silicone resin, and the silicone resin is a crosslinked product of a crosslinkable organopolysiloxane and has an elastic modulus of 0.5 to 2.5 MPa measured by a nanoindentation method. The peel strength at the interface between the support substrate and the silicone resin layer is greater than the peel strength at the interface between the silicone resin layer and the glass substrate.
The silicone resin layer 14 prevents the glass substrate 16 from being displaced until the operation for separating the glass substrate 16 and the support base 12 is performed, and prevents the glass substrate 16 and the like from being damaged by the separation operation. The surface (first main surface of the silicone resin layer) 14a of the silicone resin layer 14 in contact with the glass substrate 16 is in close contact with the first main surface 16a of the glass substrate 16 in a peelable manner. On the other hand, the silicone resin layer 14 is fixed on the support substrate 12. Therefore, the silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the peel strength (y) at the interface is the interface between the silicone resin layer 14 and the support base 12. Lower than the peel strength (x).
That is, when separating the glass substrate 16 and the support base material 12, the glass substrate 16 is peeled off at the interface between the first main surface 16 a of the glass substrate 16 and the silicone resin layer 14, and the support base material 12 and the silicone resin layer 14 are separated. It is difficult to peel off at the interface. For this reason, the silicone resin layer 14 is in close contact with the first main surface 16a of the glass substrate 16, but has a surface characteristic that allows the glass substrate 16 to be easily peeled off. That is, the silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a certain amount of bonding force to prevent the glass substrate 16 from being displaced, and at the same time, when the glass substrate 16 is peeled off. The glass substrate 16 is bonded with a bonding force that can be easily peeled without breaking the glass substrate 16. In this invention, the property which can peel this silicone resin layer 14 surface easily is called peelability. On the other hand, the 1st main surface of the support base material 12 and the silicone resin layer 14 are couple | bonded by the bonding force which cannot be peeled relatively.
The bonding force at the interface between the silicone resin layer 14 and the glass substrate 16 may change before and after the electronic device member is formed on the surface (second main surface 16b) of the glass substrate 16 of the glass laminate 10. (That is, the peel strength (x) and peel strength (y) may change). However, even after the electronic device member is formed, the peel strength (y) is lower than the peel strength (x).

The silicone resin layer 14 and the glass substrate 16 are considered to be bonded with a bonding force resulting from a weak adhesive force or van der Waals force. When the glass substrate 16 is laminated on the surface after the silicone resin layer 14 is formed, if the silicone resin of the silicone resin layer 14 is sufficiently cross-linked so as not to exhibit an adhesive force, the binding force due to van der Waals force It is thought that it is combined with. However, the silicone resin of the silicone resin layer 14 often has a certain weak adhesive force. Even when the adhesiveness is extremely low, when the electronic device member is formed on the laminated body after the glass laminated body 10 is manufactured, the silicone resin of the silicone resin layer 14 is removed from the glass substrate 16 by a heating operation or the like. It is considered that the bonding force between the silicone resin layer 14 and the glass substrate 16 is increased by adhering to the surface.
In some cases, the surface of the silicone resin layer 14 before lamination or the first main surface 16a of the glass substrate 16 before lamination can be laminated by performing a treatment for weakening the bonding force between them. By performing non-adhesive treatment or the like on the surface to be laminated and then laminating, the bonding strength at the interface between the silicone resin layer 14 and the glass substrate 16 can be weakened, and the peel strength (y) can be lowered.

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

The elastic modulus of the silicone resin layer 14 measured by the nanoindentation method is 0.5 to 2.5 MPa. Especially, 0.5-2.0 MPa is preferable and 0.5-1.2 MPa is more preferable at the point which the peelability of the glass substrate 16 is more excellent.
When the elastic modulus of the silicone resin layer 14 is less than 0.5 MPa and when the silicone resin layer 14 is broken, and when it exceeds 2.5 MPa, the glass substrate 16 and the silicone resin layer 14 are difficult to peel off. 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 silicone resin layer 14.

  In order to set the elastic modulus measured by the nanoindentation method within the above range, as described later, the silicone resin layer should be a predetermined silicone resin layer, the silicone resin layer contains silicone oil, It can be controlled by the forming method or the like.

In the present invention, the elastic modulus (Young's modulus) can be obtained by combining JKR (Johnson-Kendall-Roberts) analysis with force measurement using an atomic force microscope as a method of measuring elastic modulus by the nanoindentation method. In this method, the cantilever is moved perpendicularly to the sample surface, and the load is measured with respect to the position of the cantilever. Samples that are sufficiently hard with respect to the spring constant of the cantilever do not cause sample deformation, but soft samples can also be used to obtain a relationship between the load and the amount of sample deformation by utilizing the deformation of the sample according to the load. JKR analysis is optimal when the indentation is small and the sample is soft.
For details of the above elastic modulus measurement method, see Polymer Journal Vol. 69, no. 7, 435-442. The procedure for measuring the elastic modulus will be described in detail in an example section described later.

Although the thickness of the silicone resin layer 14 is not specifically limited, It is preferable that it is 2-100 micrometers, It is more preferable that it is 3-50 micrometers, It is further more preferable that it is 7-20 micrometers. When the thickness of the silicone resin layer 14 is within such a range, even if air bubbles or foreign matter may be present between the silicone resin layer 14 and the glass substrate 16, the occurrence of distortion defects in the glass substrate 16 is suppressed. can do. In addition, if the thickness of the silicone resin layer 14 is too thick, it takes time and materials to form it, which is not economical and the heat resistance may decrease. Moreover, when the thickness of the silicone resin layer 14 is too thin, the adhesiveness of the silicone resin layer 14 and the glass substrate 16 may fall.
The silicone resin layer 14 may be composed of two or more layers. In this case, “the thickness of the silicone resin layer 14” means the total thickness of all the layers.
Moreover, when the silicone resin layer 14 consists of two or more layers, the crosslinked silicone resin from which resin which forms each layer differs may be sufficient.

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

Among these, the crosslinkable organopolysiloxane is an organopolysiloxane having alkenyl groups at both ends and / or side chains (hereinafter referred to as appropriate) because the silicone resin layer 14 can be easily formed and is excellent in releasability of the glass substrate 16. An embodiment including an organopolysiloxane A) and an organopolysiloxane having hydrosilyl groups at both ends and / or side chains (hereinafter also referred to as organopolysiloxane B as appropriate) is preferred.
In addition, although it does not specifically limit as an alkenyl group, For example, a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, a hexynyl group etc. are mentioned, Especially from the point which is excellent in heat resistance. A vinyl group is preferred.
Examples of the group other than the alkenyl group contained in the organopolysiloxane A and the group other than the hydrosilyl group contained in the organopolysiloxane B include an alkyl group (particularly an alkyl group having 4 or less carbon atoms).

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

The number of alkenyl groups in the organopolysiloxane A is not particularly limited, but is preferably 1 to 3 per molecule and more preferably 2.
The preferred structure of the organopolysiloxane A is linear or cyclic, has two or more alkenyl groups in one molecule, and one or more alkenyl groups are present in both of two M units. Is.
The position of the hydrosilyl group in the organopolysiloxane B is not particularly limited. However, when the organopolysiloxane A is linear, the hydrosilyl group may be present in either the M unit or the D unit. It may be present in both D units. It is preferable that it exists in at least D unit from the point of a cure rate.
The number of hydrosilyl groups in the organopolysiloxane B is not particularly limited, but it is preferably at least 3 per molecule, and more preferably 3.
As a preferred structure of the organopolysiloxane B, when the organopolysiloxane A is linear or cyclic, it has two or more hydrosilyl groups in one molecule, and the molar content of hydrosilyl groups is 30% or more. It is preferable.

  The mixing ratio of the organopolysiloxane A and the organopolysiloxane B is not particularly limited, but the organopolysiloxane A and the organopolysiloxane B are used in order to keep the elastic modulus of the resulting silicone resin layer by the nanoindentation method within a predetermined range. The mixing ratio can be adjusted. The molar ratio (number of moles of alkenyl group / number of moles of hydrosilyl group) of all alkenyl groups in organopolysiloxane A and hydrosilyl groups (hydrogen atoms bonded to silicon atoms) in organopolysiloxane B is glass. It is preferable to adjust so that it may become 1/1-1 / 0.8 at the point which the peelability of a board | substrate is more excellent. Especially, it is preferable to adjust a mixing ratio so that it may become 1/1 to 1 / 0.9.

  As the structure and mixing ratio suitable for the crosslinkable organopolysiloxane, the organopolysiloxane A is linear or cyclic, has two or more alkenyl groups in one molecule, and two alkenyl groups. It is preferable that at least one of both M units is present, and the organopolysiloxane B has two or more hydrosilyl groups in one molecule, and the molar content of hydrosilyl groups is 30% or more. Preferably, the molar ratio (number of moles of alkenyl group / number of moles of hydrosilyl group) of all alkenyl groups in organopolysiloxane A and hydrosilyl groups (hydrogen atoms bonded to silicon atoms) in organopolysiloxane B is It is preferable to adjust to be 1/1 to 1 / 0.8.

As the hydrosilylation catalyst, a platinum group metal catalyst is preferably used. Examples of the platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and it is particularly preferable to use as a platinum-based catalyst from the viewpoint of economy and reactivity. As the platinum group metal catalyst, known catalysts can be used. Specifically, platinum fine powder, platinum black, chloroplatinic acid such as chloroplatinic acid, chloroplatinic acid, platinum tetrachloride, alcohol compounds of chloroplatinic acid, aldehyde compounds, platinum olefin complexes, alkenyls Examples thereof include siloxane complexes and carbonyl complexes.
The amount of the hydrosilylation catalyst used is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total mass of the organopolysiloxane A and the organopolysiloxane B. As a platinum component, 2-400 ppm is preferable with respect to 100 mass parts of total mass of organopolysiloxane A and organopolysiloxane B, and 2-300 ppm is more preferable.

The weight-average molecular weight of the crosslinkable organopolysiloxane is not particularly limited, but it is excellent in handleability, excellent in film formability, and more resistant to decomposition of the silicone resin under high temperature processing conditions. The weight average molecular weight in terms of polystyrene as measured by chromatography is preferably 1,000 to 5,000,000, and more preferably 2,000 to 3,000,000.
The viscosity of the crosslinkable organopolysiloxane is preferably 10 to 5000 mPa · s, more preferably 15 to 3000 mPa · s. In addition, in this specification, unless there is particular notice, a viscosity is a value when it measures at 25 degreeC.

In the curable silicone resin composition of the present invention, an activity inhibitor (compound also called a reaction inhibitor, a retarder, etc.) having an action of suppressing the catalyst activity is used together with the catalyst for the purpose of adjusting the catalyst activity. Is preferred. Examples of the activity inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, and organic chloro compounds. Specific examples of the acetylene compound include 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 4-ethyl-1-octin-3-ol, and the like. Furthermore, if necessary, inorganic fillers such as various silicas, calcium carbonates, iron oxides and the like may be contained within a range not impairing the effects of the present invention. Moreover, metal compounds, such as a metal oxide, may be included as a heat resistance improvement agent.
In addition, organic solvents such as hexane, heptane, octane, toluene and xylene, and dispersion media such as water are components that do not constitute a cured silicone resin, but include improved workability for application of the curable silicone resin composition. For the purpose, it can be used by blending with the curable silicone resin composition of the present invention.

The silicone resin layer 14 may contain silicone oil. Even when silicone oil is contained in the silicone resin layer, the elastic modulus of the silicone resin layer measured by the nanoindentation method can be controlled to a predetermined value. Unlike the crosslinkable organopolysiloxane, silicone oil is a non-crosslinkable (nonreactive) organopolysiloxane that does not react with the crosslinkable organopolysiloxane and does not have crosslinkability.
The type of silicone oil is not particularly limited, but straight silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc., modified silicone oils in which polyether groups, halogen groups, etc. are introduced into the side chain or terminal of straight silicone oil Is exemplified.
In addition, as a trade name or model number of silicone oil specifically marketed, as silicone oil having an aromatic group (for example, phenyl group), KTSF433 (manufactured by Momentive Performance Materials Japan GK), KF -50, KF-53, KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH550 (manufactured by Toray Dow Corning), and the like.
Examples of the silicone oil having no aromatic group include SH200 (manufactured by Toray Dow Corning), KNS-330 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

The viscosity of the silicone oil is not particularly limited, but it is easy to bleed out on the surface of the silicone resin layer 14, the peelability of the glass substrate 16 is more excellent, and the transparency of the peeled glass substrate 16 is more excellent. 6000mm is preferably ² / s, more preferably 100~3000mm ² / s, more preferably 125~1000mm ² / s.
The content ratio of the silicone oil in the silicone resin layer 14 is not particularly limited, but with respect to 100 parts by mass of the silicone resin in terms of excellent peelability of the glass substrate 16 and more excellent transparency of the peeled glass substrate. 6-20 mass parts is preferable, 6-15 mass parts is more preferable, and 8-15 mass parts is further more preferable.

[Glass laminate and manufacturing method thereof]
As described above, the glass laminate 10 of the present invention is a laminate in which the support base 12, the glass substrate 16, and the silicone resin layer 14 exist between them.
The manufacturing method in particular of the glass laminated body 10 of this invention is not restrict | limited, A well-known method can be employ | adopted. For example, the method of laminating | stacking the glass substrate 16 on the silicone resin layer 14 of the support base material 18 with the silicone resin layer by which the silicone resin layer 14 was fix | immobilized on the support base material 12 is preferable. Among them, in order to obtain a laminate having a peel strength (x) higher than the peel strength (y), a predetermined crosslinkable organopolysiloxane is crosslinked and cured on the surface of the support substrate 12 to form the silicone resin layer 14. The method is preferred. That is, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate 12, and the crosslinkable organopolysiloxane is crosslinked on the surface of the support substrate 12 to form a silicone resin layer 14 (crosslinked silicone resin). Next, the glass substrate 16 is manufactured by laminating the glass substrate 16 on the silicone resin surface of the silicone resin layer 14. Also, the elastic modulus by the nanoindentation method can be controlled within a predetermined range by crosslinking and curing a predetermined crosslinkable organopolysiloxane on the surface of the support substrate 12.
When the crosslinkable organopolysiloxane is cured on the surface of the support substrate 12, it is considered that the crosslinkable organopolysiloxane adheres due to the interaction with the surface of the support substrate 12 during the curing reaction, and the peel strength between the silicone resin and the surface of the support substrate 12 increases. . Therefore, even if the glass substrate 16 and the support base 12 are made of the same material, a difference can be provided in the peel strength between the silicone resin layer 14 and the both.
Hereinafter, a step of forming a silicone resin layer 14 by forming a layer containing a crosslinkable organopolysiloxane on the surface of the support substrate 12 and crosslinking the crosslinkable organopolysiloxane on the surface of the support substrate 12 is a resin layer forming step. The process of laminating the glass substrate 16 on the silicone resin surface of the silicone resin layer 14 to form the glass laminate 10 is referred to as a lamination process, and the procedure of each process will be described in detail.

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

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

Next, the crosslinkable organopolysiloxane on the support substrate 12 is crosslinked to form the silicone resin layer 14. More specifically, as shown in FIG. 2A, in this step, a silicone resin layer 14 is formed on the surface of at least one side of the support base 12.
As described above, the curing (crosslinking) method is appropriately selected according to the crosslinking type of the crosslinkable organopolysiloxane, and examples thereof include heat treatment and exposure treatment. In particular, when the crosslinkable organopolysiloxane is crosslinked by a hydrosilylation reaction, a condensation reaction, or a radical reaction, a silicone resin having excellent adhesion and heat resistance to the glass substrate 16 can be obtained. It is preferable to manufacture.
Hereinafter, the aspect of thermosetting is explained in full detail.

  The temperature condition for thermosetting the crosslinkable organopolysiloxane is not particularly limited as long as the heat resistance of the silicone resin layer 14 is improved and the peel strength (y) after lamination with the glass substrate 16 can be controlled as described above. However, 150-300 degreeC is preferable and 180-250 degreeC is more preferable. The heating time is usually preferably 10 to 120 minutes, more preferably 30 to 60 minutes. When the temperature of thermosetting is too low, the heat resistance and the flatness of the silicone resin layer 14 are lowered. On the other hand, when the temperature is too high, the peel strength (y) is too low, both of which are the glass substrate 16 and the silicone resin layer 14. Adhesiveness may be weakened.

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

(Lamination process)
In the laminating step, the glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14 obtained in the resin layer forming step, and the support base 12, the silicone resin layer 14, and the glass substrate 16 are provided in this order. This is a step of obtaining the glass laminate 10. More specifically, as shown in FIG. 2B, the surface (first main surface of the silicone resin layer) 14a opposite to the support base 12 side of the silicone resin layer 14 and the first main surface 16a. The glass laminate 10 is obtained by laminating the silicone resin layer 14 and the glass substrate 16 with the first principal surface 16a of the glass substrate 16 having the second principal surface 16b as a lamination surface.

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

  When pressure bonding is performed by a vacuum laminating method or a vacuum pressing method, it is more preferable because it suppresses mixing of bubbles and secures good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are less likely to cause a distortion defect of the glass substrate 16.

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

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

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

(Glass laminate)
The glass laminate 10 of the present invention can be used for various applications, for example, manufacturing electronic parts such as a display device panel, PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed on the surface, which will be described later. The use to do is mentioned. In this application, the glass laminate 10 is often exposed (for example, 1 hour or longer) under high temperature conditions (for example, 360 ° C. or higher).
Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

[Glass substrate with member and method for producing the same]
In this invention, the glass substrate with a member (glass substrate with a member for electronic devices) containing a glass substrate and the member for electronic devices is manufactured using the laminated body mentioned above.
Although the manufacturing method of this glass substrate with a member is not specifically limited, From the point which is excellent in productivity of an electronic device, the member for electronic devices is formed on the glass substrate in the said glass laminated body, and the laminated body with an electronic device member is used. A method in which the manufactured and obtained laminate with a member for electronic devices is separated into a glass substrate with a member and a supporting substrate with a silicone resin layer by using the glass substrate side interface of the silicone resin layer as a release surface is preferable.
Hereinafter, the step of forming a member for an electronic device by forming a member for an electronic device on the glass substrate in the glass laminate is a member forming step, and the glass substrate for the silicone resin layer from the laminate with the member for an electronic device. The process of separating into a glass substrate with a member and a supporting substrate with a silicone resin layer using the side interface as a release surface is called a separation process.
The materials and procedures used in each process are described in detail below.

(Member formation process)
A member formation process is a process of forming the member for electronic devices on the glass substrate 16 in the glass laminated body 10 obtained in the said lamination process. More specifically, as shown in FIG. 2C, the electronic device member 20 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 to obtain the laminate 22 with the electronic device member. .
First, the electronic device member 20 used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(Electronic device components (functional elements))
The electronic device member 20 is a member that is formed on the glass substrate 16 in the glass laminate 10 and constitutes at least a part of the electronic device. More specifically, as the electronic device member 20, a member used for an electronic component such as a display panel, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on the surface (for example, Display member, solar cell member, thin film secondary battery member, electronic component circuit).

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

(Process procedure)
The manufacturing method of the laminated body 22 with the member for electronic devices mentioned above is not specifically limited, According to the conventionally well-known method according to the kind of structural member of the member for electronic devices, the 2nd main of the glass substrate 16 of the glass laminated body 10 is used. The electronic device member 20 is formed on the surface 16b.
The electronic device member 20 is not all of the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter referred to as “all members”), but a part of all members (hereinafter referred to as “parts”). May be referred to as a member. The glass substrate with a partial member peeled from the silicone resin layer 14 can be used as a glass substrate with an all member (corresponding to an electronic device described later) in the subsequent steps.
Moreover, the other electronic device member may be formed in the peeling surface (1st main surface 16a) in the glass substrate with all the members peeled from the silicone resin layer 14. FIG. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the support substrate 12 from the laminate with all members. Furthermore, it is also possible to assemble using two laminates with all members, and then peel off the two support bases 12 from the laminate with all members to produce a glass substrate with a member having two glass substrates. it can.

  For example, when an OLED is manufactured as an example, an organic EL is formed on the surface of the glass laminate 10 opposite to the silicone resin layer 14 side of the glass substrate 16 (corresponding to the second main surface 16b of the glass substrate 16). In order to form a structure, a transparent electrode is formed, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and sealing is performed. Various layers are formed and processed, such as sealing with a plate. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.

  Further, for example, when manufacturing a TFT-LCD, a resist film is used on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a general film forming method such as a CVD method or a sputtering method. A TFT forming step of forming a thin film transistor (TFT) by patterning the formed metal film, metal oxide film, etc., and patterning a resist solution on the second main surface 16b of the glass substrate 16 of another glass laminate 10 Various processes such as a CF forming step for forming a color filter (CF) to be used for forming, a laminating step for laminating a laminated body with TFT obtained in the TFT forming step and a laminated body with CF obtained in the CF forming step, etc. Process.

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

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

(Separation process)
As shown in FIG. 2 (D), the separation step is performed by using the electronic device member-attached laminate 22 obtained in the member formation step, with the interface between the silicone resin layer 14 and the glass substrate 16 as a release surface. This is a step of separating the glass substrate 16 (member-attached glass substrate 24) on which the member 20 for use is laminated and the support base material 12 to obtain the member-equipped glass substrate 24 including the electronic device member 20 and 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 the necessary constituent members, the remaining constituent members can be formed on the glass substrate 16 after separation.

The method of peeling the glass substrate 16 and the support base material 12 is not specifically limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate 16 and the silicone resin layer 14 to give a trigger for peeling, and then a mixed fluid of water and compressed air is sprayed. Can be peeled off. Preferably, the electronic device member-attached laminate 22 is placed on the surface plate so that the support substrate 12 is on the upper side and the electronic device member 20 side is on the lower side, and the electronic device member 20 side is vacuumed on the surface plate. In this state, the blade is first allowed to enter the interface between the glass substrate 16 and the silicone resin layer 14. Then, the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. As a result, an air layer is formed on the interface between the silicone resin layer 14 and the glass substrate 16 and on the cohesive failure surface of the silicone resin layer 14, and the air layer spreads over the entire interface and cohesive failure surface, so that the supporting substrate 12 can be easily peeled off. can do.
Moreover, the support base material 12 can be laminated | stacked with a new glass substrate, and the glass laminated body 10 of this invention can be manufactured.

  When the glass substrate 24 with a member is separated from the laminated body 22 with a member for electronic devices, a piece of the silicone resin layer 14 is electrostatically adsorbed to the glass substrate 24 with a member by controlling the spraying and humidity with an ionizer. It can be suppressed more.

  The manufacturing method of the glass substrate 24 with a member mentioned above is suitable for manufacture of the small display apparatus used for mobile terminals, such as a mobile telephone and PDA. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type, and the like. Basically, the present invention can be applied to both passive drive type and active drive type display devices.

  As the glass substrate 24 with a member manufactured by the above method, a panel for a display device having a glass substrate and a member for a display device, a solar cell having a glass substrate and a member for a solar cell, a glass substrate and a member for a thin film secondary battery. Examples thereof include a thin film secondary battery, an electronic component having a glass substrate and an electronic device member. Examples of the display device panel include a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

The support base material with a silicone resin layer according to the third aspect of the present invention is a support base material with a silicone resin layer, which has a support base material and a silicone resin layer provided on the support base material surface. The support substrate with a silicone resin layer, wherein the silicone resin of the resin layer is a crosslinked product of a crosslinkable organopolysiloxane, and the elastic modulus of the silicone resin layer measured by a nanoindentation method is 0.5 to 2.5 MPa. It is.
The support substrate with the silicone resin layer is such that the same silicone resin layer as described in the first embodiment is formed on the same surface of the support substrate as described in the first embodiment. Such a support substrate with a silicone resin layer can be obtained by forming a silicone resin layer on the surface of the support substrate or by peeling a glass substrate or a glass substrate with a member from the laminate.

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

In Examples 1 to 9 and Comparative Examples 1 and 2 below, a glass plate made of non-alkali borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.2 mm, average linear expansion coefficient 38 × 10 ^−7). / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.). Moreover, as a support base material, a glass plate (240 mm long, 240 mm wide, 0.5 mm thick, average linear expansion coefficient 38 × 10 ⁻⁷ / ° C., made by Asahi Glass Co., Ltd., also made of non-alkali borosilicate glass. ")It was used.

<Example 1>
First, a supporting substrate having a thickness of 0.5 mm was cleaned with pure water, and further cleaned by UV cleaning.
Next, Arakawa Chemical Co., Ltd. main agent (ASA-V01) (100 parts by mass) and Arakawa Chemical Co., Ltd. curing agent (ASA-X01) (13 parts by mass) were blended. Arakawa Chemical's catalyst (ASA-C01) was added in an amount of 5 parts by weight per 100 parts by weight of (ASA-V01). Further, a solution X containing a crosslinkable organopolysiloxane was prepared by adding heptane. This solution X was applied onto the first main surface of the supporting substrate with a spin coater (rotation speed: 300 rpm, 15 seconds), and a layer containing an uncured crosslinkable organopolysiloxane was provided on the supporting substrate. (Coating amount 20 g / m ² ).

Next, it was heated and cured at 230 ° C. for 10 minutes in the air to form a silicone resin layer having a thickness of 10 μm on the first main surface of the support base.
Then, the glass substrate A and the silicone resin layer surface of the supporting substrate were bonded together by vacuum pressing at room temperature to obtain a glass laminate A.
In the obtained glass laminate A, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.

Next, the glass laminate A was heated at 360 ° C. for 60 minutes in a nitrogen atmosphere and cooled to room temperature. As a result, the glass substrate A was separated from the supporting substrate and the glass substrate, and the silicone resin layer was foamed or whitened. No change in appearance was observed.
And while forming the notch part of peeling by inserting the stainless steel cutting tool of thickness 0.1mm in the interface of the glass substrate and support silicone resin layer in the corner part of one place among four places of the glass laminated body A, glass The vacuum suction pad was adsorbed on the surface of the substrate and the supporting base that were not the release surfaces, and an external force was applied in the direction in which the glass substrate and the supporting base were separated from each other, thereby separating the glass substrate and the supporting base without being damaged. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Specifically, the vacuum suction pad was pulled up while spraying a static eliminating fluid continuously from the ionizer toward the formed gap.
The silicone resin layer is separated from the glass substrate together with the supporting base material. From the result, the peeling strength (x) at the interface between the supporting base material and the silicone resin layer is determined as the peeling strength (y at the interface between the silicone resin layer and the glass substrate). ) Was confirmed.
Moreover, it was 2.36 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

The measurement conditions of the nanoindentation method were as follows.
Various physical property values of the silicone resin layer were measured using TI-950 Tribo Indenter manufactured by Omicron Nanotechnology Japan Co., Ltd. That is, a Conical 5um type triangular pyramid indenter is used as the working indenter, a pushing load is applied to the constant displacement speed mode 30 nm / sec, and after reaching the maximum load of 2 μN, the pushing load is gradually reduced stepwise. The measurement is performed under a constant temperature condition of 25 ° C., and after sufficiently stabilizing the temperature of the measuring apparatus and the sample, the elastic modulus at a depth of 200 nm is measured with an indentation strength of 0.2 μN, and five continuous measurements are performed. The average value was taken as the measured value.

<Example 2>
In the same manner as in Example 1, except that methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm ² / s) was added to the solution X containing a crosslinkable organopolysiloxane, Body B was obtained.
In addition, the usage-amount of methylphenyl silicone oil was 5 mass parts with respect to 100 mass parts of silicone resins.

In the obtained glass laminate B, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate B was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate B and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
And when the glass base material B was isolate | separated from the support base material and the glass substrate by the method similar to Example 1, it isolate | separated, without damaging a glass substrate and a support base material. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.29 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

<Example 3>
A glass laminate in the same manner as in Example 2 except that the amount of methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm ² / s) was changed from 5 parts by mass to 15 parts by mass. C was obtained.

In the obtained glass laminate C, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate C was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate C and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
Then, when the glass substrate C was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.09 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

<Example 4>
A glass laminate in the same manner as in Example 2 except that the amount of methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm ² / s) was changed from 5 parts by mass to 20 parts by mass. D was obtained.

In the obtained glass laminate D, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate D was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate D and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
And when the glass base material D was isolate | separated from the support base material and the glass substrate by the method similar to Example 1, it isolate | separated, without damaging a glass substrate and a support base material. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 1.15 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

<Example 5>
Instead of using methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm ² / s), methyl phenyl silicone oil (manufactured by Toray Dow Corning, SH 200, viscosity 200 mm ² / s) was used. A glass laminate E was obtained in the same manner as in Example 2.

In the obtained glass laminate E, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate E was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate E, foaming and whitening of the silicone resin layer were observed. There wasn't.
Then, when the glass substrate E was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.34 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

<Example 6>
The glass laminate F was prepared in the same manner as in Example 5 except that the amount of methyl phenyl silicone oil (Toray Dow Corning, SH200, viscosity 200 mm ² / s) was changed from 5 parts by mass to 10 parts by mass. Obtained.

In the obtained glass laminate F, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate F was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate F, foaming or whitening of the silicone resin layer were observed. There wasn't.
Then, when the glass laminate F was separated from the support base material and the glass substrate by the same method as in Example 1, the glass substrate and the support base material were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.31 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

<Example 7>
The glass laminate G was prepared in the same manner as in Example 5 except that the amount of methyl phenyl silicone oil (Toray Dow Corning, SH200, viscosity 200 mm ² / s) was changed from 5 parts by mass to 15 parts by mass. Obtained.

In the obtained glass laminate G, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate G was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate G and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
And when the glass substrate G was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.09 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

<Example 8>
A glass laminate H was obtained in the same manner as in Example 1 except that the solution Y containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.

(Solution Y containing crosslinkable organopolysiloxane)
As the main agent, dimethyl silicone (56 mPa · s) (100 parts by mass) with one vinyl group introduced at both ends, and as the curing agent, methyl hydrogen silicone (methyl: hydrogen (molar ratio) = 2: 1, hydro The molar content of the silyl group was 33.3%, 104 mPa · s) (10 parts by mass). The Karlstedt catalyst was added at 3 ppm in terms of platinum with respect to the resin component. As a retarder, 0.2 part by mass of 1-ethynyl-1-cyclohexanol was added to the resin component. Further, a solution Y containing a crosslinkable organopolysiloxane was prepared by adding heptane. The molar ratio of the vinyl group of the main agent to the hydrogen group of the curing agent (number of moles of alkenyl group / number of moles of hydrosilyl group) is 1 mole: 0.8 mole.

In the obtained glass laminate H, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate H was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate H, foaming and whitening of the silicone resin layer were recognized. There wasn't.
Then, when the glass substrate H was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 0.65 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

<Example 9>
A glass laminate I was obtained in the same manner as in Example 1 except that the solution Z containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.

(Solution Z containing crosslinkable organopolysiloxane)
Arakawa Chemical Co., Ltd. main agent (A78) (100 parts by mass) and Arakawa Chemical Co., Ltd. curing agent (ASA-X01) (15 parts by mass) were blended. Arakawa Chemical's catalyst (ASA-C01) was added in an amount of 5 parts by weight per 100 parts by weight of (A78). Furthermore, a solution Z containing a crosslinkable organopolysiloxane was prepared by adding heptane.

In the obtained glass laminate I, the supporting substrate and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and there was no distortion defect and smoothness was good.
Next, when the glass laminate I was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate I, foaming and whitening of the silicone resin layer were observed. There wasn't.
And when the glass substrate I was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 1.10 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

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

(Solution W containing crosslinkable organopolysiloxane)
FX-T153Vi-5K (900 mPa · s) (100 parts by mass) manufactured by ADEKA and a curing agent FX-T153H-5K (1240 mPa · s) (10 parts by mass) manufactured by ADEKA were blended. Further, dodecane was added to prepare a solution W containing a crosslinkable organopolysiloxane. The alkenyl group and the hydrosilyl group were blended so that the molar ratio was 1: 1.

When the obtained glass laminate J was separated from the supporting base material and the glass substrate in the same manner as in Example 1, it was difficult for the silicone resin layer and the glass substrate to peel off, and the glass substrate was cracked, or The silicone resin layer was destroyed, and most of it was deposited on the glass substrate.
In addition, it was 0.23 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

<Comparative example 2>
A glass laminate K was obtained in the same manner as in Example 1, except that the solution V containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.

(Solution V containing crosslinkable organopolysiloxane)
Arakawa Chemical Co., Ltd. main agent (A41) (100 parts by mass) and Arakawa Chemical Co., Ltd. curing agent (ASA-X01) (13 parts by mass) so that the molar ratio of alkenyl group to hydrosilyl group is 1: 1. Blended into Arakawa Chemical's catalyst (ASA-C01) was added in an amount of 5 parts by weight per 100 parts by weight of (A41). Further, a solution V containing a crosslinkable organopolysiloxane was prepared by adding dodecane.

When the obtained glass laminate K was separated from the supporting base material and the glass substrate in the same manner as in Example 1, the silicone resin layer and the glass substrate were difficult to peel off, and the glass substrate was broken, or The silicone resin layer was destroyed, and most of it was deposited on the glass substrate.
In addition, it was 3.15 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.

The results of the above examples and comparative examples are summarized below.
In Table 1, “Peelability” means “◯” when the glass substrate can be peeled from the glass laminate without breaking the glass substrate and the silicone resin layer, and when the glass substrate is peeled, The case where the silicone resin layer was broken was indicated as “x”.

Moreover, the following peeling test was done with respect to the glass laminated bodies AK after heat processing for 360 degreeC for 60 minutes, and the peeling strength (N / 25mm) of the glass substrate was measured.
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 Autograph AG-20 / 50kNXDplus (Shimadzu Corporation). The peeling speed was 30 mm / min. The point where the load was detected was set to 0, and the peel strength at a position 1.5 mm away from the position was taken as the measured value.

As can be seen from Table 1 above, it was confirmed that when the elastic modulus of the silicone resin layer is within a predetermined range (0.5 to 2.5 MPa), the peelability of the glass substrate is excellent.
On the other hand, in Comparative Example 1 in which the elastic modulus of the silicone resin layer was too low and in Comparative Example 2 that was too high, the peelability of the glass substrate was inferior.

<Example 10>
In this example, an OLED is manufactured using the glass laminate A obtained in Example 1.
First, silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in the glass laminate A by plasma CVD. Next, low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and a dehydrogenation process is performed by heating at 450 ° C. for 60 minutes in a nitrogen atmosphere. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas. Next, a silicon 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, then molybdenum is formed by a sputtering method, and etching is performed using a photolithography method. A gate electrode is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after heat treatment is performed at 450 ° C. for 60 minutes in a hydrogen atmosphere, a passivation layer is formed by film formation of nitrogen silicon 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, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
Subsequently, by a vapor deposition method, 4,4 ′, 4 ″ -tris (3-methylphenylamino) triphenylamine as a hole injection layer and bis [(( N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene A mixture of 40% by volume of 1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer are formed in this order, and then aluminum is formed by a sputtering method. Next, another glass substrate is bonded to the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate A (hereinafter referred to as panel A) having the organic EL structure on the glass substrate is used for the electronic device of the present invention. It is a laminated body with a member (panel for display apparatuses with a supporting base material).
Subsequently, after vacuum-adsorbing the sealing body side of the panel A to the surface plate, a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner portion of the panel A, and glass Provides a trigger for peeling at the interface between the substrate and the silicone resin layer. And after adsorb | sucking the support base material surface of the panel A with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while the static elimination fluid is continuously sprayed from the ionizer toward the formed gap. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate is left, and the supporting base material with the silicone resin layer can be peeled off.
Subsequently, the separation surface of the glass substrate separated by the same method as in Example 1 was cleaned, the separated glass substrate was cut using a laser cutter or a scribe-break method, and divided into a plurality of cells. The glass substrate on which the EL structure is formed and the counter substrate are assembled, and a module forming process is performed to manufacture an OLED. The OLED obtained in this way does not have a problem in characteristics.

<Example 11>
In this example, an LCD is manufactured using the glass laminate A obtained in Example 1.
First, two glass laminates A are prepared, and silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in one glass laminate A1 by plasma CVD. Next, low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and a dehydrogenation process is performed by heating at 450 ° C. for 60 minutes in a nitrogen atmosphere. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas. Next, after a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method and a gate insulating film is formed, molybdenum is formed by a sputtering method, and the gate is etched by photolithography. An electrode is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after heat treatment is performed at 450 ° C. for 60 minutes in a hydrogen atmosphere, a passivation layer is formed by film formation of nitrogen silicon 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, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
Next, the other glass laminate A2 is heat-treated at 450 ° C. for 60 minutes in an air atmosphere. Next, a chromium film is formed on the second main surface of the glass substrate in the glass laminate A by a sputtering method, and a light shielding layer is formed by etching using a photolithography method. Next, a color resist is applied to the second main surface side of the glass substrate by a die coating method, and a color filter layer is formed by a photolithography method and heat curing. Next, a film of indium tin oxide is formed by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid is applied to the second main surface side of the glass substrate by a die coating method, and columnar spacers are formed by a photolithography method and thermal curing. Next, a polyimide resin solution is applied by a roll coating method, an alignment layer is formed by thermosetting, and rubbing is performed.
Next, a sealing resin liquid is drawn in a frame shape by the dispenser method, and after dropping the liquid crystal in the frame by the dispenser method, two glass layers are laminated using the glass laminate A1 in which the pixel electrodes are formed as described above. The second main surface sides of the glass substrate of the body A are bonded together, and an LCD panel is obtained by ultraviolet curing and thermal curing.

  Subsequently, the second main surface of the glass laminate A1 is vacuum-adsorbed on a surface plate, and a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner of the glass laminate A2. Triggering the peeling between the first main surface of the glass substrate and the peelable surface of the silicone resin layer. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while the static elimination fluid is continuously sprayed from the ionizer toward the formed gap. And after adsorb | sucking the 2nd main surface of the support base material of glass laminated body A2 with a vacuum suction pad, a suction pad is raised. As a result, it is possible to leave only the empty cell of the LCD with the supporting substrate of the glass laminate A1 on the surface plate, and to peel the supporting substrate with the silicone resin layer.

  Next, the second main surface of the glass substrate on which the color filter is formed on the first main surface is vacuum-adsorbed on a surface plate, and the thickness is formed at the interface between the glass substrate and the silicone resin layer at the corner portion of the glass laminate A1. A 0.1 mm stainless steel blade is inserted to give a trigger for peeling between the first main surface of the glass substrate and the peelable surface of the silicone resin layer. And after adsorb | sucking the 2nd main surface of the support base material of glass laminated body A1 with a vacuum suction pad, a suction pad is raised. As a result, only the LCD cell is left on the surface plate, and the supporting substrate to which the silicone resin layer is fixed can be peeled off. Thus, a plurality of LCD cells composed of a glass substrate having a thickness of 0.1 mm are obtained.

  Subsequently, it is divided into a plurality of LCD cells by a cutting step. A step of attaching a polarizing plate to each completed LCD cell is performed, and then a module forming step is performed to obtain an LCD. The LCD obtained in this way does not have a problem in characteristics.

<Example 12>
In this example, an OLED is manufactured using the glass laminate A obtained in Example 1.
First, molybdenum is deposited on the second main surface of the glass substrate in the glass laminate A by a sputtering method, and a gate electrode is formed by etching using a photolithography method. Next, a silicon nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then an indium gallium zinc oxide film is formed by a sputtering method to perform a photolithography method. An oxide semiconductor layer is formed by the etching used. Next, a silicon nitride film is further formed on the second main surface side of the glass substrate by plasma CVD to form a channel protective layer, and then molybdenum is formed by sputtering and etching using a photolithography method is performed. Thus, a source electrode and a drain electrode are formed. Next, heat treatment is performed in the atmosphere at 450 ° C. for 60 minutes. Next, a silicon nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a passivation layer, followed by an indium tin oxide film formed by a sputtering method and etching using a photolithography method. Thus, a pixel electrode is formed.
Subsequently, by a vapor deposition method, 4,4 ′, 4 ″ -tris (3-methylphenylamino) triphenylamine as a hole injection layer and bis [(( N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene A mixture of 40% by volume of 1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer are formed in this order, and then aluminum is formed by a sputtering method. Next, another glass substrate is bonded to the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate A (hereinafter referred to as panel A) having the organic EL structure on the glass substrate is used for the electronic device of the present invention. It is a laminated body with a member (panel for display apparatuses with a supporting base material).
Subsequently, after vacuum-adsorbing the sealing body side of the panel A to the surface plate, a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner portion of the panel A, and glass Provides a trigger for peeling at the interface between the substrate and the silicone resin layer. And after adsorb | sucking the support base material surface of the panel A with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while the static elimination fluid is continuously sprayed from the ionizer toward the formed gap. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate is left, and the supporting base material with the silicone resin layer can be peeled off.
Subsequently, the separation surface of the glass substrate separated by the same method as in Example 1 was cleaned, the separated glass substrate was cut using a laser cutter or a scribe-break method, and divided into a plurality of cells. The glass substrate on which the EL structure is formed and the counter substrate are assembled, and a module forming process is performed to manufacture an OLED. The OLED obtained in this way does not have a problem in characteristics.

This application is based on Japanese Patent Application No. 2012-286768 filed on Dec. 28, 2012, the contents of which are incorporated herein by reference.

DESCRIPTION OF SYMBOLS 10 Glass laminated body 12 Support base material 14 Silicone resin layer 14a 1st main surface of a silicone resin layer 16 Glass substrate 16a 1st main surface of a glass substrate 16b 2nd main surface of a glass substrate 18 Support base material with a silicone resin layer 20 Electron Device member 22 Laminated body with electronic device member 24 Glass substrate with member

Claims (8)

A support base material, a silicone resin layer, and a glass substrate are provided in this order, and the peel strength at the interface between the support base material and the silicone resin layer is greater than the peel strength at the interface between the silicone resin layer and the glass substrate. A glass laminate,
The silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane,
The elastic modulus of the silicone resin layer measured by a nanoindentation method is 0.5 to 2.5 MPa,
The silicone resin layer further contains silicone oil,
The content rate of the said silicone oil is a glass laminated body which is 6-20 mass parts with respect to 100 mass parts of said silicone resins.   The glass laminate according to claim 1, wherein the crosslinked product of the crosslinkable organopolysiloxane is a crosslinked product obtained by reacting an organopolysiloxane having an alkenyl group with an organopolysiloxane having a hydrosilyl group.   The glass laminate according to claim 2, wherein a mixing molar ratio of the alkenyl group and the hydrosilyl group (number of moles of alkenyl group / number of moles of hydrosilyl group) is 1/1 to 1 / 0.8. The viscosity of the silicone oil is 100~6000 mm ² / s, a glass laminate according to any one of claims 1 to 3.   The glass laminated body as described in any one of Claims 1-4 whose thickness of the said silicone resin layer is 2-100 micrometers.   The glass laminated body as described in any one of Claims 1-5 whose said support base material is a glass plate.   A layer containing a crosslinkable organopolysiloxane is formed on one side of the support substrate, the silicone resin layer is formed by crosslinking the crosslinkable organopolysiloxane on the surface of the support substrate, and then on the surface of the silicone resin layer The method to manufacture the glass laminated body as described in any one of Claims 1-6 which laminates | stacks a glass substrate. A support substrate with a silicone resin layer, comprising a support substrate and a silicone resin layer provided on the support substrate surface,
The silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane,
The elastic modulus of the silicone resin layer measured by a nanoindentation method is 0.5 to 2.5 MPa,
The silicone resin layer further contains silicone oil,
The content rate of the said silicone oil is a support base material with a silicone resin layer which is 6-20 mass parts with respect to 100 mass parts of said silicone resins.

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