WO2014050833A1

WO2014050833A1 - Glass laminate and manufacturing method for same, and support substrate having silicone resin layer attached thereto and manufacturing method for same

Info

Publication number: WO2014050833A1
Application number: PCT/JP2013/075762
Authority: WO
Inventors: 絢松井; 庚薫閔; 大輔内田; 純一角田
Original assignee: 旭硝子株式会社
Priority date: 2012-09-27
Filing date: 2013-09-24
Publication date: 2014-04-03
Also published as: TW201420335A; JP2015231668A

Abstract

　The present invention relates to a glass laminate which has, in the following order, a support substrate layer, a silicone resin layer and a glass substrate layer, and in which the peel strength of the interface of the support substrate layer and the silicone resin layer is higher than the peel strength of the interface of the glass substrate layer and the silicone resin layer, wherein the silicone resin of the silicone resin layer is the crosslinked product of a crosslinking organopolysiloxane containing a siloxane unit (A) represented by formula (1).

Description

GLASS LAMINATE AND METHOD FOR PRODUCING SAME, AND SUPPORT SUBSTRATE WITH SILICONE RESIN LAYER AND METHOD FOR PRODUCING SAME

The present invention relates to a glass laminate and a method for producing the same, and more particularly, to a glass laminate having a predetermined siloxane unit in a silicone resin of a silicone resin layer and a method for producing the same.
The present invention also relates to a support substrate with a silicone resin layer and a method for producing the same, and more particularly to a support substrate with a silicone resin layer on which a glass substrate is releasably laminated and a method for producing the same.

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

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

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

International Publication No. 2007/018028

In recent years, 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.
The glass laminate described in Patent Document 1 can withstand treatment at 300 ° C. for 1 hour in the air. However, according to the study by the present inventors, the silicone resin of the silicone resin layer in the glass laminate described in Patent Document 1 decomposes in a short time at 400 ° C., and a large amount of outgas is generated. Generation | occurrence | production of such an outgas contaminates the member for electronic devices formed on a glass substrate, and becomes a cause of reducing the productivity of an electronic device as a result.
In addition, cracks or the like occur in the silicone resin layer itself due to decomposition of the resin layer, the adhesion with the glass substrate laminated thereon is lowered, and the position of the glass substrate during the manufacture of the electronic device member subjected to high temperature treatment There is a concern that a deviation or the like is likely to occur, resulting in a decrease in productivity of the electronic device.
Furthermore, when separating the glass substrate from the glass laminate, a part of the thermally deteriorated silicone resin layer may adhere to the peeling surface of the glass substrate on the product side, which is very difficult to remove. There was a concern that the peelability would decrease.

The present invention has been made in view of the above problems, and is a glass laminate in which thermal decomposition of a silicone resin layer is suppressed even under high-temperature heat treatment conditions, and a glass substrate can be easily peeled even after high-temperature heat treatment. And it aims at providing the manufacturing method.
Another object of the present invention is to provide a support substrate with a silicone resin layer used for the production of the glass laminate and a method for producing the same.

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 layer, a silicone resin layer, and a glass substrate layer in this order, and the peel strength at the interface between the support base layer and the silicone resin layer is that of the glass substrate. A glass laminate having a higher peel strength at the interface between the layer and the silicone resin layer, wherein the silicone resin of the silicone resin layer contains a siloxane unit (A) represented by the formula (1) described later It is a glass laminate that is a crosslinked product of siloxane.

In the first embodiment, it is preferable that R ¹ to R ⁴ in the siloxane unit (A) are each independently an alkyl group having 4 or less carbon atoms or a phenyl group.
In the first aspect, it is preferable that the crosslinkable organopolysiloxane further includes a siloxane unit (B) represented by the formula (2) described later.
In the first embodiment, in the crosslinkable organopolysiloxane, the ratio of the siloxane unit (A) to the total of the siloxane unit (A) and the siloxane unit (B) is 30 to 90 mol%, and the siloxane unit ( The total proportion of A) and the siloxane unit (B) is preferably 80 to 100 mol%.

In the first embodiment, the siloxane unit (B) is a siloxane unit (B) in which at least one of R ⁵ and R ⁶ is an alkenyl group having 3 or less carbon atoms and is an alkyl group having 4 or less carbon atoms in the case of other than the alkenyl group. -1), and R ⁵ and R ⁶ are both selected from the group consisting of siloxane units (B-2) which are alkyl groups having 4 or less carbon atoms, and the siloxane units (B) in the crosslinkable organopolysiloxane are It is preferable that the siloxane unit (B-1) alone or the siloxane unit (B-1) and the siloxane unit (B-2).
In the first aspect, the crosslinkable organopolysiloxane is preferably an alternating copolymer of a siloxane unit (A) and a siloxane unit (B).
In the first embodiment, the thickness of the silicone resin layer is preferably 2 to 100 μm.
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 of 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 surface of the support substrate. A method for producing a glass laminate, comprising laminating a glass substrate on a surface of a resin layer opposite to a surface that contacts the support substrate.

3rd aspect of this invention is a support base material with a silicone resin layer which has a support base material and the silicone resin layer which has the peelable surface provided on the support base material surface, Silicone resin of a silicone resin layer Is a support substrate with a silicone resin layer, which is a crosslinked product of a crosslinkable organopolysiloxane containing a siloxane unit (A) represented by the formula (1) described later.
In the third aspect, the crosslinkable organopolysiloxane preferably further contains a siloxane unit (B) represented by the formula (2).
In the third aspect, the crosslinkable organopolysiloxane is preferably an alternating copolymer of a siloxane unit (A) and a siloxane unit (B).
In the third aspect, the thickness of the silicone resin layer is preferably 2 to 100 μm.
In the third aspect, the supporting substrate is preferably a glass plate.

According to a fourth aspect of the present invention, a silicone resin layer is formed by forming a crosslinkable organopolysiloxane layer on the support substrate surface and crosslinking the crosslinkable organopolysiloxane on the support substrate surface. It is the method of manufacturing the support base material with a silicone resin layer.

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

FIG. 1 is a schematic cross-sectional view of an embodiment of a glass laminate according to the present invention. 2 (A) to 2 (D) are schematic cross-sectional views showing an embodiment of a method for producing a glass substrate with a member according to the present invention in the order of steps.

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 laminate of the present invention comprises a support base material layer, a silicone resin layer, and a glass substrate layer in this order. That is, it has a silicone resin layer between the layer of the supporting substrate and the layer of the glass substrate, and therefore, the silicone resin layer has one side in contact with the layer of the supporting substrate and the other side in contact with the layer of the glass substrate. Yes.
In the glass laminate of the present invention, the silicone resin of the silicone resin layer is a cross-linked product of a cross-linkable organopolysiloxane containing a siloxane unit (A) represented by the formula (1) described later. On the other hand, it exhibits a predetermined adhesion and suppresses the decomposition of the silicone resin under high temperature treatment conditions. As a result, generation of outgas, displacement of the glass substrate, etc. are further suppressed. The reason why the decomposition of the silicone resin is suppressed is that the main chain of the crosslinkable organopolysiloxane contains a divalent aromatic hydrocarbon group (for example, a phenylene group). By including this aromatic hydrocarbon group, the bond energy of the crosslinkable organopolysiloxane is improved, the mobility of the crosslinkable organopolysiloxane is lowered, and the cleavage of the siloxane bond is difficult to proceed. As a result, generation of a cyclic compound of siloxane generated along with cleavage is suppressed, and generation of outgas, displacement of the glass substrate, and the like are further suppressed.

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 layer of the support base material 12, the layer of the glass substrate 16, and the silicone resin layer 14 exist among them. One side of the silicone resin layer 14 is in contact with the layer of the support base 12, and the other side is 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 including the layer 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 layer of the support base material 12 manufactured previously 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.

The glass laminate 10 is used until a member forming step described 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 the supporting substrate 18 with the silicone resin layer and the glass substrate with the member, and the supporting substrate 18 with the silicone resin layer is not a part constituting the electronic device. . The support base material 18 with the silicone resin layer is laminated with a new glass substrate 16 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 of the present invention (which also means a laminate with an electronic device member described later), the peel strength (x) is higher than the peel strength (y). Therefore, when the stress of the direction which peels the support base material 12 and the glass substrate 16 is applied to the glass laminated body 10 of this invention, the glass laminated body 10 of this invention will be in the interface of the silicone resin layer 14 and the glass substrate 16. FIG. It peels and isolate | separates into the glass substrate 16 and the support base material 18 with a silicone resin layer.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the silicone resin layer 14 to the support base 12 can be increased, and a relatively higher adhesion to the glass substrate 16 can be maintained after the heat treatment. .
In order to increase the adhesion of the silicone resin layer 14 to the support substrate 12, 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 bonding force of the silicone resin, which is a crosslinked product of the crosslinkable organopolysiloxane after crosslinking and curing, to the glass substrate 16 is usually lower than the bonding force generated during the crosslinking and 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.

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, Then, the manufacturing method of a glass laminated body and a glass substrate with a member is explained in full detail. .

[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 linear expansion coefficient from the glass substrate 16 and more preferably formed of the same material as the glass substrate 16. Preferably, the support base 12 is 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 being easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.

The difference in average linear expansion coefficient between the support base 12 and the glass substrate 16 at 25 to 300 ° C. is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably 300 × 10 ⁻⁷ / ° C. or less. More preferably, it is 200 × 10 ⁻⁷ / ° C. or less. If the difference is too large, the glass laminate 10 may be severely warped or the support substrate 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 can suppress that such a problem arises.

[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 preferably excellent in chemical resistance and moisture permeability and has a low thermal shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.

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

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

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

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

[Silicone resin layer]
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. The silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the peeling strength (y) at the interface is the peeling at the interface between the silicone resin layer 14 and the support base 12. Lower than 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 silicone resin layer 14 formed by the method of the present invention usually has a peelable surface.
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).

It is considered that the silicone resin layer 14 and the glass substrate 16 are bonded to each other with a bonding force due to 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 strength between the silicone resin layer 14 and the glass substrate 16 is increased by adhering to the surface. In some cases, the surface 14a 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. By such treatment, the peelability of the surface of the silicone resin layer 14 of the present invention can be adjusted.

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 the bond strength between the support base material 12 surface and the silicone resin layer 14 is given. Can be increased.
The fact that the silicone resin layer 14 and the layer of the supporting substrate 12 are bonded with a high bonding force means that the peel strength (x) at the interface between them is high.

The thickness of the silicone resin layer 14 is not particularly limited, but is preferably 2 to 100 μm, more preferably 3 to 50 μm, and even more preferably 5 to 20 μm. When the thickness of the silicone resin layer 14 is within such a range, even if air bubbles or foreign matter may be present between the silicone resin layer 14 and the glass substrate 16, the occurrence of distortion defects in the glass substrate 16 is suppressed. can do. In addition, if the thickness of the silicone resin layer 14 is too thick, it takes time and materials to form it, which is not economical and the heat resistance may decrease. Moreover, when the thickness of the silicone resin layer 14 is too thin, the adhesiveness of the silicone resin layer 14 and the glass substrate 16 may fall.
The silicone resin layer 14 may be composed of two or more layers. In this case, “the thickness of the silicone resin layer 14” means the total thickness of all the layers.
Moreover, when the silicone resin layer 14 consists of two or more layers, resin which forms each layer may consist of a different crosslinked silicone resin.

The silicone resin layer 14 preferably has excellent heat resistance.
More specifically, the 5% weight reduction temperature of the silicone resin of the silicone resin layer 14 is preferably 450 ° C. or higher, and more preferably 500 ° C. or higher. The upper limit is not particularly limited, but is usually 600 ° C. or lower in many cases. If it is in the said range, decomposition | disassembly of the silicone resin layer 14 will be suppressed also under high temperature conditions (about 400 degreeC or more), such as a manufacturing process of a TFT array, and generation | occurrence | production of the foaming in the glass laminated body 10 will be suppressed more.

The 5% weight loss temperature is determined when the sample is heated from room temperature to 700 ° C. under a nitrogen atmosphere (100 ml / min) using a thermogravimetric analyzer at a rate of temperature increase of 15 ° C./min. The temperature at which the weight is reduced by 5%.

The silicone resin of the silicone resin layer 14 is a cross-linked product of a crosslinkable organopolysiloxane containing a siloxane unit (A) represented by the formula (1) described later.
Below, the aspect of crosslinkable organopolysiloxane and its crosslinked material is explained in full detail.

(Crosslinkable organopolysiloxane and its cross-linked product)
The crosslinkable organopolysiloxane used in the present invention contains a siloxane unit (A) represented by the formula (1).
Usually, the basic structural unit of organopolysiloxane is classified according to how many monovalent organic groups represented by methyl group and phenyl group are bonded to silicon atoms. The organic group called D unit shown below is 2 Bifunctional siloxane unit with one bond, trifunctional siloxane unit with one organic group called T unit, monofunctional siloxane unit with three organic groups called M unit, called Q unit It consists of a tetrafunctional siloxane unit having no organic group. The Q unit is a unit that does not have an organic group bonded to a silicon atom (an organic group having a carbon atom bonded to a silicon atom), but is regarded as a siloxane unit in the present invention. In the following formulae, R represents a monovalent organic group represented by a methyl group or a phenyl group.

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 . More specifically, for example, in one D unit, one silicon atom is bonded to two oxygen atoms, and each oxygen atom is bonded to a silicon atom of another unit. The formula is -O _1/ _2- (R) ₂ Si-O _1/ _2- . Since there are two O _{1/2 s} , the D unit is usually expressed as (R) ₂ SiO _2/2 . However, in the present invention, in accordance with the expression of the A unit described later, the O unit _1/2 expression is used for each oxygen atom to express the M unit, D unit, T unit, and Q unit as follows.
In addition, when the terminal unit of the polymer chain is a unit other than the M unit, atoms other than the silicon atom bonded to O _1/2 of the terminal unit are ½ equivalent oxygen atoms, and one in total And represents an oxygen atom in a hydroxyl group or an alkoxy group. When expressed in the same manner as the expression of the siloxane unit below, for example, the hydroxyl group bonded to the silicon atom of the terminal unit is —O _{1/2 /} H.

In the siloxane unit (A) described later in the present invention, each of two silicon atoms is bonded to an oxygen atom, and each oxygen atom is bonded to a silicon atom outside the unit. Expressed as _1/2 . The siloxane unit (A) can be regarded as a D unit because it is bifunctional. Hereinafter, the crosslinkable organopolysiloxane will be described assuming that the siloxane unit (A) is one type of D unit in the present invention.

R ¹ to R ^{4 in} the formula (1) each independently represents a monovalent hydrocarbon group which may contain a hetero atom. Specific examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, and an alkynyl group) or a monovalent aromatic hydrocarbon group. The number of carbon atoms contained in the hydrocarbon group is not particularly limited, but is preferably 10 or less, more preferably 4 or less, in that decomposition of the silicone resin under high-temperature treatment conditions is further suppressed. Specific examples include a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, and a phenyl group.
The monovalent hydrocarbon group may contain a hetero atom, and examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. More specifically, —X ¹ —, —N (R ^a ) —, —C (═X ² ) —, —CON (R ^b ) —, —C (═X ³ ) X ⁴ —, —SO ₂ It is preferably contained in the form of N (R ^c ) —, a halogen atom, or a group combining these. X ¹ to X ⁴ each independently represents an oxygen atom and a sulfur atom, and R ^a , R ^b , and R ^c each independently represents an organic group having 4 or less carbon atoms.

R ¹ to R ⁴ are preferably an alkyl group having 4 or less carbon atoms (particularly preferred is a methyl group) or a phenyl group, from the viewpoint that decomposition of the silicone resin under high-temperature treatment conditions is further suppressed. .

In formula (1), Ar represents a divalent aromatic hydrocarbon group which may have a substituent. The two bonds of Ar are bonds of carbon atoms constituting the aromatic ring.
The number of carbon atoms contained in the divalent aromatic hydrocarbon group is not particularly limited, but is preferably 6 to 18, more preferably 6 to 12 in terms of further suppressing decomposition of the silicone resin under high temperature treatment conditions. . Specific examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, a biphenylene group, and a terphenylene group. Among these, a phenylene group is preferable in that the cost can be reduced, the flexibility of the silicone resin layer 14 is excellent, and the adhesion and peelability of the silicone resin layer 14 to the glass substrate 16 are more excellent. In addition, when it is desired to impart excellent heat resistance to the silicone resin layer 14, it is preferable to use a polycyclic aromatic hydrocarbon group as Ar.
The type of the substituent is not particularly limited, and examples thereof include a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, an arylalkyl group, an aryloxy group, a heterocyclic group, an amino group, a nitro group, And a cyano group.

The crosslinkable organopolysiloxane in the present invention is a polymer containing only a siloxane unit (A) as a siloxane unit, or a copolymer containing a siloxane unit (A) and another siloxane unit. The crosslinkable organopolysiloxane in the present invention is preferably a linear polymer, and the other siloxane units are preferably D units other than the siloxane unit (A). When the crosslinkable organopolysiloxane is a linear polymer, the crosslinkable organopolysiloxane is a polymer containing only the siloxane unit (A), a polymer containing the siloxane unit (A) and other D units, a siloxane unit ( There are polymers containing A) and M units, and polymers containing siloxane units (A), other D units and M units. However, two or more siloxane units (A), other D units, and M units may be present.
The crosslinkable organopolysiloxane in the present invention may be a non-linear polymer having a small number of branches. In this case, except for having a small number of T units and Q units that cause branching, the linear polymer has D units and optionally further M units.
The crosslinkable organopolysiloxane in the present invention is crosslinkable. For example, an organopolysiloxane consisting only of a siloxane unit (A) in which R ¹ to R ⁴ are all methyl groups and Ar is a phenylene group is crosslinkable, It can be cross-linked with UV light or the like. In order to further improve the crosslinkability, a siloxane unit (A) in which a part of R ¹ to R ⁴ is an alkenyl group or an alkynyl group can be contained.

The crosslinkable organopolysiloxane in the present invention is preferably a polymer containing only a siloxane unit (A) as a D unit, and a polymer containing a siloxane unit (A) and another D unit, and particularly a siloxane unit (A ) And other D units are preferred. The cross-linked product (silicone resin) of organopolysiloxane containing other D units has higher flexibility than the cross-linked product of polyorganosiloxane (silicone resin) not containing other D units, and the silicone resin layer for the glass substrate Good adhesion. Furthermore, when the other D unit is a D unit containing an alkenyl group, the crosslinkability is improved, and the decomposition of the cross-linked product (silicone resin) under high-temperature treatment conditions is further suppressed.
The D unit other than the siloxane unit (A) is preferably a siloxane unit (B) represented by the formula (2).

In formula (2), R ⁵ and R ⁶ each independently represent a monovalent hydrocarbon group that may contain a hetero atom. The definition of the monovalent hydrocarbon which may contain a hetero atom is the same as the case of R ¹ to R ⁴ described above. However, preferred monovalent hydrocarbon groups include alkenyl groups having 3 or less carbon atoms in addition to the above.
As R ⁵ and R ⁶ , an alkyl having 4 or less carbon atoms (particularly preferred is a methyl group) or an alkenyl group having 3 or less carbon atoms (in particular, a methyl group is preferable) in that decomposition of the silicone resin under high-temperature treatment conditions is further suppressed. In particular, a vinyl group is preferable.

As a preferred embodiment of the siloxane unit (B), the crosslinking between the crosslinkable organopolysiloxanes further proceeds, and the decomposition of the silicone resin under high temperature treatment conditions is further suppressed, so that the siloxane unit (B) is R ^At least one of ⁵ and R ⁶ is an alkenyl group having 3 or less carbon atoms, and in the case of other than the alkenyl group, any one of siloxane unit (B-1) which is an alkyl group having 4 or less carbon atoms, and R ⁵ and R ⁶ Are selected from the group consisting of siloxane units (B-2) which are alkyl groups having 4 or less carbon atoms, and the siloxane units (B) in the crosslinkable organopolysiloxane consist only of siloxane units (B-1), or And an embodiment comprising a siloxane unit (B-1) and a siloxane unit (B-2).

In the siloxane unit (B-1), at least one of R ⁵ and R ⁶ is an alkenyl group having 3 or less carbon atoms, preferably a vinyl group. When R ⁵ and R ⁶ are other than an alkenyl group, it is an alkyl group having 4 or less carbon atoms, preferably a methyl group.
A preferred embodiment of the siloxane unit (B-1) is that one of R ^{5 and} R ⁶ is a methyl group and the other is a vinyl group in that the decomposition of the silicone resin under high temperature treatment conditions is further suppressed. An embodiment is mentioned.
In the siloxane unit (B-2), both R ⁵ and R ⁶ are alkyl groups having 4 or less carbon atoms, preferably methyl groups.

When the siloxane unit (B) includes the siloxane unit (B-1) and the siloxane unit (B-2), the ratio of the siloxane unit (B-1) to the total siloxane unit (B) [siloxane unit (B- 1)] × 100 / [siloxane unit (B-1) + siloxane unit (B-2)] is not particularly limited, but the crosslinking between the crosslinkable organopolysiloxanes proceeds further, and the silicone resin under high temperature treatment conditions 30 to 80 mol% is preferable, and 40 to 60 mol% is more preferable in that the decomposition of is further suppressed and the adhesiveness and peelability of the silicone resin layer 14 to the glass substrate 16 are more excellent.

In addition, the crosslinkable organopolysiloxane may contain siloxane units (for example, M unit, T unit, Q unit) other than the siloxane unit (A) and the siloxane unit (B) described above. However, if there are many branched units (T units and Q units), the flexibility of the cross-linked product (silicone resin) is lowered, and if there are many M units, the polymer has a low number average molecular weight and has physical properties such as heat resistance. May decrease. Therefore, it is preferable that the number thereof is small. As described later, the content of units other than the D unit (siloxane unit (A) and siloxane unit (B)) is preferably 0 to 20 mol%, and 0 to 5 mol. % Is more preferable.

When the crosslinkable organopolysiloxane contains the siloxane unit (A) and the siloxane unit (B), the ratio of the siloxane unit (A) to the total of the siloxane unit (A) and the siloxane unit (B) 10 to 90 mol% is preferable, 30 to 90 mol% is more preferable, and 40 to 90 mol% is more preferable in that the decomposition of the silicone resin in the resin is further suppressed and the adhesion and peelability of the silicone resin layer 14 to the glass substrate 16 are more excellent. More preferred is ˜60 mol%.
The ratio of the total of the siloxane unit (A) and the siloxane unit (B) with respect to the total siloxane units in the crosslinkable organopolysiloxane further suppresses the decomposition of the silicone resin under high-temperature treatment conditions, and the silicone resin layer 14 80 to 100 mol% is preferable, and 95 to 100 mol% is more preferable in terms of better adhesion to the glass substrate 16 and peelability.
Further, the bonding type of the siloxane unit (A) and the siloxane unit (B) in the crosslinkable organopolysiloxane is not particularly limited, and may be any of a random copolymer, a block copolymer, and an alternating copolymer. Also good. Especially, an alternating copolymer is preferable at the point by which decomposition | disassembly of the silicone resin under high temperature processing conditions is suppressed more.
In the present invention, the alternating copolymer of the siloxane unit (A) and the siloxane unit (B) is a bond between the siloxane unit (A) and the siloxane unit (B), and a bond between the siloxane unit (A) and the siloxane unit (A). And a copolymer much more than the sum of the bonds of siloxane units (B) and siloxane units (B). These three types of bonds can be distinguished by, for example, ¹ H NMR measurement and ²⁹ Si NMR measurement, and the relative number ratio of these bonds can be calculated by the measurement. The alternating copolymer of the siloxane unit (A) and the siloxane unit (B) in the present invention may contain a small number of random bond portions or block bond portions. The proportion of the siloxane units (A) and siloxane units (B) in the alternating copolymer is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, based on the total of the above three types of bonds. More preferred is 95 to 100 mol%. In addition, although it does not distinguish whether it is an alternating copolymer, when the crosslinkable polysiloxane in this invention is an alternating copolymer, the siloxane unit (A) in the alternating copolymer and a siloxane unit (B The ratio of the siloxane unit (A) to the total of 50) is preferably 50 ± 5 mol%.
The alternating copolymer in the present invention may be one kind of silicone resin, or a mixture ratio of siloxane units (A) and siloxane units (B) by mixing two or more kinds of silicone resins. It may be obtained by adjusting so as to have a desirable ratio.

The number average molecular weight of the crosslinkable organopolysiloxane is not particularly limited, but it is excellent in handleability, excellent in film formability, and is more resistant to decomposition of the silicone resin under high temperature processing conditions. The number average molecular weight in terms of polystyrene as measured by chromatography is preferably 5,000 to 30,000, more preferably 10,000 to 20,000.
The number average molecular weight of the crosslinkable organopolysiloxane can be adjusted by controlling the reaction conditions. For example, the molecular weight can be controlled by changing the amount and type of terminal groups and the monomer mixing ratio. When the amount of terminal groups is increased, a low molecular weight product is obtained, and when the amount is decreased, a high molecular weight is obtained. Further, when the monomer ratio is biased, a low molecular weight product is obtained, and when the ratio is made equal, a high molecular weight product is obtained.

The method for producing the crosslinkable organopolysiloxane is not particularly limited as long as the siloxane unit (A) represented by the above formula (1) is included. For example, the silane compound represented by the formula (3) can be produced by polymerizing by a condensation reaction or a hydrolysis / condensation reaction. In the case of a crosslinkable organopolysiloxane having a siloxane unit (B), it can be produced using a silane compound represented by the formula (4). Furthermore, the crosslinkable organopolysiloxane having other siloxane units can be produced using a silane compound having at least one silanol group or hydrolyzable group. The polymerization reaction is usually carried out in an inert solvent, and the reaction can be carried out only by heating in the absence of a catalyst. If necessary, a reaction catalyst can be used.
A crosslinkable organopolysiloxane having a siloxane unit (A) and a method for producing the same are basically known, and are described in, for example, Japanese Patent Application Laid-Open No. 9-59387 and Japanese Patent Application Laid-Open No. 2008-280402. . As the crosslinkable organopolysiloxane and the method for producing the same in the present invention, those described in the known literature can be used.

In the formula (3) and ^(4), R 1 ~ ^{R 6} have the same meanings as ^R 1 ~ ^{R 6} in the formula (1) and (2).
In the formula (3), X and Y each independently represent a hydroxyl group or a hydrolyzable group (for example, primary to tertiary amino groups such as amino group, monoalkylamino group, dialkylamino group, halogen group, alkoxy group) Etc.).

The alternating copolymer can be obtained by polymerizing two kinds of monomers having different reactivities. For example, X is a polymerization reactive group of the silane compound represented by the above formula (3) to be the siloxane unit (A) and a polymerization reactive group of the silane compound represented by the above formula (4) to be the siloxane unit (B). Y having a mutual reactivity higher than both the reactivity between X and the reactivity between Y is selected, and a substantially equimolar amount of the two silane compounds is reacted. Thus, an alternating copolymer can be produced. By making the reactivity of X and Y higher than both the reactivity of X and the reactivity of Y, an alternating copolymer with fewer random bonds or block bonds can be obtained.
When producing an alternating copolymer, it is preferable that one of X and Y is a hydroxyl group, and the other is a primary to tertiary amino group such as an amino group, a monoalkylamino group, or a dialkylamino group. In particular, one is preferably a hydroxyl group and the other is a dialkylamino group, more preferably X is a hydroxyl group and Y is a dialkylamino group. The alkyl group in the monoalkylamino group or dialkylamino group is preferably an alkyl group having 4 or less carbon atoms, and particularly preferably a methyl group.
Alternating copolymers of organopolysiloxanes and their production methods are basically known. For example, Macromolecules 1998, 31, 8501 or Journal of Applied Polymer Science, Vol. 106, 1007, 2007). The polymer and its manufacturing method are described. As the alternating copolymer and the production method thereof in the present invention, those described in these known documents can be used.
As a specific production method, for example, an organic solvent solution of a silane compound represented by the above formula (3) (where X is a hydroxyl group) and a silane compound represented by the above formula (4) (Y is a dimethylamino group) A method of mixing an organic solvent solution of a certain thing at a ratio in which both silane compounds are equimolar amounts and reacting while heating and stirring, dividing one organic solvent solution into another organic solvent solution with heating and stirring, or continuously Alternatively, an alternating copolymer can be produced by a method of reacting while adding them.

The crosslinkable organopolysiloxane is cross-linked and cured through a predetermined cross-linking reaction to become a cross-linked product which is the silicone resin in the present invention. 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 silanol group condensation reaction, a heat treatment, a high energy ray treatment, or a radical reaction with 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 crosslinkable product (silicone resin) is crosslinked by a reaction between radical reactive groups via the radical reaction. It becomes.
Moreover, when crosslinkable organopolysiloxane has a silanol group, it crosslinks by the condensation reaction of silanol groups, and turns into a crosslinked material.
Further, when the crosslinkable organopolysiloxane has a hydrogen atom bonded to an alkenyl group or a silicon atom, it is crosslinked by a hydrosilylation reaction in the presence of a hydrosilylation catalyst (for example, a platinum-based catalyst) to form a crosslinked product.
Among the above-mentioned crosslinking forms, the form through radical reaction is preferable in that the generation of by-products due to the reaction is suppressed and a denser and excellent heat-resistant silicone resin can be obtained.
In the cross-linking reaction, a cross-linkable organopolysiloxane containing two or more types of siloxane units (A) represented by the formula (1) may be used in combination, or the siloxane units represented by the formula (1). You may use together other crosslinkable organopolysiloxane other than the crosslinkable organopolysiloxane containing (A).
Hereinafter, forming a silicone resin as a crosslinked product by crosslinking and curing the crosslinkable organopolysiloxane is simply referred to as curing of the crosslinkable organopolysiloxane.

[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 method for producing the glass laminate 10 of the present invention is not particularly limited, but in order to obtain a laminate having a peel strength (x) higher than the peel strength (y), a predetermined crosslinkable organopolysiloxane is formed on the surface of the support substrate 12. A method of forming the silicone resin layer 14 by curing siloxane is preferable. That is, a layer of a crosslinkable organopolysiloxane is formed on the surface of the support substrate 12, the crosslinkable organopolysiloxane is cured on the surface of the support substrate 12 to form the silicone resin layer 14, and then the silicone resin layer 14 This is a method of manufacturing the glass laminate 10 by laminating the glass substrate 16 on the silicone resin surface.
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 crosslinkable organopolysiloxane layer on the surface of the support substrate 12 and curing the crosslinkable organopolysiloxane on the surface of the support substrate 12 is a resin layer formation 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 of a crosslinkable organopolysiloxane is formed on the surface of the support base 12, and the crosslinkable organopolysiloxane is cured on the surface of the support base 12 to form the silicone resin layer 14.
In order to form a crosslinkable organopolysiloxane layer on the support substrate 12, a coating composition in which the crosslinkable organopolysiloxane is dissolved in a solvent is used, and this composition is applied onto the support substrate 12. It is preferable to form a solution layer and then remove the solvent to form a crosslinkable organopolysiloxane layer. The thickness of the crosslinkable organopolysiloxane layer 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. Specifically, toluene, xylene, THF, chloroform etc. can be illustrated, for example.

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.

Next, the crosslinkable organopolysiloxane on the support substrate 12 is cured 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, as the curing method, an optimum method is appropriately selected according to the crosslinking type of the crosslinkable organopolysiloxane. Especially, when the crosslinkable organopolysiloxane has a radical polymerizable group, it is preferable to produce the silicone resin layer 14 by thermosetting in that a silicone resin excellent in adhesion to the glass substrate 16 and heat resistance can be obtained. 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, 300 to 475 ° C. is preferable, and 350 to 450 ° C. is more preferable. The heating time is usually preferably 10 to 300 minutes, more preferably 20 to 120 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 is preferably cured by precuring (precuring) and then curing (main curing). By performing precure, the silicone resin layer 14 excellent in heat resistance can be obtained. Precuring is preferably carried out 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 of the crosslinkable organopolysiloxane and the step of precuring. The removal of the solvent is preferably performed by heating to 100 ° C. or higher, and precure can be continued by heating to 150 ° C. or higher. The temperature at which the solvent is removed and precured and the heating time are preferably 100 to 420 ° C. and 5 to 60 minutes, more preferably 150 to 300 ° C. and 10 to 30 minutes. A silicone resin layer that is easily peeled when the temperature is 420 ° C. or lower is obtained.

(Lamination process)
In the laminating step, the glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14 obtained in the resin layer forming step, and the layer of the supporting base 12, the silicone resin layer 14, and the glass substrate 16 are laminated. This is a step of obtaining the glass laminate 10 provided in this order. 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.

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

When laminating the glass substrate 16, it is preferable that the surface of the glass substrate 16 in contact with the silicone resin layer 14 is sufficiently washed and laminated in an environment with a high 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. In view of this, it is preferable to perform heat treatment at 300 ° C. or higher (preferably 300 to 400 ° C.) for 5 minutes or longer (preferably 5 to 30 minutes).

In addition, formation of the silicone resin layer 14 which provided the difference in the peeling strength with respect to the 1st main surface of the glass substrate 16 and the peeling strength with respect to the 1st main surface of the support base material 12 is not restricted to the said 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, 400 ° 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, etc. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
In addition, as a circuit for an electronic component, in a CCD or CMOS, a metal of a conductive part, a silicon oxide or a silicon nitride of an insulating part, and the like, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board And various members corresponding to a rigid flexible printed circuit board.

(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, the laminated body with all members can be assembled, and then the support substrate 18 with the silicone resin layer can be peeled from the laminated body with all members to manufacture an electronic device. Furthermore, the laminate with all members is assembled using two sheets, and then the two support bases 18 with the silicone resin layer are peeled from the laminate with all members to form a glass substrate with a member having two glass substrates. It can also be manufactured.

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

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

(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. The process which isolate | separates into the glass substrate 16 (glass substrate with a member) on which the member 20 for lamination | stacking laminated | stacked, and the support base material 18 with a silicone resin layer, and obtains the glass substrate 24 with a member containing the member 20 for electronic devices and the glass substrate 16 It is.
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 is 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 separating the glass substrate 24 with a member from the glass laminate 10, it is more likely that the fragments of the silicone resin layer 14 are electrostatically adsorbed to the glass substrate 24 with a member by controlling the spraying and humidity with an ionizer. Can be suppressed.

The above-described method for manufacturing the glass substrate with member 24 is suitable for manufacturing a small display device used for a mobile terminal such as a mobile phone or a 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.

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

In Examples 1 to 3 and Comparative Example 1 below, as a glass substrate, a glass plate made of non-alkali borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.3 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., Asahi Glass Co., Ltd. trade name “AN100”) was used. Further, as the supporting base material, a glass plate (240 mm long, 240 mm wide, 0.4 mm thick, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd., also made of non-alkali borosilicate glass. )It was used.

<Production Example 1> Production of liquid containing crosslinkable organopolysiloxane (S1) 1,4-bis (hydroxydimethylsilyl) benzene (35 parts by mass, gelest) as a compound constituting siloxane unit (A) in a nitrogen atmosphere Was added to toluene (90 parts by mass) to prepare a reaction solution. Next, the reaction solution was heated to 110 ° C., and bis (dimethylamino) dimethylsilane (11 parts by mass, manufactured by Gerest) and bis (dimethylamino) methylvinylsilane (12 parts by mass, manufactured by Gerest) were converted into toluene (40 The solution dissolved in (part by mass) was dropped into the reaction solution over about 5 minutes. Thereafter, the reaction solution was stirred at 110 ° C. for 1 hour. After completion of the stirring, the reaction solution was naturally cooled to room temperature, and the reaction solution was added to methanol (3250 parts by mass) for reprecipitation treatment. Next, the precipitate was collected and vacuum-dried to obtain a colorless and transparent liquid crosslinkable organopolysiloxane (S1).

The obtained crosslinkable organopolysiloxane (S1) had a number average molecular weight (polystyrene conversion) by GPC (gel permeation chromatography) of 1.2 × 10 ⁴ . Further, by using a thermogravimetric analyzer (manufactured by TA Instruments Inc.), the temperature is increased from room temperature to 700 ° C. in a nitrogen atmosphere (100 ml / min) at a rate of temperature increase of 15 ° C./min. The 5% weight loss temperature of the functional organopolysiloxane (S1) was measured and found to be 535 ° C. Furthermore, the structure of the crosslinkable organopolysiloxane (S1) was identified by ¹ H NMR measurement, ²⁹ Si NMR measurement, and ¹³ C NMR measurement. ^For assignment of spectra in ¹ H NMR measurement and ²⁹ Si NMR measurement, Journal of Applied Polymer Science, 2007, 106, 1007-1013 was referred.
¹ H NMR, ²⁹ Si NMR, and ¹³ C NMR measuring apparatus: ECA600 manufactured by JEOL RESONANCE
¹ H NMR measurement method: CDCL ₃ was added to a sample to prepare a sample concentration of 10% by mass. Tetramethylsilane was used as a standard.
²⁹ Si NMR measurement method: CDCL ₃ was added to a sample to prepare a sample concentration of 30% by mass. Moreover, acetylacetone chromium salt was added as a relaxation reagent, and it prepared so that it might become 0.1 mass% with respect to a sample. Tetramethylsilane was used as a standard.
¹³ C NMR measurement: CDCL ₃ was added to the sample to prepare a sample concentration of 10% by mass. Tetramethylsilane was used as a standard.
The composition of the copolymer is determined from the ¹ H NMR measurement. Each assignment was determined for the spectrum obtained from ¹ H NMR measurement by the method described in Journal of Applied Polymer Science, 2007, 106, 1007-1013. As a result, 7.55 ppm derived from the phenylene group of the siloxane unit (A), 0.337 pp and 0.142 ppm derived from the methyl group of the siloxane units (B-1) and (B-2), the siloxane unit (B— 5.9 ppm derived from the vinyl group of 2) was confirmed. The ratio (mol%) of each unit of the obtained copolymer was calculated by ¹ H-NMR measurement and shown in Table 1.
²⁹ Si NMR and ¹³ C NMR give information about the bonds.
Each assignment of the spectrum obtained from ²⁹ Si NMR measurement was determined by the method described in Journal of Applied Polymer Science, 2007, 106, 1007-1013.
In the formulas represented by the following formulas (α) to (δ), the spectra of −19.5 ppm, −33.4 ppm, −2.5 ppm, and −1.6 ppm, which are the attribution of Si underlined, are respectively shown. confirmed. Moreover, the spectrum of the silicon atom to which the same siloxane unit was connected was not observed, or even when observed, the concentration was extremely low. It was confirmed that the siloxane unit (A) and the siloxane unit (B) were alternating copolymers in which the siloxane units (B) were alternately arranged. Further, from the integral values of the spectra of -19.5 ppm and -33.4 ppm, it was confirmed that the bond between the siloxane unit (A) and the siloxane unit (B) was 90 mol% in the crosslinkable organopolysiloxane (S1). It was.

Next, a crosslinkable organopolysiloxane (S1) (30 parts by mass) was dissolved in xylene (70 parts by mass) to prepare a liquid material containing the crosslinkable organopolysiloxane (S1).

<Production Examples 2 to 4> Production of Crosslinkable Organopolysiloxanes (S2) to (S4) and Liquid Products Organos obtained in the same manner as in Production Example 1 for crosslinkable organopolysiloxanes (S2) to (S4) It manufactured so that each unit in polysiloxane might become the composition ratio (molar ratio) shown in Table 1. Next, the obtained crosslinkable organopolysiloxanes (S2) to (S4) were dissolved in xylene to prepare liquid materials each containing the crosslinkable organopolysiloxanes (S2) to (S4).

<Example 1>
First, a support substrate having a thickness of 0.4 mm was cleaned with pure water, and further cleaned with UV.
Next, a liquid material containing the crosslinkable organopolysiloxane (S1) was applied on the first main surface of the support substrate with a spin coater (coating amount 120 g / m ² ).
Next, it was heat-cured in the air at 375 ° C. for 30 minutes to form a 6 μm-thick silicone resin layer on the first main surface of the support substrate.

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 450 ° 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.
In addition, 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 layer and the silicone resin layer is determined as the peeling strength at the interface between the silicone resin layer and the glass substrate. It was confirmed that it was higher than (y).

<Example 2>
In the same manner as in Example 1, a crosslinkable organopolysiloxane (S2) was heat-cured on the first main surface of the support substrate to form a 6 μm silicone resin layer.
Subsequently, a glass laminate B was obtained in the same manner as in Example 1.
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 the glass laminated body B was isolate | separated by the method similar to Example 1, without damaging a glass substrate and a support base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate layer and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.

<Example 3>
In the same manner as in Example 1, a crosslinkable organopolysiloxane (S3) was heat-cured on the first main surface of the support substrate to form a 6 μm thick silicone resin layer.
Subsequently, a glass laminate C was obtained in the same manner as in Example 1.
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.
And the glass laminated body C was isolate | separated by the method similar to Example 1, without damaging a glass substrate and a support base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate layer and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.

<Comparative Example 1>
After the support substrate is cleaned with pure water cleaning, UV cleaning, or the like, a crosslinkable organopolysiloxane (S4) is applied onto the support substrate with a spin coater (coating amount 10 g / m ² ), 180 A silicone resin layer having a film thickness of 16 μm was obtained by heating and curing in the air at 30 ° C. for 30 minutes.
After cleaning the surface of the glass substrate that contacts the silicone resin layer with pure water cleaning, UV cleaning, etc., the silicone resin layer forming surface of the support substrate and the glass substrate are bonded together by a vacuum press at room temperature. A glass laminate P having an addition polymerization type silicone resin layer was obtained.
Next, when the glass laminate P was subjected to the same heat treatment as in Example 1, changes in appearance such as foaming of the silicone resin layer and whitening were confirmed. In the glass laminate P, the glass substrate was partially separated.

Since Examples 1 to 3 were glass laminates having the silicone resin layer of the present invention, the decomposition of the silicone layer was not confirmed even when subjected to high temperature treatment, and the glass substrate could be easily peeled off. In addition, as shown in Examples 1 and 3, in the case of the crosslinkable organopolysiloxane containing more siloxane units (A), it was confirmed that the 5% weight loss temperature was higher and the heat resistance was superior.
On the other hand, in the comparative example 1 corresponding to the embodiment described in the example column of Patent Document 1, as described above, the silicone resin layer is decomposed during the treatment under the high temperature condition, and the silicone resin layer is foamed. And whitening was confirmed. Moreover, partial peeling of the glass substrate was also confirmed with foaming.

<Example 4>
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 vapor deposition, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine is formed on the second main surface side of the glass substrate, and bis [ (N-naphthyl) -N-phenyl] benzidine, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] to 8-quinolinol aluminum complex (Alq ₃ ) as the light emitting layer A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer are formed in this order, and then aluminum is formed by sputtering, followed by photolithography. Next, another glass substrate is formed on the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. The organic EL structure is formed on the glass substrate by the above procedure, and the glass laminate A (hereinafter referred to as panel A) having the organic EL structure on the glass substrate is used in the present invention. It is a laminated body (panel for display apparatuses with a support base material) with a member for electronic devices.
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 5>
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 process. 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 6>
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 vapor deposition, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine is formed on the second main surface side of the glass substrate, and bis [ (N-naphthyl) -N-phenyl] benzidine, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] to 8-quinolinol aluminum complex (Alq ₃ ) as the light emitting layer A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer are formed in this order, and then aluminum is formed by sputtering, followed by photolithography. Next, another glass substrate is formed on the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. The organic EL structure is formed on the glass substrate by the above procedure, and the glass laminate A (hereinafter referred to as panel A) having the organic EL structure on the glass substrate is used in the present invention. It is a laminated body (panel for display apparatuses with a support base material) with a member for electronic devices.
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. 2012-2114060 filed on Sep. 27, 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

A support substrate layer, a silicone resin layer, and a glass substrate layer are provided in this order, and the peel strength at the interface between the support substrate layer and the silicone resin layer is the interface between the glass substrate layer and the silicone resin layer. It is a glass laminate that is higher than the peel strength of
A glass laminate in which the silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane containing a siloxane unit (A) represented by the formula (1):

In the formula (1), R 1 to R 4 each independently represents a monovalent hydrocarbon group which may contain a hetero atom. Ar represents a divalent aromatic hydrocarbon group which may have a substituent.
The glass laminate according to claim 1, wherein R 1 to R 4 in the siloxane unit (A) are each independently an alkyl group having 4 or less carbon atoms or a phenyl group.
The glass laminate according to claim 1 or 2, wherein the crosslinkable organopolysiloxane further contains a siloxane unit (B) represented by the formula (2):

In Formula (2), R 5 and R 6 each independently represent a hydrocarbon group that may contain a hetero atom.
In the crosslinkable organopolysiloxane, the ratio of the siloxane unit (A) to the total of the siloxane unit (A) and the siloxane unit (B) is 30 to 90 mol%, and the siloxane unit (A ) And the siloxane unit (B) in a total amount of 80 to 100 mol%.
When the siloxane unit (B) is at least one of R 5 and R 6 is an alkenyl group having 3 or less carbon atoms and is not the alkenyl group, the siloxane unit (B-1) is an alkyl group having 4 or less carbon atoms, and , R 5 and R 6 are both selected from the group consisting of siloxane units (B-2) which are alkyl groups having 4 or less carbon atoms,
The siloxane unit (B) in the crosslinkable organopolysiloxane consists only of the siloxane unit (B-1), or consists of the siloxane unit (B-1) and the siloxane unit (B-2). The glass laminated body of Claim 3 or 4.
The glass laminate according to any one of claims 3 to 5, wherein the crosslinkable organopolysiloxane is an alternating copolymer of the siloxane unit (A) and the siloxane unit (B).
The glass laminate according to any one of claims 1 to 6, wherein the silicone resin layer has a thickness of 2 to 100 µm.
The glass laminate according to any one of claims 1 to 7, wherein the supporting substrate is a glass plate.
A layer of a crosslinkable organopolysiloxane is formed on one side of the support substrate, the crosslinkable organopolysiloxane is crosslinked on the surface of the support substrate to form a silicone resin layer, and then the support group of the silicone resin layer is formed. The method for producing a glass laminate according to any one of claims 1 to 8, wherein a glass substrate is laminated on a surface opposite to a surface in contact with the material.
A support substrate with a silicone resin layer, comprising a support substrate and a silicone resin layer having a peelable surface provided on the support substrate surface;
The support substrate with a silicone resin layer, wherein the silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane containing a siloxane unit (A) represented by the formula (1):

In the formula (1), R 1 to R 4 each independently represents a monovalent hydrocarbon group which may contain a hetero atom. Ar represents a divalent aromatic hydrocarbon group which may have a substituent.
The support substrate with a silicone resin layer according to claim 10, wherein the crosslinkable organopolysiloxane further contains a siloxane unit (B) represented by the formula (2):

In formula (2), R 5 and R 6 each independently represent a monovalent hydrocarbon group that may contain a hetero atom.
The support substrate with a silicone resin layer according to claim 11, wherein the crosslinkable organopolysiloxane is an alternating copolymer of the siloxane unit (A) and the siloxane unit (B).
The support substrate with a silicone resin layer according to any one of claims 10 to 12, wherein the silicone resin layer has a thickness of 2 to 100 µm.
The support substrate with a silicone resin layer according to any one of claims 10 to 13, wherein the support substrate is a glass plate.
15. A silicone resin layer is formed by forming a crosslinkable organopolysiloxane layer on a support substrate surface and crosslinking the crosslinkable organopolysiloxane on the support substrate surface. The method to manufacture the support base material with a silicone resin layer as described in any one of Claims.