KR20150070978A - Manufacturing method of support substrate with resin layer, manufacturing method of glass laminated body and manufacturing method of electronic device - Google Patents

Abstract

The present invention relates to a method for manufacturing a support substrate with an attached resin layer which includes a support substrate and a silicon resin layer and is used to manufacture a glass laminate by laminating a glass substrate on the silicon resin layer. The method includes: an application process of forming a curable silicon composition layer on the support substrate by applying a curable silicon composition including curable silicon and a solvent on the support substrate, and then obtaining a curable layer attachment support substrate including the support substrate and the silicon composition layer; an insertion process of inserting the curable layer attachment support substrate into a heat processing apparatus and then stacking the curable layer attachment support substrate on support pins in the heat processing apparatus; a first heating process of arranging a heating plate on an upper side of the curable silicon composition layer of the curable layer attachment support substrate, executing ventilation, performing a heating process on the curable layer attachment support substrate at a first temperate or lower, and removing the solvent remaining on the curable silicon composition layer; a moving process of placing the curable silicon composition layer apart from the heating plate after the first heating process; an extraction process of extracting the curable layer attachment support substrate from the heating process apparatus; and a second heating process of performing a heat process on the curable layer attachment support substrate at a second temperature higher than the first temperature.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a manufacturing method of a supporting substrate with a resin layer, a method of manufacturing a glass laminate, and a manufacturing method of an electronic device,

The present invention relates to a method of manufacturing a supporting substrate with a resin layer, a method of manufacturing a glass laminate, and a method of manufacturing an electronic device.

Recently, devices (electronic devices) such as a solar cell (PV), a liquid crystal panel (LCD), and an organic EL panel (OLED) have been made thinner and lighter in weight. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate in the manufacturing process of the device is deteriorated.

In recent years, in order to cope with the above problem, a glass laminate in which a glass substrate and a reinforcing plate are laminated is prepared, an electronic device member such as a display device is formed on a glass substrate of the glass laminate, (See, for example, Patent Document 1). The reinforcing plate has a supporting substrate and a silicon resin layer fixed on the supporting substrate, and the silicon resin layer and the glass substrate are brought into close contact with each other to be peelable. The reinforcing plate is peeled from the interface between the silicon resin layer of the glass laminate and the glass substrate and the reinforcing plate separated from the glass substrate is laminated with the new glass substrate and can be reused as the glass laminate.

International Publication No. 2007/018028

On the other hand, there is known a method in which a support substrate on which a coating film is disposed is placed on top of a plurality of support pins and heated and dried. As a method of heating and drying, there is known a method using a heat treatment apparatus provided with a heating plate.

The present inventors have found that when a reinforcing plate is manufactured according to the method described in Patent Document 1, a support substrate on which a coating film serving as a silicone resin layer is heated by heating is placed on the top of a plurality of support pins provided in a heat treatment apparatus, A post bake treatment was performed to form a silicone resin layer, and then a glass substrate was laminated on the silicone resin layer to prepare a glass laminate. Subsequently, the obtained glass laminate was heat-treated to evaluate the peelability of the glass substrate. As a result, it was found that a part of the silicon resin layer was cohesively broken and adhered to the surface of the glass substrate.

If the silicone resin is adhered to the glass substrate, the obtained electronic device is not suitable for use as a product, so that the yield of the electronic device is lowered and the productivity is lowered.

SUMMARY OF THE INVENTION The present invention has been made in view of the problems described above, and it is an object of the present invention to provide a method for manufacturing a glass substrate having a silicon substrate layer and a silicon substrate layer, And a method thereof.

It is another object of the present invention to provide a method for manufacturing a glass laminate using a resin layer-attached support substrate manufactured by the method for manufacturing a supporting substrate with a resin layer and a method for manufacturing an electronic device using the glass laminate.

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems and have completed the present invention.

That is, according to a first aspect of the present invention, there is provided a method for manufacturing a glass laminate, comprising the steps of: forming a resin layer on a support substrate, the support substrate having a silicon resin layer formed on one side of a support substrate and a support substrate, A method of making a curable silicone composition comprising a curable silicone composition comprising a curable silicone and a solvent on a support substrate to form a layer of curable silicone composition on the support substrate and to obtain a curable layer bonded support substrate having a support substrate and a layer of curable silicone composition A carrying step of carrying a supporting substrate with a curable layer in a heating processing apparatus and carrying a supporting substrate with a curable layer on a supporting pin in the heating processing apparatus; A plate is placed and exhausted, and the cured layer-attached support substrate is heated at a first temperature or lower A first heating step of performing heat treatment to remove the solvent remaining in the curable silicone composition layer; a moving step of moving the curable silicone composition layer and the heating plate subjected to the heat treatment to a distance from the heating plate after the first heating step; And a second heating step of performing a heating treatment at a second temperature higher than the first temperature and a second heating step of obtaining a silicon resin layer on the supporting substrate with the curable layer in this order A method for manufacturing a supporting substrate with a layered structure.

In the first aspect, it is preferable that the curable silicone comprises an organoalkenyl polysiloxane having an alkenyl group and an organohydrogen polysiloxane having a hydrogen atom bonded to a silicon atom.

In the first aspect, it is preferable that the first temperature satisfies the ultracentrifugation point of the solvent-30 deg. C < the first temperature < solvent > + 30 deg.

A second mode of the present invention is a laminated glass comprising a glass substrate laminated on a silicon resin layer in a resin layer-attached supporting substrate produced in the first form to obtain a glass laminate having a supporting substrate, a silicone resin layer and a glass substrate in this order And a process for producing the glass laminate.

A third aspect of the present invention is a method for manufacturing a semiconductor device, comprising: a member forming step of forming a member for an electronic device on a surface of a glass substrate of a glass laminate manufactured in the second form, And removing the resin layer-attached supporting substrate from the adhered laminate to obtain an electronic device having a glass substrate and a member for an electronic device.

According to the present invention, it is possible to provide a method for producing a supporting substrate with a resin layer having a supporting substrate and a silicone resin layer, which is used for producing a glass laminate in which cohesive failure of the silicone resin layer is further suppressed when the glass substrate is peeled have.

According to the present invention, there can also be provided a manufacturing method of a glass laminate using a resin layer-attached support substrate manufactured by the manufacturing method of the supporting substrate with the resin layer and a method of manufacturing an electronic device using the glass laminate.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a manufacturing process of a method of manufacturing a supporting substrate with a resin layer according to the present invention. Fig.
2 (A) and 2 (B) are schematic cross-sectional views showing one embodiment of a manufacturing method of a supporting substrate with a resin layer according to the present invention in the order of process.
3 is a schematic cross-sectional view showing a configuration of a heat treatment apparatus.
4 is a schematic cross-sectional view of the glass laminate of the present invention.
5A and 5B are schematic cross-sectional views showing an embodiment of a method of manufacturing an electronic device according to the present invention in the order of process.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention. have.

The inventors of the present invention have found that when the curable silicone composition layer is dried using a heating plate disposed on the upper side of the curable silicone composition layer, the solvent remaining in the curable silicone composition layer is volatilized, It is found that one of the reasons is that it stays between the composition layers. When such a volatile solvent is present in a large amount, the remaining solvent is difficult to volatilize from the curable silicone composition layer, and when the supporting substrate with the curable layer is carried out from the heat treatment apparatus, the solvent is returned to the curable silicone composition layer, It is presumed that the curability of the composition layer is lowered, and as a result, cohesive failure tends to progress.

Therefore, after the heating is completed, the heating plate and the curable silicone composition layer are separated from each other to expand the space between them, thereby promoting the exhaust of the solvent, lowering the solvent concentration and decreasing the influence on the silicon resin layer, It is presumed to be obtained.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a flowchart showing a manufacturing process in a manufacturing method of a resin substrate with a resin layer according to the present invention. FIG. As shown in Fig. 1, a method of manufacturing a supporting substrate with a resin layer includes a coating step S102, a carrying-in step S104, a first heating step S106, a moving step S108, a carrying-out step S110 and a second heating step S112.

Hereinafter, the material used in each step and the procedure thereof will be described in detail. First, the application step S102 will be described in detail.

<Coating Step>

The coating step S102 is a step of coating a curable silicone composition comprising a curable silicone and a solvent onto a support substrate to form a layer of curable silicone composition on the support substrate and obtaining a curable layer-attached support substrate having a support substrate and a layer of curable silicone composition Process. By performing the corresponding step S102, the curable silicone composition layer 12 is formed on the supporting substrate 10 as shown in Fig. 2A, and the supporting substrate 14 with the curable layer is obtained.

Hereinafter, the material (support substrate, curable silicone composition) used in the present step S102 will be described in detail, and then the procedure of the step S102 will be described in detail.

(Supporting substrate)

The support substrate 10 has two main surfaces, that is, a front surface and a back surface, and supports the glass substrate 20 to be described later in cooperation with the silicon resin layer 16 to be described later. Cracks, breakage, and the like of the glass substrate 20 at the time of manufacturing the electronic device member. Further, when a glass substrate having a thickness thinner than that of the conventional one is used, by using a glass laminate having the same thickness as that of the conventional glass substrate, it is possible to use a manufacturing technique or a manufacturing facility suitable for a conventional glass substrate Is one of the purposes of using the supporting substrate 10.

As the supporting substrate 10, for example, a metal plate such as a glass plate, a plastic plate, an SUS plate, a ceramic plate, or the like is used. The supporting substrate 10 is preferably formed of a material having a smaller coefficient of linear expansion than that of the glass substrate 20 in the case where the member forming step involves heat treatment and more preferably formed of the same material as the glass substrate 20 Do. That is, the supporting substrate 10 is preferably a glass plate. In particular, the supporting substrate 10 is preferably a glass plate containing the same glass material as the glass substrate 20.

The thickness of the support substrate 10 may be thicker or thinner than that of the glass substrate 20. The thickness of the support substrate 10 is preferably selected based on the thickness of the glass substrate 20, the thickness of the resin layer 16, and the thickness of the glass laminate. For example, the present member forming process is designed to process a substrate having a thickness of 0.5 mm. When the sum of the thickness of the glass substrate 20 and the thickness of the resin layer 16 is 0.1 mm, the thickness of the support substrate 10 Is set to 0.4 mm. The thickness of the support substrate 10 is preferably 0.2 to 5.0 mm in general.

When the support substrate 10 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for ease of handling and difficulty in breaking. The thickness of the glass plate is preferably not more than 1.0 mm from the viewpoint of the rigidity required to warp properly without breaking when peeling off after formation of the electronic device member.

The difference in average linear expansion coefficient (hereinafter simply referred to as "average linear expansion coefficient") of the support substrate 10 and the glass substrate 20 at 25 to 300 ° C is preferably 500 × 10 ^-7 / ° C or less, Is not more than 300 × 10 ^-7 / ° C, and more preferably not more than 200 × 10 ^-7 / ° C. If the difference is too large, there is a possibility that the glass laminate will vigorously warp during heating and cooling in the member forming process, or the glass substrate 20 and the resin layer-attached supporting substrate 18 described later may peel off. When the material of the glass substrate 20 and the material of the support substrate 10 are the same, the occurrence of such a problem can be suppressed.

(Curable silicone composition)

The curable silicone composition contains at least a curable silicone and a solvent. By applying the curable silicone composition on the support substrate 10 as described later, a curable silicone composition layer containing curable silicone is obtained.

Hereinafter, the materials contained in the composition will be described in detail.

The curable silicone is a compound or composition which is cured to become a silicone resin. These curable silicones are classified into condensation reaction type silicon, addition reaction type silicone, ultraviolet ray curable type silicone and electron beam curable type silicone depending on the curing mechanism, and they can all be used. Of these, addition reaction type silicon is preferable. This is because the curing reaction is easy, the degree of peeling property when the silicone resin layer is formed is good, and the heat resistance is high.

The addition reaction type silicone is a curable composition containing a subject and a crosslinking agent and curing in the presence of a catalyst such as a platinum-based catalyst. The curing of the addition reaction type silicon is promoted by the heat treatment. The subject in the addition reaction type silicon is preferably an organopolysiloxane having an alkenyl group (vinyl group, etc.) bonded to a silicon atom (that is, an organoalkenyl polysiloxane, preferably a straight chain), and an alkenyl group, Point. The crosslinking agent in the addition reaction type silicone is preferably an organopolysiloxane having a hydrogen atom (hydrosilyl group) bonded to a silicon atom (that is, an organohydrogenpolysiloxane, more preferably a straight chain), and a hydrosilyl group or the like It becomes a crosslinking point.

The addition reaction type silicone is cured by the addition reaction of the cross-linking points of the subject and the cross-linking agent. The molar ratio of the hydrogen atoms bonded to the silicon atoms of the organohydrogenpolysiloxane with respect to the alkenyl group of the organoalkenyl polysiloxane is preferably 0.5 to 2 in view of better heat resistance derived from the crosslinked structure.

Curable silicone compositions include solvents. The solvent is preferably a solvent capable of easily dissolving various components and capable of easily removing volatiles. Specific examples thereof include butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF, chloroform and the like. Among these, saturated hydrocarbons are preferable, and various saturated hydrocarbon solvents substantially consisting of one or more kinds of saturated hydrocarbons (straight chain saturated hydrocarbon, branched chain saturated hydrocarbon, alicyclic saturated hydrocarbon) are used. (Manufactured by ExxonMobil Co., Ltd.), Isopar H (manufactured by ExxonMobil Co., Ltd.), Isopar M (manufactured by ExxonMobil Co., Ltd.), Norther 13 (Exxon Mobil Co., Ltd.), Norther 15 (Exxon Mobil Co., Ltd.), Exol D40 (Exxon Mobil Co., Ltd.), Exol D60 (Manufactured by Chuo Chemical Industry Co., Ltd.) and IP solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.).

Among them, as described later, it is preferable to use a solvent having an ultra violet spot (atmospheric pressure reduction) of 210 DEG C or lower from the viewpoint that the solvent easily volatilizes in the first heating step.

When the curable silicone contained in the curable silicone composition is an addition reaction type silicone, the curable silicone composition may further contain a catalyst (in particular, a platinum group metal-based catalyst) or a reaction inhibitor.

The platinum group metal catalyst (platinum group metal catalyst for hydrosilylation) is a catalyst for promoting and promoting the hydrosilylation reaction of an alkenyl group in the organoalkenyl polysiloxane and a hydrogen atom in the organohydrogenpolysiloxane. Examples of the platinum group metal catalyst include platinum, palladium, and rhodium catalysts. Particularly, a platinum catalyst is preferred from the viewpoints of economy and reactivity.

The reaction inhibitor (reaction inhibitor for hydrosilylation) is a so-called available time lengthener (also referred to as a retarder) that inhibits the catalytic activity of the catalyst (particularly, the platinum group metal catalyst) at room temperature and lengthens the pot life of the curable silicone composition . Examples of the reaction inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, and organic chlorine compounds. Particularly, acetylenic compounds (for example, acetylenic alcohols and silylated acetylenic alcohols) are suitable.

(Process procedure)

The method of applying the curable silicone composition on the supporting substrate is not particularly limited, and a known method can be adopted. Examples of the coating method include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing and gravure coating. Among these methods, it can be appropriately selected depending on the kind of the curable silicone composition.

In addition, the thickness of the curable silicone composition layer is not particularly limited, and is appropriately adjusted so as to obtain a silicone resin layer having a suitable thickness described later.

<Transportation Process>

The carrying-in step S104 is a step of carrying the supporting substrate with the curable layer in the heating processing apparatus and loading the supporting substrate with the curable layer on the supporting pin in the heating processing apparatus. By carrying out this step, the support substrate 14 with the curable layer is loaded on the top of the support pin 34 in the heat treatment apparatus 30, as shown in Fig. The support pin 34 supports the back surface (the surface opposite to the side on which the curable silicone composition layer is provided) of the support substrate 10 in the support substrate 14 having the curable layer.

Hereinafter, the heat treatment apparatus 30 used in the present step will be described in detail.

3 is a cross-sectional view schematically showing an example of a heat treatment apparatus 30 according to the present invention. The heat treatment apparatus 30 is a device for performing heat treatment in the first heating step S106 described later, and is a so-called pre-baking apparatus.

The heat treatment apparatus 30 includes a support pin 34 for supporting the support substrate 14 with a curable layer in the heating chamber 32, a support base 36 for supporting the support pin 34, And a plate-shaped heating plate 38 disposed on the upper portion of the heating plate 14.

Although only two support pins 34 are shown in Fig. 3, the number of support pins 34 is not particularly limited. Further, the heat treatment apparatus 30 has a lifting mechanism for lifting and lowering a heating plate 38 (not shown), and the heating plate 38 is movable up and down in Fig.

An exhaust pipe 40 connected to exhaust means (not shown) is provided in the upper portion of the heat treatment apparatus 30. The exhaust pipe 40 is connected to the exhaust pipe 40 through a gas supply port The solvent or the like volatilized from the composition layer 12 is exhausted from the exhaust pipe 40. Further, a loading / unloading port 42 for loading / unloading the support substrate 14 with a curable layer is provided on the side of the heat treatment apparatus 30. [

As the procedure of this step S104, the supporting substrate 14 with the curable layer is brought into the heat treatment apparatus 30 through the loading / unloading port 42, and the supporting substrate 14 with the curable layer is loaded on the supporting pin 34 .

&Lt; First Heating Step &

In the first heating step S106, the heating plate is placed on the curable silicone composition layer of the supporting substrate with the curable layer, and the supporting substrate with the curable layer is subjected to heat treatment at a temperature not higher than the first temperature while evacuating, And removing the solvent. This step S106 is a so-called pre-baking step. By performing this step S106, the surface of the curable silicone composition can be smoothed by removing the solvent remaining in the curable silicone composition layer and heating at an appropriate temperature. After the pre-baking treatment, the post-baking treatment is performed in the second heating step S112 described later to remove the solvent remaining in the formed silicone resin layer to further flatten the surface shape, .

In this step S106, the heating plate 38 is disposed on the upper portion of the support substrate 14 having the curable layer as shown in Fig. 3, and heat treatment is performed. Further, as shown in Fig. 3, the heating plate 38 faces the curable silicone composition layer 12.

Although the distance between the heating plate 38 and the curable silicone composition layer 12 is not particularly limited, it is preferable that the distance between the heating plate 38 and the curable silicone composition layer 12 is in the range of 30 to 100 mm, More preferably 60 to 90 mm.

In the present step S106, the heat treatment may be performed while changing the distance between the heating plate 38 and the curable silicone composition layer 12 step by step. For example, the heat treatment may be performed while the distance between the heating plate 38 and the layer of the curable silicone composition 12 is gradually decreased. More specifically, the heating process is performed under the condition that the heating plate 38 and the curable silicone composition layer 12 are at a distance X, and then the heating plate 38 and the curable silicone composition layer 12 are moved apart from the distance X (The distance Y between the heating plate 38 and the curable silicone composition layer 12> distance X).

As the conditions of the heat treatment in this step S106, an optimum condition is appropriately selected according to the kind of the solvent to be used and the curable silicone, but the solvent removability is better, the surface of the curable silicone composition layer becomes flat, It is preferable that the first temperature is within the range of the ultracentrifugation point of the solvent-30 deg. C to the ultracentrifugation point of the solvent + 30 deg. In other words, the first temperature preferably satisfies the following relational expression.

expression The ultracentrifugation point of the solvent-30 ° C ≤ the first temperature ≤ the ultracentrifugation point of the solvent + 30 ° C

Further, the ultrafiltration point of the solvent means a value measured according to JIS K0066 (1992). The contents of JIS K0066 (1992) are incorporated herein by reference.

The first temperature in the first heating step is preferably not higher than 210 占 폚 in that the surface of the curable silicone composition layer becomes flat and decomposition of the curable silicone is further suppressed. Among them, the temperature is preferably from 150 to 210 占 폚, more preferably from 180 to 205 占 폚 in that the cohesive failure of the silicone resin layer can be further suppressed.

The heating time is not particularly limited and the optimum conditions are appropriately selected depending on the kinds of the solvent used and the curable silicone. From the viewpoint of the removability of the residual solvent and the productivity, the heating time is preferably 1 to 5 minutes, more preferably 2 to 3 minutes .

In this step S106, heat treatment is performed while exhausting. As shown in Fig. 3, an exhaust pipe 40 is provided in the heat treatment apparatus 30, and exhaust gas is exhausted from the exhaust pipe 40 during the heating process. The exhaust amount is not particularly limited, but is preferably 100 L / min or more, and more preferably 900 L / min or more, from the viewpoint that the removal of the solvent proceeds more efficiently. The upper limit is not particularly limited, but is preferably 2000 L / min or less from the viewpoints of performance and economical efficiency of the apparatus.

The exhaust amount is preferably 50% or more, more preferably 75% or more, and even more preferably 100% when 100% of the exhaust gas is completely exhausted from the exhaust pipe 40.

In the present step S106, gas may be supplied from a gas supply port (not shown). By supplying the gas, the volatile solvent in the heating chamber 32 can be efficiently removed. The kind of gas to be supplied is not particularly limited, and inert gas such as air or nitrogen can be mentioned.

The supply amount of the gas is not particularly limited, but is preferably 100 L / min or more, and more preferably 900 L / min or more, from the viewpoint that removal of the solvent proceeds more efficiently. The upper limit is not particularly limited, but is preferably 2000 L / min or less from the viewpoints of performance and economical efficiency of the apparatus.

As the gas to be supplied, heated air is preferable because it is more excellent in the removability of the remaining solvent in the curable silicone composition layer. The temperature of the heated air is not particularly limited, but is preferably 100 to 150 DEG C from the viewpoint of solvent removal and surface smoothness of the curable silicone composition layer.

<Moving Process>

The moving step S108 is a step of moving the curable silicone composition layer subjected to the heat treatment and the heating plate away from each other after the first heating step S106. More specifically, in FIG. 3, the heating plate 38 is moved in the direction of the arrow so that the curable silicone composition layer 12 and the heating plate 38 are moved away from each other, thereby expanding the space between them. By carrying out this step S108, the concentration of the solvent retained between the curable silicone composition layer 12 and the heating plate 38 can be reduced, the removability of the solvent can be improved, and the curable silicone composition layer 12 can be formed, It is possible to suppress the re-adhesion of the solvent to the phase.

As described above, the heat treatment apparatus 30 is provided with a lifting mechanism for lifting the heating plate 38 (not shown) so that the heating plate 38 is moved away from the curable silicone composition layer 12 Move.

The distance between the curable silicone composition layer 12 and the heating plate 38 is preferably 20 mm or more apart from the distance in the first heating step S106 and more preferably 40 mm or more. The upper limit is not particularly limited, but is usually 100 mm or less in view of the problem of size on the apparatus.

The movement time of the heating plate 38 is not particularly limited, but is preferably within 5 seconds and more preferably within 3 seconds from the viewpoint of productivity.

3, the distance between the curable silicone composition layer 12 and the heating plate 38 is increased due to the movement of the heating plate 38. However, the procedure of this step S108 is not limited to this embodiment, The curable layer-attached supporting substrate 14 including the layer of the curable silicone composition 12 may be moved to distant them. For example, if the support pin is a so-called lift pin, after the first heating step S106, the lift pin supporting the curable layer-attached supporting substrate may be lowered to separate the curable silicone composition layer from the heating plate.

<Exporting process>

The carrying-out step S110 is a step of carrying out the supporting substrate with the curable layer from the heat treatment apparatus.

In this step S110, the supporting substrate 14 with the curable layer is taken out from the inside of the heat treatment apparatus 30 through the loading / unloading port 42 of the heating / That is, the loading / unloading port 42 is opened to recover the curable layer-attached supporting substrate 14 from the inside of the heating processing device 30. [

&Lt; Second heating step &

The second heating step S112 is a step of performing heat treatment at the second temperature higher than the first temperature to the cured layer-attached supporting substrate recovered in the carrying-out step S110 to obtain a silicon resin layer. The present step S112 is a so-called post-baking process. By performing this step S112, the solvent in the curable silicone composition layer is further removed, curing of the curable silicone proceeds, and a silicon resin layer is obtained. By carrying out this step, a resin-layer-attached supporting substrate 18 having a supporting substrate 10 and a silicone resin layer 16 is obtained as shown in Fig. 2 (B).

The method of the heat treatment in this step S112 is not particularly limited, and a known heating device such as an oven can be used.

The heat treatment temperature condition in this step S112 is performed at a temperature higher than the first temperature in the first heating step S106 described above. The difference between the first temperature and the second temperature is not particularly limited and may be appropriately selected depending on the type of curable silicone or solvent used. From the viewpoint that the cohesive failure of the silicone resin layer is further suppressed, And more preferably 30 to 70 ° C.

Of these, the second temperature is preferably higher than 210 deg. It is preferable that the temperature is higher than 210 deg. C and 250 deg. C or lower from the viewpoint of better solvent removal and curing reaction from the curable silicone composition layer 12. [ The heating time is appropriately selected in accordance with the material to be used, but is preferably 10 to 120 minutes, more preferably 20 to 60 minutes from the viewpoints of productivity and removability of the solvent.

(Supporting substrate with resin layer)

Through the above process, a resin-layer-attached supporting substrate 18 having a supporting substrate 10 and a silicon resin layer 16 fixed on the supporting substrate 10 is obtained.

The supporting substrate 18 with the resin layer is used for producing the glass laminate 100 by laminating the glass substrate 20 on the silicon resin layer 16 as shown in Fig.

The silicon resin layer 16 in the support substrate 18 with the resin layer attached is fixed on one side of the support substrate 10 by performing the curing reaction of the curable silicone composition layer 12 on the support substrate 10, Which is in contact with the glass substrate 20. The silicon resin layer 16 prevents the positional deviation of the glass substrate 20 until the operation of separating the glass substrate 20 and the support substrate 10 is performed and removes the glass substrate 20 from the glass substrate 20 So that the glass substrate 20 or the like is prevented from being broken by the separating operation. The silicone resin layer 16 is fixed to the support substrate 10 and the silicone resin layer 16 and the support substrate 10 are not peeled off in the separation operation, 18) is obtained.

The surface of the silicone resin layer 16 in contact with the glass substrate 20 is in close contact with the first main surface of the glass substrate 20 in a peelable manner. In the present invention, the property of easily peeling off the surface of the silicone resin layer 16 is referred to as peelability (peelability).

In the present invention, there is a difference in peel strength (i.e., stress required for peeling) in the fixed and peelable close contact, and fixing means a large peeling strength in close contact. The peelable adhesion means peelable and peelable without causing peeling of the fixed surface. Concretely, in the case of performing the operation of separating the glass substrate 20 and the support substrate 10 in the glass laminate of the present invention, it means that the glass substrate 20 is peeled from the adhered surface and not peeled off from the fixed surface. Therefore, when the operation for separating the glass substrate 20 and the support substrate 10 from each other in the glass laminate is performed, the glass laminate is separated into two parts, that is, the glass substrate 20 and the supporting substrate 18 with resin layer.

That is, the bonding force of the silicon resin layer 16 to the surface of the support substrate 10 is relatively higher than the bonding force of the silicon resin layer 16 to the first main surface of the glass substrate 20.

The thickness of the silicone resin layer 16 is not particularly limited, but is preferably 2 to 100 占 퐉, more preferably 3 to 50 占 퐉, and further preferably 7 to 20 占 퐉. If the thickness of the silicon resin layer 16 is within this range, the occurrence of distortion defects of the glass substrate 20 can be suppressed even if bubbles or foreign matter intervene between the silicon resin layer 16 and the glass substrate 20 . Further, if the thickness of the silicone resin layer 16 is too thick, it takes time and materials to form it, which is not economical and the heat resistance may be lowered. If the thickness of the silicon resin layer 16 is too small, the adhesion between the silicon resin layer 16 and the glass substrate 20 may be deteriorated.

&Lt; Production method of glass laminate >

As described above, the support substrate with a resin layer obtained through the above steps is used for producing a glass laminate by laminating a glass substrate on a silicon resin layer.

The method for producing the glass laminate is not particularly limited. However, a method of laminating a glass substrate on a silicon resin layer in a supporting substrate with a resin layer to obtain a glass laminate having a supporting substrate, a silicone resin layer and a glass substrate in this order It is preferable to carry out the process.

Hereinafter, the procedure of the laminating step will be described in detail.

(Lamination step)

In the laminating step, the glass substrate 20 is laminated on the surface of the silicon resin layer 16 in the resin layer-attached supporting substrate 18, and the supporting substrate 10, the silicon resin layer 16 and the glass substrate 20 are laminated And the glass laminate 100 provided in this order. More specifically, as shown in Fig. 4, the surface 16a of the silicon resin layer 16 opposite to the side of the support substrate 10, the glass substrate 16 having the first main surface 20a and the second main surface 20b, The silicon resin layer 16 and the glass substrate 20 are laminated by using the first main surface 20a of the glass substrate 20 as a lamination surface to obtain the glass laminate 100. [

The glass substrate 20 to be used will be described later in detail.

The method of laminating the glass substrate 20 on the silicone resin layer 16 is not particularly limited and a known method can be adopted.

For example, a method of overlapping the glass substrate 20 on the surface of the silicon resin layer 16 under an atmospheric pressure environment. If necessary, the glass substrate 20 may be overlaid on the surface of the silicon resin layer 16, and then the glass substrate 20 may be pressed against the silicon resin layer 16 using a roll or press. The bubbles mixed in between the silicon resin layer 16 and the glass substrate 20 are relatively easily removed by pressing by roll or press.

It is more preferable to press the silicon resin layer 16 and the glass substrate 20 by the vacuum laminating method or the vacuum press method because the mixing of the bubbles is suppressed and the good adhesion is ensured. The bubbles do not grow due to heating even when minute bubbles remain, and it is difficult to cause strain defects of the glass substrate 20.

When the glass substrate 20 is laminated, it is preferable that the surface of the glass substrate 20 contacting the silicon resin layer 16 is thoroughly cleaned and laminated in an environment with high cleanliness. The higher the cleanliness is, the better the flatness of the glass substrate 20 becomes.

Further, after the glass substrate 20 is laminated, a pre-annealing treatment (heat treatment) may be performed if necessary. By performing the pre-annealing process, the adhesion of the laminated glass substrate 20 to the silicon resin layer 16 is improved, and an appropriate peel strength can be obtained. In the member forming process described later, the position of the electronic device member It is less likely to cause misalignment and the like, and the productivity of the electronic device is improved.

The conditions of the pre-annealing process are appropriately selected in accordance with the type of the silicon resin layer 16 to be used. From the point of making the peeling strength between the glass substrate 20 and the silicon resin layer 16 more appropriate , And at least 300 ° C (preferably 300 to 400 ° C) for 5 minutes or more (preferably 5 to 30 minutes).

(Glass substrate)

The glass substrate 20 is provided with the electronic device member on the second main surface 20b which is in contact with the silicon resin layer 16 on the first main surface 20a and on the opposite side of the silicon resin layer 16 side.

The type of the glass substrate 20 may be a general one, and examples thereof include glass substrates for display devices such as LCDs and OLEDs. The glass substrate 20 is excellent in chemical resistance and moisture permeability, and has a low heat shrinkage rate. The coefficient of thermal expansion specified in JIS R 3102 (revised in 1995) is used as an index of the heat shrinkage ratio. The contents of JIS R 3102 (revised 1995) are incorporated herein by reference.

If the coefficient of linear expansion of the glass substrate 20 is large, a member forming process described later often involves heat treatment, and thus various problems are likely to occur. For example, in the case of forming the thin film transistor (TFT) on the glass substrate 20, if the glass substrate 20 on which the TFT is formed under heating is cooled, the positional deviation of the TFT due to heat shrinkage of the glass substrate 20 may be excessive .

The glass substrate 20 is obtained by melting a glass raw material and molding the molten glass into a plate. Such a forming method may be a general one, and for example, a float method, a fusion method, a slot down-draw method, a fur co-ling method, a lub bus method, and the like are used. In particular, the glass substrate 20 having a small thickness can be obtained by heating the glass molded into a plate shape at one time, heating the glass at a molding temperature, and stretching it by means of drawing or the like (thinning method).

The kind of the glass of the glass substrate 20 is not particularly limited, but is preferably an alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, or other oxide-based glass mainly containing silicon oxide. As the oxide-based glass, glass having a silicon oxide content of 40 to 90 mass% in terms of an oxide is preferable.

As the glass of the glass substrate 20, glass suitable for the kind of the electronic device member and the manufacturing process thereof is adopted. For example, a glass substrate for a liquid crystal panel includes a glass (alkali-free glass) substantially free from an alkali metal component in that the elution of the alkali metal component tends to affect the liquid crystal (note that the alkali- Included). As described above, the glass of the glass substrate 20 is appropriately selected based on the type of the applied device and the manufacturing process thereof.

The thickness of the glass substrate 20 is preferably 0.3 mm or less, more preferably 0.15 mm or less, and still more preferably 0.10 mm or less from the viewpoints of reducing the thickness and / or weight of the glass substrate 20. When the thickness is 0.3 mm or less, it is possible to impart good flexibility to the glass substrate 20. When the thickness is 0.15 mm or less, the glass substrate 20 can be rolled up.

The thickness of the glass substrate 20 is preferably 0.03 mm or more for ease of manufacture of the glass substrate 20, ease of handling of the glass substrate 20, and the like.

Further, the glass substrate 20 may include two or more layers, and in this case, the materials for forming the respective layers may be the same or different materials. In this case, "the thickness of the glass substrate 20" means the total thickness of all the layers.

(Glass laminate)

The glass laminate 100 is a laminate having a support substrate 10, a glass substrate 20, and a silicon resin layer 16 interposed therebetween. One side of the silicon resin layer 16 is in contact with the supporting substrate 10 and the other side of the silicon resin layer 16 is in contact with the first main surface 20a of the glass substrate 20. [

This glass laminate 100 is used until a member forming process described later. That is, the glass laminate 100 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 20b of the glass substrate 20. Thereafter, the glass laminate formed with the electronic device member is separated into the supporting substrate 18 with the resin layer and the electronic device, and the supporting substrate 18 with the resin layer does not constitute the part constituting the electronic device. A new glass substrate 20 is laminated on the supporting substrate 18 with the resin layer attached thereto, and can be reused as a new glass laminate body 100.

The interface between the support substrate 10 and the silicon resin layer 16 has a peel strength x and a stress in the peeling direction exceeding the peel strength x is applied to the interface between the support substrate 10 and the silicon resin layer 16 The peeling occurs at the interface between the support substrate 10 and the silicon resin layer 16. [ The interface between the silicon resin layer 16 and the glass substrate 20 has a peel strength y and a stress in the peeling direction exceeding the peel strength y is exerted on the interface between the silicon resin layer 16 and the glass substrate 20 The peeling occurs at the interface between the silicon resin layer 16 and the glass substrate 20. [

As described above, in the glass laminate 100 (also referred to as a laminate having an electronic device member described later), the peel strength x is higher (higher) than the peel strength y. The glass laminate 100 is bonded to the surface of the glass substrate 20 at the interface between the silicon resin layer 16 and the glass substrate 20. When the stress is applied to the glass laminate 100 in the direction in which the supporting substrate 10 and the glass substrate 20 are separated, And separated into the glass substrate 20 and the resin-layer-attached supporting substrate 18.

That is, the silicon resin layer 16 is fixed on the supporting substrate 10 to form the supporting substrate 18 having the resin layer, and the glass substrate 20 is in close contact with the silicon resin layer 16 in a peelable manner .

The peel strength (x) is preferably sufficiently high as compared with the peel strength (y). Raising the peel strength x means that the adhesion force of the silicone resin layer 16 to the support substrate 10 is increased and the adhesion force can be maintained relatively higher than that of the glass substrate 20 after the heat treatment .

The improvement in adhesion of the silicone resin layer 16 to the support substrate 10 is achieved by crosslinking and curing the curable silicone composition layer 12 on the support substrate 10 to form the silicone resin layer 16 as described above. The silicone resin layer 16 bonded to the support substrate 10 with high bonding force can be formed by the adhesive force at the time of crosslinking curing.

On the other hand, the bonding force of the layer of the curable silicone composition 12 to the cured glass substrate 20 is generally lower than the bonding force generated at the time of crosslinking curing.

The glass laminate 100 can be used for various purposes and includes, for example, an application for manufacturing electronic parts such as a display panel, a PV, a thin film secondary battery, a semiconductor wafer on which a circuit is formed on a surface, have. Further, in the intended use, the glass laminate 100 is often exposed (for example, 1 hour or more) at a high temperature condition (for example, 360 ° C or more).

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

&Lt; Electronic device (member-attached glass substrate) >

In the present invention, an electronic device (member-attached glass substrate) including a glass substrate and a member for an electronic device is manufactured using the above-described glass laminate.

The production method of the electronic device is not particularly limited, but from the point of view of productivity of the electronic device, a member for electronic devices is formed on the glass substrate in the glass laminate to manufacture a laminate with a member for an electronic device, It is preferable to separate the glass substrate side interface of the silicon resin layer from the laminate of the usable material attachment layer into the electronic device and the supporting substrate with the resin layer separated therefrom.

Hereinafter, the step of forming the electronic device member on the glass substrate in the glass laminate to produce the laminate of electronic device member laminate is referred to as a member forming step, a step of forming a glass substrate side surface of the silicon resin layer The step of separating the electronic device from the support substrate with the resin layer is referred to as a separation step.

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

(Member forming process)

The member forming step is a step of forming an electronic device member on the glass substrate 20 in the glass laminate 100 obtained in the laminating step. More specifically, as shown in Fig. 5A, the electronic device member 22 is formed on the second main surface 20b (exposed surface) of the glass substrate 20, (24).

First, the electronic device member 22 used in this process will be described in detail, and the procedure of the subsequent process will be described in detail.

(Member for electronic device (functional element))

The member 22 for the electronic device is a member formed on the glass substrate 20 in the glass laminate 100 and constituting at least a part of the electronic device. More specifically, the electronic device member 22 may be a member used for a display device panel, a solar cell, a thin-film secondary battery, or an electronic component such as a semiconductor wafer on which a circuit is formed (for example, Member for solar cell, member for thin film secondary battery, circuit for electronic parts).

For example, as a member for a solar cell, a transparent electrode such as a tin oxide of a positive electrode in a silicon type, a silicon layer and a metal of a negative electrode which are represented by p layer / i layer / n layer, And various members corresponding to a quantum dot type or the like.

Examples of members for a thin film secondary battery include a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode in a lithium ion type, a lithium compound in an electrolyte layer, a metal in a current collecting layer, a resin as a sealing layer, Various members corresponding to small size, polymer type, ceramics electrolyte type, and the like.

As a circuit for an electronic component, a metal of a conductive part, a silicon oxide of an insulating part and silicon nitride can be cited in a CCD or a CMOS. In addition, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board, And the like.

(Process procedure)

The method of manufacturing the above-described electronic device-mounting member laminate 24 is not particularly limited and may be carried out by a known method according to the type of the constituent member of the electronic device member, And the electronic device member 22 is formed on the second main surface 20b.

The electronic device member 22 is not limited to all of the members finally formed on the second main surface 20b of the glass substrate 20 (hereinafter referred to as &quot;Quot; partial member &quot;). The glass substrate with a partial member peeled off from the silicon resin layer 16 may be made a glass substrate with an entire member (corresponding to an electronic device described later) in the subsequent step.

Further, another electronic device member may be formed on the peeling surface (first main surface 20a) of the glass substrate with the whole member peeled off from the silicon resin layer 16. [ Alternatively, the electronic device may be manufactured by assembling the whole member-mounted laminate, and thereafter peeling the resin-layer-attached supporting substrate 18 from the laminate with the whole member. Further, the electronic device is assembled by using two sheets of the whole-member-stacked laminate, and then the two sheets of the resin-layer-attached supporting substrate 18 are peeled from the laminate of the whole member laminate to manufacture an electronic device having two glass substrates It is possible.

For example, in the case of manufacturing an OLED, for example, a glass substrate 20 of a glass laminate 100 on the surface opposite to the side of the silicon resin layer 16 (on the second main surface 20b of the glass substrate 20) , A hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and the like are deposited on a surface on which a transparent electrode is formed to form an organic EL structure, a back electrode is formed, Various layers such as sealing with a plate are formed and treated. Specific examples of such layer formation and treatment include film forming treatment, vapor deposition treatment, and adhesion treatment of a sealing plate.

In the case of manufacturing a TFT-LCD, for example, a method of manufacturing the TFT-LCD is a method in which a resist solution is used on the second main surface 20b of the glass substrate 20 of the glass laminate 100, A TFT forming step of forming a thin film transistor (TFT) by forming a pattern on a metal film and a metal oxide film formed by a general film forming method, and a step of forming a second main surface 20b of the glass substrate 20 of another glass laminate 100 ), A CF forming step of forming a color filter (CF) by using a resist solution on the pattern formation, and a bonding step of laminating CF laminate obtained in the TFT laminate and CF forming step obtained in the TFT forming step And has various processes.

In the TFT forming step and the CF forming step, a TFT or a CF is formed on the second main surface 20b of the glass substrate 20 by using a well-known photolithography technique or an etching technique. At this time, a resist solution is used as the coating liquid for pattern formation.

Further, the second main surface 20b of the glass substrate 20 may be cleaned before forming the TFT or CF, if necessary. As the cleaning method, well-known dry cleaning or wet cleaning can be used.

In the bonding step, the thin film transistor formation surface of the laminate with TFT and the color filter formation surface of the CF laminate are bonded to each other by using a sealing agent (for example, an ultraviolet curing type sealing agent for forming a cell). Thereafter, the liquid crystal material is injected into the cells formed by the laminate of the TFT-attached laminate and the CF laminate. As a method of injecting the liquid crystal material, for example, there are a reduced pressure injection method and a dropping injection method.

(Separation step)

5 (B), the interface between the silicon resin layer 16 and the glass substrate 20 is peeled off from the laminate 24 for electronic device member assembly obtained in the above member forming step The electronic device 22 including the electronic device member 22 and the electronic device including the glass substrate 20 are separated by the glass substrate 20 (electronic device) in which the electronic device member 22 is laminated and the supporting substrate 18 with the resin layer 26).

If the electronic device member 22 on the glass substrate 20 at the time of peeling is a part of the formation of all necessary constituent members, the remaining constituent members may be formed on the glass substrate 20 after the detachment.

The method of peeling the glass substrate 20 and the resin layer-attached supporting substrate 18 is not particularly limited. Specifically, for example, a sharp blade-like shape may be inserted into the interface between the glass substrate 20 and the silicone resin layer 16, and a mixed fluid of water and compressed air may be sprayed after giving a moment of peeling . Preferably, the support substrate 10 of the member stack 24 for electronic devices is provided on the upper surface side, and the electronic device member 22 side is provided on the lower surface side, (In the case where the supporting substrates are stacked on both surfaces thereof), and in this state, the blade is first introduced into the interface between the glass substrate 20 and the silicone resin layer 16. Thereafter, the support substrate 10 side is adsorbed by the plurality of vacuum adsorption pads, and the vacuum adsorption pad is raised in order from the vicinity of the position where the blade is inserted. An air layer is formed on the interface between the silicon resin layer 16 and the glass substrate 20 and on the cohesive failure surface of the silicone resin layer 16 and the air layer spreads over the entire surface of the interface or the cohesive failure surface, Can easily be peeled off.

Further, the support substrate 10 can be laminated with a new glass substrate to produce the glass laminate 100 of the present invention.

When the electronic device 26 is detached from the electronic device 26 for mounting the electronic device, the pieces of the silicone resin layer 16 are prevented from being electrostatically charged in the electronic device 26 by controlling the spraying and the humidity by the ionizer Adsorption can be further inhibited.

The above-described manufacturing method of the electronic device 26 is suitable for manufacturing a small-sized display device used in a mobile terminal such as a cellular phone or a PDA. The display device is mainly an LCD or an OLED, and the LCD includes TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type and the like. It can basically be applied to any of passive drive type and active drive type display devices.

As the electronic device 26 manufactured by the above method, there can be used a display panel having a glass substrate and a display device member, a solar cell having a glass substrate and a solar cell member, a thin film secondary cell having a glass substrate and a member for a thin- , Electronic parts having a glass substrate and a member for an electronic device, and the like. The display panel includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

<Examples>

Hereinafter, the present invention will be described in detail by way of examples and the like, but the present invention is not limited to these examples.

In the following examples and comparative examples, a glass plate (880 mm in length, 680 mm in width, 0.2 mm in plate thickness, and a coefficient of linear expansion of 38 x 10 &lt; ^-7 &gt; / [deg.] C, manufactured by Asahi Glass Co., ) Were used. As a supporting substrate, a glass plate (920 mm in length, 730 mm in width, 0.5 mm in plate thickness, and a coefficient of linear expansion of 38 10 ^-7 / ° C, manufactured by Asahi Glass Co., Ltd., trade name "AN100") containing an alkali-free borosilicate glass was used .

&Lt; Example 1 >

First, the surface of the support substrate was cleaned with an alkaline aqueous solution and then cleaned with pure water.

Subsequently, a solution S to be described later was applied on the first main surface of the support substrate with a die coater (coating speed: 40 mm / s, discharge amount: 8 ml) to form a layer (curable silicone composition layer) containing uncured, crosslinkable organopolysiloxane Was formed on the support substrate to obtain a support substrate having a curable layer (application amount 20 g / m ² ).

(Solution S)

As the component (A), the mol% of the vinyl group in the linear vinyl methylpolysiloxane (trade name "VDT-127" manufactured by Ajax Co., Ltd., viscosity at 25 ° C: 700-800 cP (centipoise), 1 mol of the organopolysiloxane) : 0.325) and a linear methylhydrogenpolysiloxane (trade name: "HMS-301" manufactured by Ajax Co., Ltd., viscosity at 25 ° C: 25-35 cP (centipoise)) as a component (B) (Hydrogen atoms / vinyl groups) of the entire vinyl groups and silicon atoms bonded to silicon atoms was 0.9, and 100 parts by weight of the siloxane mixture was used as component (C) And 1 part by mass of a silicon compound having an acetylenic unsaturated group represented by the following formula (1) (boiling point: 120 占 폚) were mixed.

HC≡CC (CH ₃ ) ₂ -O-Si (CH ₃ ) ₃ ????? (1)

Subsequently, a platinum catalyst (trade name "CAT-PL-56" manufactured by Shin-Etsu Silicones Co., Ltd.) was added so that the platinum metal concentration in terms of platinum was 100 ppm based on the total amount of the components (A), (B) Was added to obtain a mixed solution of the organopolysiloxane composition. Further, to 100 parts by weight of the obtained mixed solution, 150 parts by weight of IP solvent 2028 (ultra-high point: 200 캜, manufactured by Idemitsu Kosan Co., Ltd.) was added to obtain a mixed solution.

Then, the supporting substrate with the curable layer was loaded into the heating chamber through the loading / unloading port in the heating processing apparatus shown in Fig. 3, the supporting substrate with the curable layer was loaded on the tip of a plurality of supporting pins provided on the bottom of the heating chamber, I closed the entrance door. In addition, the tip of the support pin was in contact with the surface of the back side of the support substrate (the side opposite to the side where the curable silicone composition layer was present) in the supporting substrate with the curable layer.

As shown in Fig. 3, a heating plate was disposed on the upper portion of the curable silicone composition layer of the supporting substrate with the curable layer, and the distance between the curable silicone composition layer and the heating plate was 70 mm.

First, the supporting substrate with the curable layer was heated at 200 占 폚 for 60 seconds by the heating plate, then the distance between the curable silicone composition and the heating plate was changed to 80 mm, and the heating was performed for 90 seconds.

In addition, in the heat treatment, the exhaust air was supplied at a rate of 960 L / min (the exhaust amount from the exhaust pipe was fully opened), and heated air (temperature 120 캜) was supplied at a rate of 1000 L / min.

After the end of the heat treatment, the heating plate was moved 50 mm away from the curable silicone composition layer. Thereafter, the curing-layer-attached supporting substrate on which the heat treatment was performed by opening the entrance / exit port of the heat treatment apparatus was taken out from the inside of the heat treatment apparatus.

Thereafter, the support substrate with the curable layer after the heat treatment was placed in another heat treatment apparatus and subjected to a heat treatment (post-baking treatment) at 250 DEG C for 1450 seconds to form a silicon wafer having a thickness of 8 mu m Strata.

Subsequently, the glass substrate and the surface of the silicon resin layer on the support substrate were joined together by an atmospheric pressure press at room temperature to obtain a glass laminate S1.

In the obtained glass laminate S1, the supporting substrate and the glass substrate were in close contact with each other without generating air bubbles between the supporting substrate and the silicon resin layer, without distortion defects and with good smoothness. In the glass laminate S1, the peel strength at the interface between the silicon resin layer and the support substrate layer was larger than the peel strength at the interface between the glass substrate layer and the silicon resin layer.

&Lt; Example 2 >

A glass laminate S2 was produced in the same manner as in Example 1 except that the amount of exhaust during heating was changed from 960 L / min to 500 L / min, and the amount of heated air supplied was changed from 1000 L / min to 600 L / min . In the glass laminate S2, the peel strength at the interface between the silicon resin layer and the support substrate layer was larger than the peel strength at the interface between the glass substrate layer and the silicon resin layer.

&Lt; Comparative Example 1 &

A glass laminate C was produced in the same manner as in Example 1, except that the supporting plate with the curable layer after the heat treatment was removed from the heat treatment apparatus without moving the heating plate after the completion of the heating treatment.

&Lt; Evaluation of cohesive failure &

The glass laminate obtained in the above Examples and Comparative Examples was cut into a size of 100 mm x 75 mm and subjected to a heat treatment at 350 DEG C for 60 minutes in a nitrogen atmosphere.

Then, the heat-treated glass laminate was cut into 25 mm x 75 mm, and a stainless steel blade having a thickness of 0.1 mm was inserted 10 mm into the interface between the glass substrate and the silicone resin layer in one of the four corners, And a glass substrate and a supporting substrate were separated from each other by applying an external force in a direction in which the glass substrate and the supporting substrate were separated from each other.

(25 mm x 65 mm) in contact with the silicone resin layer of the peeled glass substrate was visually observed to determine the adhesion rate (%) of the silicon resin layer {(attached to the surface of the peeled glass substrate on the side of the silicon resin layer on the peeled glass substrate) Area of the silicone resin layer / observation area) x 100} was obtained and evaluated according to the following criteria. The larger the adhesion rate, the more the cohesive failure of the silicon resin layer.

&Quot; ○ &quot;: When the adhesion rate is less than 5%

&Quot; DELTA &quot;: When the adhesion rate is 5% or more and less than 10%

&Quot; x &quot;: When the adhesion rate is 10% or more

As a result of the cohesive failure evaluation, evaluation results were "?" In Example 1, "?" In Example 2, and "x" in Comparative Example 1.

From the results, it was confirmed that the cohesive failure of the silicone resin layer tends to progress in the Comparative Example 1 in which the treatment for distancing the distance between the heating plate and the curable silicone composition layer was not performed.

From the results of Example 1 and Example 2, it was confirmed that the coagulation failure was further suppressed in the case where the exhaust amount was large.

&Lt; Example 3 >

In this example, an OLED is manufactured using the glass laminate S1 obtained in the first embodiment.

First, a film of silicon nitride, silicon oxide, and amorphous silicon is formed in this order on the second main surface of the glass substrate in the glass laminate S1 by the plasma CVD method. Subsequently, low-concentration boron is implanted into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment. Then, the amorphous silicon layer is crystallized by a laser annealing apparatus. Then, low-concentration phosphorus is injected into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method to form N-type and P-type TFT areas. Subsequently, 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, and then molybdenum is formed by a sputtering method, and a gate electrode is formed by etching using a photolithography method. Subsequently, boron and phosphorus at a high concentration are implanted into desired areas of N type and P type, respectively, by photolithography and ion doping apparatus to form a source area and a drain area. Subsequently, an interlayer insulating film is formed on the second main surface side of the glass substrate by the plasma CVD method by the silicon oxide film formation, and a TFT electrode is formed by the sputtering method by aluminum film formation and etching by photolithography. Subsequently, a heat treatment is performed in a hydrogen atmosphere to perform a hydrogenation treatment, and then a passivation layer is formed by film formation of silicon nitride by a plasma CVD method. Subsequently, an ultraviolet curing 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. Subsequently, indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as a hole injection layer on the second main surface side of the glass substrate by vapor deposition, and bis [(N-naphthyl) (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-1-carboxylate was added to 8-quinolinol aluminum complex (Alq ₃ ) , And 5-dicarbononitrile (BSN-BCN) in an amount of 40% by volume, and Alq ₃ as an electron transporting layer are formed in this order on the aluminum film. Subsequently, aluminum is deposited by sputtering and is etched by photolithography Next, another glass substrate is bonded to the second main surface side of the glass substrate via an adhesive layer of ultraviolet curing type and sealed, thereby forming an organic EL structure on the glass substrate by the above procedure. A glass laminate S1 having an organic EL structure on a substrate (hereinafter referred to as panel A) Member for an electronic device is attached to the laminate.

Subsequently, a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the resin layer at the corner of the panel A after the sealing member side of the panel A was vacuum-adsorbed on the surface of the plate, Give the instrument. After the support substrate surface of the panel A is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the blade is carried out while spraying an antistatic fluid on the interface from an ionizer (manufactured by KYENS). Subsequently, the vacuum adsorption pad is pulled up while injecting the antistatic fluid from the ionizer toward the formed gap, and further adding water to the peeling wire. As a result, the support substrate with the resin layer can be peeled off, leaving only the glass substrate on which the organic EL structure is formed.

Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method, and divided into a plurality of cells. Then, a glass substrate on which the organic EL structure is formed and a counter substrate are assembled to form a module, do. The characteristics of the OLED thus obtained do not occur.

Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on Japanese Patent Application No. 2013-260253 filed on December 17, 2013, the contents of which are incorporated herein by reference.

10: Support substrate
12: Curable silicone composition layer
14: Curable layer-attached supporting substrate
16: Silicone resin layer
16a: a surface of the silicon resin layer opposite to the support substrate side
18: Support layer with resin layer
20: glass substrate
20a: a first main surface of the glass substrate
20b: a second main surface of the glass substrate
22: member for electronic device
24: Member laminate for electronic device
26: Electronic device
30: Heat treatment apparatus
32: Heating chamber
34: Support pin
36: Support
38: Heating plate
40: Exhaust pipe
42: Incoming exit
100: Glass laminate

Claims (5)

A method of manufacturing a resin-bonded substrate having a support substrate and a silicon resin layer formed on one side of the support substrate, the glass substrate being laminated on the silicon resin layer to produce a glass laminate,
Applying a curable silicone composition comprising curable silicone and a solvent onto said support substrate to form a layer of curable silicone composition on said support substrate to obtain a curable layer deposited support substrate comprising said support substrate and said curable silicone composition layer A coating step,
A carrying step of bringing the curable layer-attached supporting substrate into a heating processing apparatus and loading the supporting substrate with the curable layer onto a supporting pin in the heating processing apparatus;
A heating plate is disposed on the curable silicone composition layer of the curable layer-attached supporting substrate to heat the curable layer-attached supporting substrate at a first temperature or lower while the air is being exhausted, A first heating step of removing the solvent,
A moving step of moving the curable silicone composition layer subjected to the heat treatment and the heating plate away from each other after the first heating step;
A carrying-out step of carrying out the curable layer-attached supporting substrate from the heat treatment apparatus,
A second heating step of heating the substrate with the curable layer attached thereto at a second temperature higher than the first temperature to obtain a silicon resin layer
Wherein the resin layer is provided on the supporting substrate. The method according to claim 1, wherein the curable silicone comprises an organoalkenyl polysiloxane having an alkenyl group and an organohydrogen polysiloxane having a hydrogen atom bonded to a silicon atom. The method according to claim 1 or 2, wherein the first temperature satisfies an outgassing point of the solvent-30 deg. C &lt; = first temperature &lt; = ultra violet spot of the solvent + 30 deg. A glass substrate having a support substrate, a silicon resin layer, and a glass substrate stacked in this order on the silicon resin layer in a resin substrate-attached support substrate produced by the manufacturing method according to any one of claims 1 to 3, A method for producing a glass laminate having a lamination step of obtaining a sieve. A member forming step of forming a member for an electronic device on the surface of the glass substrate of the glass laminate manufactured by the manufacturing method of claim 4 and obtaining a laminate with member for electronic device;
And removing the resin layer-attached supporting substrate from the laminate for electronic device member attachment to obtain an electronic device having the glass substrate and the electronic device member.

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