KR20150070977A - 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 glass laminate having a support substrate, a silicon resin layer, and a glass substrate in order. The method includes: a hating process of supporting, with a plurality of support pins, a support substrate, having a first main side and a second main side, and a curable layer attachment support substrate including a curable silicon composition layer arranged on the first side of the support substrate from the second main side of the support substrate, heating the curable layer attachment support substrate, and forming a silicon resin layer; a laminating process of laminating the glass substrate on the silicon resin layer after the heating process; and a surface treating process of executing, on the second main side of the support substrate, at least one treatment selected from the group consisting of corona treatment, plasma treatment, and UV ozone treatment.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for manufacturing a glass laminate,

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.

Further, in the formed glass laminate, a polishing process is sometimes performed to polish the surface of the glass substrate (Patent Document 2).

International Publication No. 2007/018028 Japanese Patent Laid-Open Publication No. 2013-149713

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.

The inventors of the present invention have found that when a reinforcing plate is manufactured according to the method described in Patent Document 1, a supporting substrate on which a coating film that becomes a silicone resin layer by heating is disposed on the top surface of a plurality of support pins is subjected to heat treatment, After that, a glass substrate was laminated on the silicone resin layer to prepare a glass laminate. Thereafter, the glass laminate on the side of the support substrate in the obtained glass laminate was placed on a predetermined substrate toward the predetermined substrate side, and the glass laminate for the electronic device on the glass substrate in the glass laminate as described in Patent Document 1 or 2 Thereby forming a member and polishing the surface of the glass substrate. Thereafter, when the glass laminate is to be removed from the predetermined substrate, the predetermined laminate is fixed on the predetermined substrate, and the removal can not be facilitated. As a result, productivity has been reduced due to prolonged process time, and production yield of electronic devices has been lowered.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method for manufacturing a glass laminate capable of easily producing a glass laminate that can be peeled off from a substrate after being mounted on various substrates toward a support substrate The purpose.

It is another object of the present invention to provide a method of manufacturing an electronic device using a glass laminate manufactured by the method for manufacturing a 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, a first aspect of the present invention is a method for producing a glass laminate having a support substrate, a silicone resin layer, and a glass substrate in this order, comprising the steps of forming a support substrate having a first main surface and a second major surface, Wherein the curable layer-attached support substrate having the curable silicone composition layer disposed on the support substrate is supported by a plurality of support pins from the second main surface side of the support substrate to heat the curable layer-attached support substrate, A lamination step of laminating a glass substrate on the silicon resin layer after the heating step, and a laminating step of laminating the glass substrate on the second main surface of the supporting substrate at least before the laminating step after the laminating step or after the laminating step, by corona treatment, plasma treatment, and UV ozone treatment And a surface treatment step of performing at least one treatment selected from the group consisting of the following.

In the first aspect, it is preferable that the curable silicone composition layer contains at least 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 heating step includes a first heating step of performing a heating treatment at a first temperature and a second heating step of performing a heating treatment at a second temperature higher than the first temperature in this order Do.

In a first aspect, a curable layer-attached support substrate is formed by applying a curable silicone composition comprising a curable silicone and a solvent on a first major surface of a support substrate, wherein the first temperature is higher than an ultra- It is preferable that the temperature < the ultra violet spot of the solvent + 30 deg.

In the first aspect, it is preferable to carry out the surface treatment step after the laminating step.

In the first aspect, a plurality of electrode pairs each having a high-voltage electrode and a ground electrode opposed to each other with a conveying path through which the glass laminate obtained in the laminating step is conveyed in the surface treatment step are arranged along the conveying direction of the glass laminate , One of the adjacent electrode pairs is disposed on one side of the conveying path and the other of the high voltage electrodes is disposed on the other side of the conveying path and the glass laminate is conveyed along the conveying path, It is preferable that corona treatment is performed on the glass laminate by applying a high-frequency voltage to the electrode.

A second aspect of the present invention is a method of manufacturing a semiconductor device, comprising: a member forming step of forming an electronic device member on a surface of a glass substrate of a glass laminate manufactured by the manufacturing method of the first aspect, And removing the resin layer-attached supporting substrate having the silicon resin layer and the supporting substrate from the member-mounting laminate for electronic devices 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 of manufacturing a glass laminate capable of easily producing a glass laminate that can be peeled off from a substrate after being mounted on various substrates toward a support substrate.

Further, according to the present invention, it is also possible to provide a method of manufacturing an electronic device using a glass laminate manufactured by the method for manufacturing a glass laminate.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a manufacturing process of the first embodiment of the method for producing a glass laminate according to the present invention. Fig.
2 (A), 2 (B) and 2 (C) are schematic cross-sectional views showing a first embodiment of the method for producing a glass laminate according to the present invention in the order of process.
3 is a schematic diagram showing the arrangement state of the curable layer-attached supporting substrate in the heating step.
4 is a side view showing one embodiment of the corona treating apparatus.
Fig. 5 is a flow chart showing the manufacturing process of the second embodiment of the method for producing a glass laminate according to the present invention.
6A and 6B are schematic cross-sectional views showing, in order of an embodiment, a method of manufacturing an electronic device of the present invention.

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.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted studies on the above problems and found that silicon resin adheres to the second main surface (back surface) side of the support substrate after the heating step or after the production of the glass laminate (after the laminating step) Respectively.

More specifically, the silicone resin is adhered to the second main surface side of the support substrate, in which the silicon resin or the raw material thereof is partially volatilized and supported by the support pins during the heating process. Therefore, when the glass laminate on the side of the support substrate of the glass laminate is placed on a predetermined substrate toward the predetermined substrate side, a predetermined amount of the silicon laminate is held by the silicone resin existing between the predetermined substrate and the support substrate in the glass laminate The peeling strength between the substrate and the support substrate of the substrate was increased, making it difficult for both to peel off. Therefore, it has been found that the above-described problems can be solved by performing various treatments on the second main surface side of the support substrate after the production of the glass laminate to remove the silicone resin.

The method for producing a glass laminate according to the present invention comprises a heating step of applying a heat treatment to a support substrate having a curable layer, a laminating step of laminating a glass substrate, and a surface treatment step of performing surface treatment. Further, the surface treatment step is performed after the laminating step or after the heating step and before the laminating step. Hereinafter, the former form will be described as the first form and the latter form as the second form.

<< First Embodiment >>

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a manufacturing process in a first embodiment of a method for producing a glass laminate according to the present invention. Fig. As shown in Fig. 1, the first embodiment includes a heating step S102, a laminating step S104, and a surface treatment step S106 in this order.

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

<Heating process>

Heating step S102 is a step in which the supporting substrate having the first major surface and the second major surface and the curable layer attachment supporting substrate having the curable silicone composition layer disposed on the first main surface of the supporting substrate are bonded to the second main surface Layer side) of the support substrate with a plurality of support pins and heat-treating the support substrate with the curable layer to form a silicone resin layer. More specifically, by performing the corresponding process S102 on the curable layer-attached supporting substrate 14 having the supporting substrate 10 and the curable silicone composition layer 12 in Fig. 2A, A resin-layer-attached supporting substrate 18 having a supporting substrate 10 and a silicon resin layer 16 is obtained as shown in Fig.

Hereinafter, the member / material (supporting substrate, curable silicone composition layer) used in step S102 will be described in detail and the procedure of the subsequent step S102 will be described in detail.

(Supporting substrate)

The supporting substrate 10 has two main surfaces, that is, a first main surface and a second main surface. The supporting substrate 10 supports the glass substrate 20 to be described later in cooperation with the silicon resin layer 16 to be described later, Deformation, scratches, breakage, and the like of the glass substrate 20 at the time of manufacturing the electronic device member in the manufacturing process of 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 layer)

The curable silicone composition layer is a layer of a composition capable of forming a silicone resin layer in the present step S102.

The layer of curable silicone composition includes curable silicone which cures to become a silicone resin. These curable silicones are classified into condensation reaction type silicones, addition reaction type silicones, ultraviolet ray curable silicones and electron beam curable silicones 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.

When the curable silicone contained in the curable silicone composition layer is an addition reaction type silicone, the curable silicone composition layer 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.

The method of applying the layer of the curable silicone composition on the supporting substrate is not particularly limited, and a known method can be adopted. For example, a method of applying a curable silicone composition containing the above-mentioned curable silicone on a support substrate. The method of applying 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.

The curable silicone composition may contain a solvent as required. 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, when the step S102 is carried out in two stages, it is preferable to use a solvent having an ultra-high point (under atmospheric pressure) of 210 DEG C or lower from the viewpoint that the solvent easily volatilizes in the first heating step.

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.

(Process procedure)

In this step S102, the supporting substrate with the curable layer is supported by a plurality of supporting pins from the second main surface side of the supporting substrate, and heat treatment is performed. That is, the heating is carried out while the support substrate with the curable layer is supported by the support pins. More specifically, as shown in Fig. 3, a support substrate 14 with a curable layer is disposed on the top of a support pin 52 spaced apart from the support base 50, and in this state, The layer-attached supporting substrate 14 is subjected to heat treatment. 3, the support pins 52 support the second main surface 10a of the support substrate 10 in the support substrate 14 having the curable layer.

In Fig. 3, only three support pins 52 are shown, but the number thereof is not particularly limited and may be ten or more. The positions of the support pins 52 are not particularly limited, and they may be arranged at predetermined intervals or at random. The shape of the support pin 52 is not particularly limited and may be any shape such as a cylindrical shape or a polygonal shape.

3, the support pin 52 is in contact with a part of the support substrate 10 on the side of the second main surface 10a, and therefore, on the second main surface 10a side of the support substrate 10, There is an area which is not in contact with the substrate 52.

The method of applying the heat treatment to the curable layer-attached support substrate is not particularly limited as long as it can be heated while the support substrate with the curable layer is supported by the support pin. For example, Can be used. More specifically, the present invention relates to a method of using a heat treatment apparatus having a hot plate (for example, a method of heating in a heat treatment apparatus provided with a hot plate on a curable silicone composition layer in a support substrate with a curable layer disposed on a support pin ).

The heating conditions for thermally curing the curable silicone composition layer are appropriately selected in accordance with the kind of the curable silicone to be used. Among them, heat treatment is preferably performed at 150 to 300 占 폚 (preferably 180 to 250 占 폚) for 10 to 120 minutes (preferably 30 to 60 minutes) in view of the curing rate of the curable silicone and the heat resistance of the silicone resin layer to be formed .

As a preferable mode of the present step S102, it is preferable that the heat treatment is performed in two steps under different temperature conditions. That is, it is more preferable to include a step of performing a heat treatment at a first temperature and a step of performing a heat treatment at a second temperature higher than the first temperature. By performing the heat treatment in two steps, the surface shape of the silicon resin layer 16 to be formed is better, and adhesion with the glass substrate 20 described later is further improved. When the heating process is performed in two steps, the first heating process and the second heating process may be performed by a separate heat treatment apparatus.

In addition, when the curable layer-attached supporting substrate is formed by applying the curable silicone composition containing the curable silicone and the solvent onto the supporting substrate, the removability of the solvent 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. C in that decomposition of the curable silicone is further suppressed. 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 difference between the first temperature and the second temperature is not particularly limited, but is preferably 10 ° C or higher, more preferably 30 ° C or higher. The upper limit is not particularly limited, but is usually 100 ° C or lower, more preferably 70 ° C or lower.

The first temperature is preferably 210 DEG C or lower. That is, it is preferable to include a first heating step of performing heat treatment at 210 占 폚 or lower and a second heating step of performing heat treatment at 210 占 폚 or higher. If the temperature is 210 占 폚 or less, the volatility of the solvent and the silicone resin are further suppressed, and the surface shape of the silicon resin layer 16 to be formed is more excellent. Hereinafter, the first heating step and the second heating step in the temperature condition will be described in detail.

The first heating step is a so-called pre-baking step, in which the volatile components such as the solvent remaining in the curable silicone composition layer 12 are removed, thereby preventing the solvent from rubbing in the second heating step described later. The temperature condition in the first heating step is preferably 210 占 폚 or lower, and more preferably 150 占 폚 to 210 占 폚, because the surface shape of the silicone resin layer 16 is more excellent. The heating time is appropriately selected in accordance with the material to be used, but is preferably 1 to 5 minutes, more preferably 2 to 3 minutes from the viewpoints of productivity and removability of the solvent.

The second heating process is a so-called post-baking process, which mainly promotes the curing of the curable silicone composition layer 12 and forms the silicone resin layer 16. [ The temperature condition of the second heating process is preferably higher than 210 deg. C, more preferably 210 deg. C or higher and 250 deg. C or lower in view of better solvent removal and curing reaction of the curable silicone composition layer 12. The heating time is suitably selected in accordance with the material to be used, but is preferably 10 to 120 minutes, more preferably 30 to 60 minutes from the viewpoints of productivity and removability of the solvent.

The silicon resin layer 16 formed through the step S102 is fixed on one side of the support substrate 10 by performing a curing reaction of the curable silicone composition layer 12 on the support substrate 10, And is in close contact with the substrate 20 in a peelable manner. 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 first major surface of the support substrate 10 is relatively higher than the bonding force of the silicon resin layer 16 to the first major 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; Lamination step &

In the laminating step S104, the glass substrate 20 is laminated on the surface of the silicon resin layer 16 obtained in the step S102, and the supporting substrate 10, the silicon resin layer 16 and the glass substrate 20 are laminated in this order To obtain a glass laminate (100). More specifically, as shown in Fig. 2 (C), the surface 16a of the silicon resin layer 16 opposite to the side of the support substrate 10, 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 having the first main surface 20a as the lamination surface to obtain the glass laminate 100. [ The glass laminate 100 obtained as described below is a glass laminate prior to the surface treatment step S106 to be described later and is formed on the silicon resin layer 16 of the support substrate 10 of the glass laminate 100, (The second main surface 10a of the supporting substrate 10) on the side opposite to the side of the silicon substrate or the silicon substrate.

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 first main surface of the support 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 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.

<Surface Treatment Step>

The surface treatment step S106 includes at least one step of performing at least one treatment selected from the group consisting of corona treatment, plasma treatment, and UV ozone treatment on at least a second main surface (a surface opposite to the side having the silicon resin layer) to be. In the first aspect, it is intended to perform the above treatment on the second main surface of the support substrate in the glass laminate formed as described above. More specifically, the above process is performed on the second main surface 10a of the support substrate 10 of Fig. 2 (C). By carrying out this step S106, the silicon resin adhered to the second main surface 10a of the support substrate 10, the raw material components, etc. are volatilized in the heating step S102, (10a) is cleaned. That is, by performing the above treatment on the glass laminate obtained in the laminating step S104, a treated glass laminate is obtained. As described later, in the present step S106, the above-described treatment may be performed on the exposed surface of the glass substrate in the glass laminate together with the second main surface of the support substrate in the glass laminate.

As the corona treatment (corona cleaning) performed in this step S106, a known corona treatment is performed. The corona treatment is a surface treatment technique for modifying the surface of a treated substrate such as a plastic film, paper, and metal foil by corona discharge irradiation. When a high frequency / high voltage generated from the high frequency power supply is applied between the high voltage electrode and the ground electrode, a corona discharge occurs.

The corona treatment method is not particularly limited. For example, a corona discharge is performed by applying a high voltage between a conveying roll for supporting a glass laminate and an electrode provided so as to face the glass laminate, and the glass laminate is sequentially moved during the surface treatment Is preferable. Specific examples of the apparatus for corona treatment include a device including a high-frequency power source (high-frequency oscillator), a high-voltage transformer, and a discharge electrode, and a conveyer for conveying the glass laminate before and after the high- The frequency of the high-frequency oscillator is not particularly limited, but is preferably 0.1 to 100 kHz, for example, and preferably has a maximum output of about 0.5 to 50 kW. The conveying speed (processing speed) of the glass laminate is not particularly limited, but is preferably 1 to 10 m / min.

When the surface treatment step S106 is performed after the laminating step S104, it is preferable to use the corona treatment apparatus described below.

4 is a side view showing one embodiment of the corona treating apparatus. The corona treatment apparatus 60 includes at least a first high voltage electrode 62, a first ground electrode 64, a second high voltage electrode 66, and a second ground electrode 68. The first high voltage electrode 62 and the first ground electrode 64 are disposed opposite to each other at a predetermined interval to constitute the first electrode pair 70. The first high voltage electrode 62 and the first ground electrode 64 A discharge space is formed. The second high voltage electrode 66 and the second ground electrode 68 are opposed to each other with a predetermined gap to constitute the second electrode pair 72, A discharge space is formed between the discharge cells 68. As shown in FIG. 4, the first electrode pair 70 and the second electrode pair 72 correspond to the direction in which the glass laminate X having the support substrate, the silicone resin layer, and the glass substrate obtained in the laminating step S104 in this order is conveyed Respectively. 4, the glass laminate X is conveyed by the conveying roll 74 and is conveyed between the first high-voltage electrode 62 and the first ground electrode 64 and between the second high-voltage electrode 66 and the second high- And runs between the second ground electrodes 68.

Further, the first high-voltage electrode 62 is connected to the first high-frequency power supply 76, and a high-frequency voltage is applied. Further, the second high-voltage electrode 66 is connected to the second high-frequency power supply 78, and a high-frequency voltage is applied. 4, the first RF power supply 76 and the second RF power supply 78 are used. However, the first RF power supply 76 and the second RF power supply 78 ) May use the same power source (shared).

The first high voltage electrode 62 and the second high voltage electrode 66 are disposed on the upper side (one side) and the lower side (the other side) with the path (transport path) in which the glass laminate X in FIG. . In other words, the first high voltage electrode 62 and the second high voltage electrode 66 are staggered along the transport direction of the glass laminate X.

When the glass laminate X is conveyed to the corona treatment apparatus 60 by using the conveying roll 74, the first high voltage electrode 62 and the second high voltage electrode 66 are respectively connected to one side of the conveyance path of the glass laminate X And the other side of the glass laminate X to be conveyed can be effectively corona-treated. That is, the corona treatment can be performed on the second major surface (the surface opposite to the silicon resin layer side) of the support substrate in the glass laminate X and the exposed surface (the surface opposite to the silicon resin layer side) of the glass substrate.

The preferable ranges of the conditions of the high frequency power source and the conditions of the conveying speed (processing speed) of the glass laminate X are as described above.

4, the first high voltage electrode 62 is disposed on the upper side of the drawing and the second high voltage electrode 66 is disposed on the lower side of the drawing. However, the present invention is not limited to this and the positional relationship may be reversed.

When the corona treatment is to be performed only strongly on the single side surface (the second main surface of the support substrate) of the glass laminate X, the first high voltage electrode 62 and the second high voltage electrode 66 are both provided on the upper side or the lower side As shown in FIG.

In Fig. 4, there is described a corona treatment apparatus including two pairs of a first electrode pair 70 and a second electrode pair 72, but the number of electrode pairs is not limited to this.

As the first high voltage electrode 62, the second high voltage electrode 66, the first ground electrode 64, and the second ground electrode 68, a metal electrode or a dielectric coated electrode can be used. The discharge for the corona treatment At least one of the first high voltage electrode 62 and the first ground electrode 64 disposed opposite to each other and the second high voltage electrode 66 and the second ground electrode 68 disposed opposite to each other It is preferable that at least one of them is covered with a dielectric. More preferably, both the first high voltage electrode 62 and the first ground electrode 64 and both the second high voltage electrode 66 and the second ground electrode 68 are covered with a dielectric. Thereby, the distance between the high voltage electrode and the ground electrode can be increased, and it is easy to stably transport the glass laminate X.

As a dielectric-coated electrode (dielectric-coated electrode), a ceramics electrode in which ceramics is coated on the surface of a conductive core material such as a metal such as stainless steel or aluminum is preferable. Generally, when the resin film is subjected to corona treatment, a rubber electrode coated with a rubber material as a dielectric coated electrode is used. Since the diameter is large due to the relationship between weight and rigidity, the corona treating apparatus 60 becomes large, There is a case where the transporting of the thin glass laminate X having an empty part between the transport rolls may be obstructed. Since the ceramics electrode is light in weight and high in rigidity, the diameter of the ceramic electrode is smaller than that of the rubber electrode.

Further, since the rubber film is liable to be damaged by the discharge, it is difficult to fix the rubber electrode. For this reason, it is general that a rubber electrode is provided with a rotating mechanism and is used while being rotated. However, there is a problem that the apparatus becomes complicated and large. It is not necessary to provide such a rotation mechanism because the ceramic electrode is not broken even if the discharge is repeated at the same place.

Plasma treatment (plasma cleaning) includes atmospheric (or normal pressure) plasma treatment and low pressure, low temperature plasma treatment.

In the atmospheric pressure plasma treatment, discharge energy is applied to the gas, and ionization is performed under atmospheric pressure to generate plasma. One of the features is that since it is an atmospheric pressure process, it is not necessary to make a vacuum, and the facility is simple and productivity is high. As a method, there is a pulse type atmospheric plasma in which a rare gas based atmospheric pressure plasma and a glow discharge are controlled by controlling an applied voltage. Any of them may be used.

In the low-pressure low-temperature plasma treatment, the glass laminate is passed through a decompression-resistant low-temperature plasma processing apparatus, and the atmosphere in the apparatus is maintained at an atmosphere of an inorganic gas, while maintaining the pressure at 0.001 to 10 Torr, preferably 0.01 to 1 Torr. To 13.6 MHz. A power of 0.1 to 50 kW is applied and a glow discharge is caused to generate a low-temperature plasma of the inorganic gas. A glass laminate is provided in the substrate to treat the supporting substrate. When the glass laminate is continuously processed, the surface of the glass laminate is subjected to plasma treatment while moving the laminate sequentially. As the inorganic gas, a rare gas such as helium, neon, or argon, and oxygen, nitrogen, air, carbon dioxide, ammonia, or the like can be used. These gases are not limited to one species but may be a mixture of two or more species.

In any case of the normal-pressure plasma treatment and the low-pressure low-temperature plasma treatment, the plasma treatment time is preferably 0.1 to 1,000 seconds, more preferably 1 to 100 seconds.

UV ozone treatment is a treatment for irradiating UV (ultraviolet rays), changing oxygen in the air into ozone, and purifying the surface to be irradiated by the ozone and ultraviolet rays.

The UV light source is not particularly limited as long as it can change oxygen to ozone by UV irradiation. As a UV light source, a low-pressure mercury lamp can be mentioned. Low-pressure mercury lamps generate UV light at 185 nm and 254 nm, and 185 nm lines can change oxygen to ozone. The illuminance at the time of irradiation differs depending on the light source to be used, but generally several tens to several hundreds of mW / cm ² are used. Further, the illuminance can be changed by condensing or diffusing. The irradiation time varies depending on the illuminance of the lamp and the kind of the untreated layer, but is usually from 1 minute to 24 hours. The treatment temperature is usually 10 to 200 占 폚. The amount of UV irradiation (i.e., ultraviolet ray dose) is usually 1 mJ / cm ² or more, preferably 1 to 100000 mJ / cm ² , and more preferably 10 to 100000 mJ / cm ² .

By performing the above-described step S106, the adherend attached to the second main surface 10a side of the support substrate 10 is removed.

The difference in water contact angle of the second main surface 10a of the support substrate 10 before and after the step S106 (water contact angle before treatment-water contact angle after treatment) is preferably 30 degrees or more, more preferably 50 degrees or more desirable. The upper limit is not particularly limited, but is usually 70 degrees or less.

<< Second Embodiment >>

5 is a flowchart showing a manufacturing process in a second embodiment of the method for manufacturing a glass laminate according to the present invention. As shown in Fig. 5, the second embodiment includes a heating step S102, a surface treatment step S106, and a laminating step S104 in this order.

Except that the order of the surface treatment step S106 differs from that of the first embodiment described above, the respective steps of the above-described first embodiment and the method of the treatment are the same. More specifically, in the second embodiment, the supporting substrate having the resin layer is manufactured in the heating step S102, and then the above-mentioned surface treatment (for example, corona treatment) is performed on the second main surface side of the supporting substrate, And then a glass substrate is laminated on the silicon resin layer in the support substrate with the resin layer attached thereto to obtain a glass laminate. A desired glass laminate can be obtained even in the present embodiment.

Further, when the first and second embodiments are compared with each other, the first embodiment is preferable. In the case of the first embodiment, since the glass substrate is laminated before the surface treatment step S106 after the silicon resin layer is formed, impurities are hardly adhered to the silicon resin layer and the adhesion of the glass substrate is more excellent.

An electronic device (a glass substrate with a member including a glass substrate and a member for an electronic device) is manufactured using the glass laminate obtained in the first and second modes described above. Further, if necessary, the glass substrate of the glass laminate is polished.

Hereinafter, the procedures of these polishing processes and electronic device manufacturing processes (member forming process and separation process) will be described in detail.

<Polishing process>

The polishing step is a step of polishing the second main surface 20b of the glass substrate 20 in the glass laminate 100 thus obtained. By providing this step, minute irregularities and scratches on the second main surface 20b of the glass substrate 20 can be removed, and the flatness of the surface on which the electronic device member is formed can be improved. Therefore, the reliability of the electronic device as a product can be enhanced. This effect is remarkable for a glass substrate having a thickness of 0.3 mm or less used in the present invention. This is because the glass substrate having a thickness of 0.3 mm or less is difficult to be polished singly, and it is difficult to polish the glass substrate 100 before it is used in the production of the glass laminate 100.

The method of polishing is not particularly limited and a known method can be adopted, and mechanical polishing (physical polishing) or chemical polishing (chemical polishing) can be used. Examples of the mechanical polishing include a sand blasting method of spraying and grinding ceramic abrasive grains, a polishing method using a lapping sheet or a grinding stone, a chemical mechanical polishing (CMP) method using abrasive grains and a chemical solvent in combination.

As the chemical polishing (sometimes referred to as wet etching), a method of polishing the surface of a glass substrate by using a chemical liquid can be used.

Among them, chemical mechanical polishing is preferable because the flatness and cleanliness of the second main surface 20b of the glass substrate 20 after polishing are higher. As abrasives used in chemical mechanical polishing, known abrasives such as cerium oxide can be used.

&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. 6A, 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 total vinyl groups bonded to the silicon atoms is 0.9, and 100 parts by mass of the siloxane mixture is used as the 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 mass of the obtained mixed solution, 150 parts by mass of IP solvent 2028 (extreme point: 200 캜, manufactured by Idemitsu Kosan) was added to obtain a mixed solution.

Subsequently, the support substrate with the curable layer was mounted on the tip of a plurality of support pins provided on the bottom of the heat treatment apparatus. The tip of the support pin is in contact with the surface of the second main surface side (the side opposite to the side on which the curable silicone composition layer is provided) of the support substrate in the curable layer-attached support substrate and the second main surface side of the support substrate is in contact with the support pin There was no area.

In the heat treatment apparatus, a heating plate was disposed above the curable silicone composition layer of the supporting substrate with a curable layer, and the supporting substrate with the curable layer was heated (prebaked heating) at 200 캜 for 3 minutes by the heating plate.

Subsequently, the support substrate with the curable layer after the heat treatment was subjected to heat treatment (post-baking treatment) at 250 DEG C for 1450 seconds to form a silicon resin layer having a thickness of 8 mu m on the first main surface of the support substrate.

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

In the obtained glass laminate A, 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, and were free from distortion defects and had good smoothness. In the glass laminate A, 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.

Then, corona treatment (electric power 1 kW, processing speed 4 m / min) was applied to the second main surface of the support substrate in the obtained glass laminate A.

The water contact angle before and after the corona treatment on the second main surface of the support substrate in the glass laminate A was measured to be 70 degrees before the corona treatment and 5 degrees after the corona treatment. From these measurement results, it was confirmed that the silicone resin adhered to the second main surface side of the support substrate was removed by the corona treatment.

(Peeling evaluation)

The glass laminate A was placed on the table pad so that the support substrate in the glass laminate A subjected to the corona treatment contacted with the urethane tabletop. Subsequently, the glass laminate A was pressed on a table pad at 100 g / cm ² for 120 seconds. After press bonding, air and water were sprayed between the support substrate and the table pad, and both were peeled off as a result of peeling.

Further, the same results as above were obtained when the processing speed in the corona treatment was changed to 1 m / min and 6 m / min.

&Lt; Comparative Example 1 &

A glass laminate B was obtained in the same manner as in Example 1 except that the corona treatment was not performed.

As a result of the above (peeling evaluation) using the glass laminate B instead of the glass laminate A, the glass laminate B could not be peeled off.

&Lt; Example 2 >

In this example, an OLED is manufactured by using the glass laminate A subjected to the corona treatment obtained in Example 1.

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 A 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 from 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 sputtering 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. Next, aluminum is deposited by a sputtering method 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 A 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 first main surface of the support substrate of the panel A is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the 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 is 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. 2013-260453 filed on December 17, 2013, the contents of which are incorporated herein by reference.

10: Support substrate
10a: a second main surface of the supporting 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
50: Support
52: Support pin
60: Corona treating device
62: first high voltage electrode
64: first ground electrode
66: second high voltage electrode
68: second ground electrode
70: first electrode pair
72: second electrode pair
74: conveying roll
76: First high frequency power source
78: Second high frequency power source
100: Glass laminate
X: Glass laminate

Claims (7)

A method for producing a glass laminate having a support substrate, a silicone resin layer and a glass substrate in this order,
A curable layer-attached support substrate having a support substrate having a first main surface and a second major surface and a curable silicone composition layer disposed on the first main surface of the support substrate is provided from the second main surface side of the support substrate to a plurality of supports A heating step of supporting the curable layer-attached supporting substrate with a pin to form a silicon resin layer by performing heat treatment;
A laminating step of laminating a glass substrate on the silicon resin layer after the heating step,
Wherein after the laminating step or after the heating step and before the laminating step at least the second main surface of the supporting substrate is subjected to at least one treatment selected from the group consisting of corona treatment, Treatment process
Wherein the glass laminate is a glass laminate. The process for producing a glass laminate according to claim 1, wherein the curable silicone composition layer contains at least 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 heating step includes a first heating step of performing a heating treatment at a first temperature and a second heating step of performing a heating treatment at a second temperature higher than the first temperature Wherein the glass laminate is provided in this order. 4. The method of claim 3, wherein the curable layer-attached support substrate is formed by applying a curable silicone composition comprising curable silicone and a solvent on the first major surface of the support substrate,
Wherein the first temperature satisfies an ultracentrifugation point of the solvent - 30 deg. C &lt; = first temperature &lt; = ultra violet spot of the solvent + 30 deg. The method of manufacturing a glass laminate according to any one of claims 1 to 4, wherein a surface treatment step is performed after the laminating step. The glass laminate according to claim 5, wherein in the surface treatment step, an electrode pair including a high-voltage electrode and a ground electrode opposed to each other with a transport path through which the glass laminate obtained in the laminating step is transported, And one of the adjacent electrode pairs is arranged on one side with the high voltage electrode between the conveyance paths and the other high voltage electrode on the other side across the conveyance path,
Applying a high-frequency voltage to the high voltage electrode while conveying the glass laminate along the conveyance path to conduct corona treatment to the glass laminate. A member forming step of forming a member for an electronic device on a surface of the glass substrate of a glass laminate manufactured by the manufacturing method of any one of claims 1 to 6 to obtain a member laminate for an electronic device;
Removing the resin layer-attached supporting substrate having the silicon resin layer and the supporting substrate from the electronic device-member mounting laminate to obtain an electronic device having the glass substrate and the electronic device member
Wherein the step of forming the electronic device comprises the steps of:

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