TWI627148B - 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, which is a method for manufacturing a glass laminate having a supporting substrate, a polysiloxane resin layer, and a glass substrate in this order, and includes a heating step for The support substrate of the main surface and the second main surface, and the support substrate with a hardening layer of the curable polysiloxane composition layer disposed on the first main surface of the support substrate are from the second main surface of the support substrate. On the side, a plurality of support pins are used for support, and the support substrate with a hardening layer is heated to form a polysiloxane resin layer. The lamination step is a step of laminating glass on the polysiloxane resin layer after the heating step. A substrate; and a surface treatment step after the above lamination step, or after the heating step and before the lamination step, at least the second main surface of the support substrate is selected from corona treatment, plasma treatment, and At least one of a group consisting of UV ozone treatment.

Description

Manufacturing method of glass laminated body and manufacturing method of electronic device

The present invention relates to a method for manufacturing a glass laminate and a method for manufacturing an electronic device.

In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL (Electroluminescence) panels (OLEDs) have become thinner and lighter, and the glass used in these devices The thinning of the substrate is continuously developing. If the strength of the glass substrate is insufficient due to thinning, the operability of the glass substrate is reduced in the manufacturing steps of the device.

Recently, in order to cope with the above-mentioned problems, a method has been proposed in which a glass laminate having a glass substrate and a reinforcing plate is prepared, and a member for electronic devices such as a display device is formed on the glass substrate of the glass laminate, and the reinforcing plate is removed from the glass The substrate is separated (for example, refer to Patent Document 1). The reinforcing plate has a support substrate and a silicone resin layer fixed on the support substrate, and the silicone resin layer and the glass substrate are adhered in a peelable manner. The reinforcing plate is peeled off at the interface between the polysiloxane resin layer of the glass laminate and the glass substrate. The reinforcing plate separated from the glass substrate can be laminated with a new glass substrate and reused as a glass laminate.

Furthermore, there may be a case where the formed glass laminate is subjected to a polishing treatment in order to polish the surface of a glass substrate (Patent Document 2).

[Prior technical literature] [Patent Literature]

[Patent Document 1] International Publication No. 2007/018028

[Patent Document 2] Japanese Patent Laid-Open No. 2013-149713

On the other hand, a method of heating and drying a support substrate on which a coating film is disposed on the top of a plurality of support pins has been known from the past.

When the present inventors produced a reinforcing plate in accordance with the method described in Patent Document 1, a support substrate on which a coating film that becomes a polysiloxane layer by heating was placed on the surface was placed on top of a plurality of support pins. After heating and drying to form a polysiloxane resin layer, a glass substrate is laminated on the polysiloxane resin layer to prepare a glass laminate. Thereafter, the support substrate side in the obtained glass laminate is directed toward a specific substrate side, and the glass laminate is placed on a specific substrate, as described in Patent Document 1 or 2, in the glass in the glass laminate A member for an electronic device is formed on a substrate, or a surface of a glass substrate is polished. Thereafter, when the glass laminate is to be removed from a specific substrate, the specific substrate is in close contact with the support substrate, and the glass laminate is fixed to the specific substrate and cannot be easily removed. Therefore, a reduction in productivity due to a prolonged process time or a reduction in the manufacturing yield of an electronic device is caused.

This invention was made in view of the said subject, and an object of this invention is to provide the manufacturing method of the glass laminated body which can manufacture the glass laminated body which can be easily peeled from a board | substrate after mounting a support substrate side toward various boards.

Another object of the present invention is to provide a method for manufacturing an electronic device using a glass laminate manufactured by the method for manufacturing a glass laminate.

The present inventors have made intensive studies in order to solve the above problems, and as a result, have completed the present invention.

That is, the first aspect of the present invention is a method for manufacturing a glass laminate, which is a method for manufacturing a glass laminate having a support substrate, a polysiloxane resin layer, and a glass substrate in this order. In addition, the method includes a heating step for adding a hardening layer including a supporting substrate having a first main surface and a second main surface, and a hardening polysiloxane composition layer disposed on the first main surface of the supporting substrate. The support substrate is supported by a plurality of support pins from the second main surface side of the support substrate. The support substrate with a hardening layer is subjected to a heat treatment to form a polysiloxane resin layer; the lamination step is performed after the heating step, A glass substrate is laminated on the siloxane resin layer; and a surface treatment step is performed after the lamination step, or after the heating step and before the lamination step, at least the second main surface of the supporting substrate is selected from corona treatment and plasma treatment. And UV (Ultra Violet, ultraviolet) ozone treatment of at least one of the group consisting of.

In the first aspect, the hardenable polysiloxane composition layer preferably contains at least an organic alkenyl polysiloxane having an alkenyl group and an organic hydrogen polysiloxane having a hydrogen atom bonded to a silicon atom. alkyl.

In the first aspect, the heating step preferably includes a first heating step in which a heat treatment is performed at a first temperature, and a second heating step in which a heat treatment is performed at a second temperature higher than the first temperature.

In the first aspect, the supporting substrate with a hardening layer is formed by applying a hardening polysiloxane composition containing a hardening polysiloxane and a solvent to the first main surface of the supporting substrate, and The first temperature preferably satisfies the initial boiling point of the solvent -30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C.

In the first aspect, the surface treatment step is preferably performed after the lamination step.

In the first aspect, preferably, in the surface treatment step, a plurality of pairs of electrode pairs including the high-voltage electrode and the ground electrode opposite to each other through the transport path through which the glass laminate obtained in the lamination step is transported are along the glass. Arrange the conveying direction of the laminated body, arrange the high-voltage electrode of one of the adjacent electrode pairs on one side across the conveyance path, and arrange the other high-voltage electrode on the other side across the conveyance path, and one side The glass laminate is transported along the conveyance path, and a high-frequency voltage is applied to the high-voltage electrode, and the glass laminate is applied. Corona treatment.

A second aspect of the present invention is a method for manufacturing an electronic device, including a component forming step for forming an electronic device on a surface of a glass substrate of a glass laminate manufactured by the manufacturing method of the first aspect. To obtain a laminated body with a member for an electronic device; and a separation step of removing a supporting substrate having a polysiloxane resin layer and a supporting layer with a resin layer from the laminated body with an electronic device member and obtaining a glass having Electronic device of substrate and member for electronic device.

According to the present invention, it is possible to provide a method for manufacturing a glass laminate, which can manufacture a glass laminate that can be easily peeled from the substrate after the support substrate side is placed toward various substrates.

In addition, according to the present invention, it is possible to provide a method for manufacturing an electronic device using the glass laminated body manufactured by the glass laminated body manufacturing method.

10‧‧‧ support substrate

10a‧‧‧ 2nd main surface of supporting substrate

12‧‧‧ hardening polysiloxane composition layer

14‧‧‧ Support substrate with hardening layer

16‧‧‧Polysiloxane layer

16a‧‧‧ The surface of the polysiloxane layer opposite to the support substrate side

18‧‧‧ Support substrate with resin layer

20‧‧‧ glass substrate

20a‧‧‧The first main surface of the glass substrate

20b‧2nd main surface of glass substrate

22‧‧‧ Components for electronic devices

24‧‧‧ Laminated body with components for electronic devices

26‧‧‧Electronic device

50‧‧‧ support desk

52‧‧‧Support sales

60‧‧‧Corona treatment device

62‧‧‧The first high voltage electrode

64‧‧‧The first ground electrode

66‧‧‧Second high voltage electrode

68‧‧‧ 2nd ground electrode

70‧‧‧ 1st electrode pair

72‧‧‧ 2nd electrode pair

74‧‧‧ transporting roller

76‧‧‧1st high frequency power supply

78‧‧‧ 2nd high frequency power supply

100‧‧‧ glass laminate

X‧‧‧ glass laminated body

FIG. 1 is a flowchart showing manufacturing steps in a first aspect of a method for manufacturing a glass laminate according to the present invention.

2 (A), (B), and (C) are schematic cross-sectional views showing a first aspect of the method for manufacturing a glass laminate of the present invention in the order of steps.

FIG. 3 is a schematic diagram showing an arrangement state of a supporting substrate with a hardening layer in a heating step.

Fig. 4 is a side view showing an embodiment of the corona treatment device.

FIG. 5 is a flowchart showing the manufacturing steps of the second aspect of the method for manufacturing a glass laminate of the present invention.

6 (A) and 6 (B) are schematic sectional views showing an embodiment of a method for manufacturing an electronic device according to the present invention in the order of steps.

Hereinafter, the preferred embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited by the following embodiments, and various kinds of embodiments can be applied to the following embodiments without departing from the scope of the present invention. Change and replacement.

When the present inventors studied the above problems, they found that the silicone resin adhered to the second main surface (back surface) side of the support substrate after the heating step or after the glass laminate was produced (after the lamination step), which is the above problem One of the reasons.

More specifically, during the heating step, the silicone resin or one of its raw materials is partially volatilized, so that the silicone resin adheres to the second main surface side of the support substrate supported by the support pin. Therefore, when the support substrate side of the glass laminate is directed toward a specific substrate side and the glass laminate is placed on a specific substrate, the polysilicon existing between the specific substrate and the support substrate in the glass laminate Resin increases the peeling strength of a specific substrate and a support substrate, making it difficult for both to peel. Therefore, it has been found that after the glass laminate is produced, various treatments are performed on the second main surface side of the support substrate to remove the silicone resin, thereby solving the above problems.

The manufacturing method of the glass laminated body of the present invention includes: a heating step of applying a heat treatment to a supporting substrate with a hardenable layer; a step of laminating a laminated glass substrate; and a surface treatment step of performing a surface treatment. Moreover, the surface treatment step is performed after the above-mentioned lamination step, or after the above-mentioned heating step and before the above-mentioned lamination step. Hereinafter, the former aspect will be described as a first aspect, and the latter aspect will be described as a second aspect.

<< 1st aspect >>

FIG. 1 is a flowchart showing manufacturing steps in a first aspect of a method for manufacturing a glass laminate according to the present invention. As shown in FIG. 1, the first aspect sequentially includes a heating step S102, a lamination step S104, and a surface treatment step S106.

The materials and procedures used in each step are described in detail below. First, the heating step S102 will be described in detail.

<Heating step>

The heating step S102 is a step of using a plurality of support pins to include a support substrate having a first main surface and a second main surface and a layer of a hardening polysiloxane composition disposed on the first main surface of the support substrate. The supporting substrate with a hardening layer is formed by supporting the second main surface of the supporting substrate (the surface opposite to the side having the hardening polysiloxane composition layer), and heating the supporting substrate with a hardening layer to form the supporting substrate. Silicone resin layer. More specifically, for the supporting substrate 14 with a hardening layer including the supporting substrate 10 and the hardening polysiloxane composition layer 12 in FIG. 2 (A), this step S102 is performed, thereby obtaining a graph as shown in FIG. 2 ( B) A support substrate 18 including a support substrate 10 and a silicone resin layer 16 with a resin layer as shown.

In the following, first, the members and materials (supporting substrate, curable polysiloxane composition layer) used in this step S102 will be described in detail, and then the procedure of step S102 will be described in detail.

(Support substrate)

The supporting substrate 10 has two main surfaces, a first main surface and a second main surface. The supporting substrate 10 supports and reinforces the glass substrate 20 described below in cooperation with the silicone layer 16 described below. (Procedure for manufacturing electronic device member) In the manufacturing of the electronic device member, deformation, damage, breakage, etc. of the glass substrate 20 are prevented. In addition, in the case of using a thinner glass substrate than before, a glass laminate having the same thickness as the previous glass substrate can be used, and a manufacturing method suitable for the previous thickness of the glass substrate can be used in the component formation step or Manufacturing equipment is also one of the purposes of using the supporting substrate 10.

As the support substrate 10, for example, a metal plate such as a glass plate, a plastic plate, or a SUS (Steel Use Stainless) plate, a ceramic plate, or the like can be used. When the component forming step is accompanied by a heat treatment, the support substrate 10 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 20, and more preferably formed of the same material as the glass substrate 20. That is, the support 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.

Regarding the thickness of the support substrate 10, it may be thicker than the glass substrate 20 or thinner than the glass substrate 板 20。 Plate 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 current component forming step is designed for processing 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 0.4mm. The thickness of the support substrate 10 is preferably 0.2 to 5.0 mm in a normal case.

In the case where the support substrate 10 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons such as easy operation and difficulty in breakage. In addition, the thickness of the glass plate is preferably 1.0 mm or less for the reason that it is desired to have a rigidity that is moderately curved without being broken when the electronic device member is peeled off.

The difference between the average linear expansion coefficient (hereinafter referred to as the "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, and more preferably 300 × 10 ^-7 / ° C or lower, more preferably 200 × 10 ^-7 / ° C or lower. If the difference is too large, the glass laminate may be violently bent during heating and cooling in the member forming step, or the glass substrate 20 and the supporting substrate 18 with a resin layer described below may peel off. When the material of the glass substrate 20 and the material of the support substrate 10 are the same, the above-mentioned problems can be suppressed from occurring.

(Hardening polysiloxane composition layer)

The curable polysiloxane composition layer is a composition composition layer capable of forming a polysiloxane resin layer in step S102.

The curable polysiloxane composition layer contains a curable polysiloxane that is cured to become a polysiloxane resin. This type of hardening polysiloxane is classified into condensation reaction type polysiloxane, addition reaction type polysiloxane, ultraviolet hardening type polysiloxane, and electron beam hardening type polysiloxane based on its hardening mechanism. Any type of hardened polysiloxane. Among these, an addition reaction type polysiloxane is preferable. The reason for this is that the hardening reaction is easy to proceed, the degree of peelability when the silicone resin layer is formed is good, and the heat resistance is also high.

The addition reaction type polysiloxane is a curable composition containing a main agent and a cross-linking agent and hardened in the presence of a catalyst such as a platinum catalyst. The hardening of the addition reaction type polysiloxane Promoted by heat treatment. The main agent in the addition reaction-type polysiloxane is preferably an organic polysiloxane (i.e., an organic alkenyl polysiloxane) having an alkenyl group (vinyl group, etc.) bonded to a silicon atom; It is linear), and the alkenyl group and the like become a crosslinking point. The cross-linking agent in the addition reaction type polysiloxane is preferably an organic polysiloxane (ie, an organohydrogen polysiloxane) having a hydrogen atom (hydrosilyl group) bonded to a silicon atom; more preferably, It is linear), and a hydrogenated silane group or the like becomes a crosslinking point.

The addition reaction type polysiloxane is hardened by the addition reaction of the crosslinking point of the main agent and the crosslinking agent. In addition, in terms of heat resistance derived from a cross-linked structure, the hydrogen atom bonded to the silicon atom of the organic hydrogen polysiloxane is compared with the mole of the organic alkenyl polysiloxane alkenyl group. It is preferably 0.5 ~ 2.

When the hardening polysiloxane contained in the hardening polysiloxane composition layer is an addition reaction type polysiloxane, the hardening polysiloxane composition layer may further contain a catalyst (especially a platinum group metal system Catalyst), or reaction inhibitor.

Platinum group metal catalysts (platinum metal catalysts for hydrosilylation) are used to promote and promote the hydrosilylation of alkenyl groups in the organic alkenyl polysiloxanes and hydrogen atoms in the organic hydrogen polysiloxanes. Catalyst for reaction. Examples of the platinum group metal catalyst include platinum-based, palladium-based, and rhodium-based catalysts. In terms of economy and reactivity, a platinum-based catalyst is particularly preferably used.

Reaction inhibitors (reaction inhibitors for hydrosilylation) are so-called catalysts that inhibit the catalyst activity of the above catalysts (especially platinum group metal catalysts) at room temperature, thereby increasing the life of the hardening polysiloxane composition. Pot life extender (also known as delay agent). Examples of the reaction inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene-based compounds, oxime compounds, and organic chlorine compounds. Particularly preferred are acetylene-based compounds (for example, acetylene alcohols and silylates of acetylene alcohol).

The method for forming a hardenable polysiloxane composition layer on a support substrate is not particularly limited, and a known method can be adopted. For example, the method of apply | coating the above-mentioned curable polysiloxane containing curable polysiloxane to a support substrate is mentioned. Furthermore, the method of coating The method is not particularly limited, and a known method can be adopted. Examples of the coating method include a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, and a gravure coating method. From the above methods, it can be appropriately selected depending on the kind of the curable polysiloxane composition.

In the hardening polysiloxane composition, a solvent may be contained as needed. The solvent is preferably one that can easily dissolve various components and can be easily removed by evaporation. Specific examples include butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF (Tetrahydrofuran, tetrahydrofuran), and chloroform. Among them, saturated hydrocarbons are preferred, and one or two or more kinds of saturated hydrocarbons (straight-chain saturated hydrocarbons, branched-chain saturated hydrocarbons, and alicyclic saturated hydrocarbons) can be used as practical saturated hydrocarbon solvents. Examples include: Isopar G (made by Exxon Mobil Co., Ltd.), Isopar L (made by Exxon Mobil Co., Ltd.), Isopar H (made by Exxon Mobil Co., Ltd.), Isopar M (made by Exxon Mobil Co., Ltd.), NORPAR 13 (Exxon Mobil Co., Ltd.) (Made by the company), NORPAR 15 (made by Exxon Mobil Co., Ltd.), Exxsol D40 (made by Exxon Mobil Co., Ltd.), Exxsol D60 (made by Exxon Mobil Co., Ltd.), Exxsol D80 (made by Exxon Mobil Co., Ltd.), Neothiosol (Central Chemical Corporation Limited) (Manufactured by the company), IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.).

Among them, in the case where step S102 is performed in two stages as described below, it is preferable to use a solvent having an initial boiling point (under atmospheric pressure) of 210 ° C. or lower in the first heating stage.

In addition, the thickness of the curable polysiloxane composition layer is not particularly limited, and it is appropriately adjusted so that a polysiloxane resin layer having a preferable thickness described below can be obtained.

(Order of steps)

In this step S102, a support substrate with a hardening layer is supported from the second main surface side of the support substrate by a plurality of support pins, and a heat treatment is performed. That is, the support substrate with the hardening layer is supported by the support pins while being heated. More specifically, as shown in Figure 3 As shown in the figure, a support substrate 14 with a hardening layer is disposed on the top (top) of a plurality of support pins 52 arranged at intervals on the support table 50. In this state, the support substrate 14 with a hardening layer is heat-treated. The support pin 52 supports the second main surface 10 a of the support substrate 10 in the support substrate 14 with a hardening layer as shown in FIG. 3.

Only three support pins 52 are shown in FIG. 3, but the number of support pins is not particularly limited, and may be ten or more. In addition, the arrangement position of the support pin 52 is not particularly limited, and it can be arranged at a specific interval or randomly. Furthermore, the shape of the support pin 52 is not particularly limited, and may be any of a cylindrical shape, a polygonal shape, and the like.

Furthermore, as shown in FIG. 3, the support pin 52 is in contact with a part of the second main surface 10 a side of the support substrate 10, and therefore, there is an area not in contact with the support pin 52 on the second main surface 10 a side of the support substrate 10 .

The method of heating the support substrate with a hardening layer is not particularly limited as long as it can be heated in a state where the support substrate with a hardening layer is supported by the above-mentioned support pins. For example, it can be used in a heating room provided with a support pin. A well-known heat treatment device such as an oven. More specifically, a method using a heat treatment device including a hot plate (for example, a method in which an upper portion of a hardening polysiloxane composition layer provided in a supporting substrate with a hardening layer disposed on a supporting pin is provided, is provided. A method of heating in a heating device of a hot plate).

The heating conditions for thermally curing the curable polysiloxane composition layer are appropriately selected depending on the type of the curable polysiloxane used. Among them, in terms of the hardening speed of the hardening polysiloxane and the heat resistance of the formed polysiloxane resin layer, it is preferably performed at 150 to 300 ° C (preferably 180 to 250 ° C) for 10 to 120. Minute (preferably 30 to 60 minutes) heat treatment.

As a preferred aspect of this step S102, a condition in which the heat treatment is performed in two stages under different temperature conditions is preferred. 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. borrow By performing the heat treatment in two stages, the surface shape of the formed silicone resin layer 16 is more excellent, and the adhesion with the glass substrate 20 described below is further improved. When the heat treatment is performed in two stages, the first heating step and the second heating step may be performed using different heat treatment devices.

Furthermore, in the case where the support substrate with a hardening layer is formed by coating a hardening polysiloxane composition containing a hardening polysiloxane and a solvent on the support substrate, the removal property of the solvent is more excellent. On the other hand, the surface of the hardening polysiloxane composition layer becomes flat and the decomposition of the hardening polysiloxane is more suppressed. The first temperature is preferably -30 ° C to the initial distillation point of the solvent. Point within the range of + 30 ° C. In other words, the first temperature preferably satisfies the following relational expression.

The initial boiling point of the solvent -30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C

The initial boiling point of a solvent means a value measured in accordance with 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, and more preferably 30 ° C or higher. The upper limit is not particularly limited, but is usually preferably 100 ° C or lower, and more preferably 70 ° C or lower.

The first temperature is preferably 210 ° C or lower. That is, it is preferable to include a first heating step for performing a heat treatment at 210 ° C or lower, and a second heating step for performing a heat treatment at a temperature exceeding 210 ° C. If it is 210 ° C. or lower, the bumping of the solvent or the volatilization of the silicone resin is more suppressed, so that the surface shape of the formed silicone resin layer 16 is more excellent. Hereinafter, the first heating step and the second heating step under the temperature conditions will be described in detail.

The first heating step is a so-called pre-baking step, which mainly removes volatile components such as solvents remaining in the curable polysiloxane composition layer 12 and prevents the solvent from boiling in the second heating step described below. The temperature condition of the first heating step is preferably 210 ° C. or lower, and in terms of the surface profile of the silicone resin layer 16 being more excellent, it is more preferably 150 to 210 ° C. Heating time The optimum conditions are appropriately selected according to the materials used. In terms of productivity and solvent removal, it is preferably 1 to 5 minutes, and more preferably 2 to 3 minutes.

The second heating step is a so-called post-baking step, which mainly promotes the hardening of the curable polysiloxane composition layer 12 to form a polysiloxane resin layer 16. The temperature condition in the second heating step is preferably more than 210 ° C. In terms of better solvent removal and hardening reaction of the curable polysiloxane composition layer 12, it is more preferably more than 210 ° C and 250 ° C or less. The heating time is appropriately selected according to the materials used. In terms of productivity and solvent removal, it is preferably 10 to 120 minutes, and more preferably 30 to 60 minutes.

The silicone resin layer 16 formed through this step S102 is fixed on one side of the support substrate 10 by the curing reaction of the hardening silicone composition layer 12 on the support substrate 10, and is peelable. This method is in close contact with the glass substrate 20 described below. The polysiloxane resin layer 16 prevents misalignment of the glass substrate 20 until the operation of separating the glass substrate 20 from the support substrate 10 is performed, and it is prevented from being easily peeled from the glass substrate 20 due to the separation operation. damaged. In addition, the polysiloxane resin layer 16 is fixed to the support substrate 10, and the polysiloxane resin layer 16 and the support substrate 10 are not separated during the separation operation. The support substrate 18 with a resin layer can be obtained by the separation operation.

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

In the present invention, there is a difference in peel strength (that is, the stress required for peeling) for the above-mentioned fixed and peelable adhesion. Fixation means that the peel strength is greater than the adhesion. In addition, the so-called peelable adhesion means peeling and peeling without causing peeling of the fixed surface. Specifically, when the operation of separating the glass substrate 20 from the support substrate 10 is performed in the glass laminate of the present invention, it means a case where it is peeled off on the surface that is in close contact, and it is not peeled off on the fixed surface. Therefore, in the glass laminate, if the operation of separating the glass substrate 20 and the support substrate 10 is performed, the glass laminate is laminated. The body is divided into both a glass substrate 20 and a support substrate 18 with a resin layer.

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

The thickness of the polysiloxane resin layer 16 is not particularly limited, but is preferably 2 to 100 μm, more preferably 3 to 50 μm, and even more preferably 7 to 20 μm. If the thickness of the silicone resin layer 16 is within the above range, even if there are bubbles or foreign matter between the silicone resin layer 16 and the glass substrate 20, the generation of deformation defects of the glass substrate 20 can be suppressed. Further, if the thickness of the silicone resin layer 16 is too thick, it may be uneconomical due to the time and material required for the formation, and the heat resistance may be reduced. When the thickness of the silicone resin layer 16 is too thin, the adhesion between the silicone resin layer 16 and the glass substrate 20 may be reduced.

<Lamination step>

The laminating step S104 is a step of laminating a glass substrate 20 on the surface of the polysiloxane resin layer 16 obtained in the above step S102 to obtain a support substrate 10, a polysiloxane resin layer 16, and a glass substrate 20 in this order. The glass laminate 100. More specifically, as shown in FIG. 2 (C), the surface 16a of the silicone resin layer 16 on the side opposite to the support substrate 10 side, and the glass substrate having the first main surface 20a and the second main surface 20b The first main surface 20 a of 20 is a build-up layer, and the polysiloxane resin layer 16 and the glass substrate 20 are laminated to obtain a glass laminate 100. Furthermore, as described below, the obtained glass laminate 100 is a glass laminate before the following surface treatment step S106 is performed, and it is estimated that the support substrate 10 and the polysiloxane layer 16 of the glass laminate 100 The surface opposite to the side (the second main surface 10a of the support substrate 10) is adhered with a silicone resin or a raw material thereof.

The glass substrate 20 to be used is described in detail below.

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 superposing the glass substrate 20 on the surface of the silicone resin layer 16 under a normal pressure environment can be mentioned. Furthermore, if necessary, it may be superposed on the surface of the polysiloxane layer 16 After the glass substrate 20, the glass substrate 20 is pressure-bonded to the silicone resin layer 16 using a roller or pressure. It is relatively easy to remove the air bubbles mixed between the silicone resin layer 16 and the glass substrate 20 by using a roller or a pressure contact, so it is preferable.

If the silicone resin layer 16 and the glass substrate 20 are pressure-bonded by a vacuum lamination method or a vacuum pressure method, it is more preferable to prevent the inclusion of bubbles or to ensure a good adhesion. There is also an advantage that by performing pressure bonding under vacuum, even when there are tiny bubbles remaining, there is no case where the bubbles grow due to heating and it is difficult to cause deformation defects of the glass substrate 20.

When the glass substrate 20 is laminated, it is preferable that the surface of the glass substrate 20 that is in contact with the polysiloxane resin layer 16 is sufficiently cleaned and laminated in an environment with high cleanliness. The higher the cleanliness, the better the flatness of the glass substrate 20 is, so it is preferable.

In addition, after the glass substrate 20 is laminated, a pre-annealing treatment (heating treatment) may be performed as necessary. By performing this pre-annealing treatment, the adhesion of the laminated glass substrate 20 to the silicone resin layer 16 is improved, and appropriate peeling strength can be achieved. However, it becomes difficult to produce electronic devices during the following member formation steps. Dislocation of components, etc., and the productivity of electronic devices is improved.

The conditions of the pre-annealing treatment are appropriately selected depending on the type of the silicone resin layer 16 used, so that the peeling strength between the glass substrate 20 and the silicone resin layer 16 becomes more appropriate. In other words, the heat treatment is preferably performed at a temperature of 300 ° C. or higher (preferably 300 to 400 ° C.) for 5 minutes or more (preferably 5 to 30 minutes).

(Glass base board)

The glass substrate 20 has a first main surface 20 a in contact with the silicone resin layer 16, and a second main surface 20 b on the side opposite to the silicone resin layer 16 side is provided with a member for an electronic device.

The type of the glass substrate 20 may be ordinary, and examples thereof include glass substrates for display devices such as an LCD (liquid crystal display) and an OLED (Organic Light-Emitting Diode). Chemical resistance of glass substrate 20 Excellent in moisture resistance and moisture permeability, and has a low thermal shrinkage. As an index of thermal shrinkage, a linear expansion coefficient prescribed by JIS R 3102 (revised in 1995) can be used. The contents of JIS R 3102 (as amended in 1995) are incorporated herein by reference.

When the linear expansion coefficient of the glass substrate 20 is large, since the following member formation steps are often accompanied by heat treatment, various problems are likely to occur. For example, when a thin film transistor (TFT) is formed on the glass substrate 20, there is a possibility that if the glass substrate 20 on which the TFT is formed is cooled under heating, the TFT will be displaced due to the thermal contraction of the glass substrate 20 Become too big.

The glass substrate 20 is obtained by melting glass raw materials and shaping the molten glass into a plate shape. Such a molding method may be a common one, and for example, a float method, a melt method, a downhole method, a Fuco method, a Ruber method, or the like can be used. In addition, in particular, the thin glass substrate 20 can be formed by heating the glass that has been temporarily formed into a plate shape to a formable temperature, and stretching it by a method such as stretching to thin the glass (retraction method). And get.

The type of glass of the glass substrate 20 is not particularly limited, and alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses containing silicon oxide as a main component are preferred. The oxide-based glass is preferably a glass having a silicon oxide content of 40 to 90% by mass based on oxide conversion.

As the glass of the glass substrate 20, a glass suitable for the type of a member for an electronic device or a manufacturing process thereof is used. For example, the glass substrate for a liquid crystal panel is likely to affect the liquid crystal due to the elution of an alkali metal component, and therefore is composed of a glass (alkali-free glass) that does not substantially contain an alkali metal component (including an alkaline earth metal component). As described above, the glass of the glass substrate 20 is appropriately selected based on the type of the device to be applied and its manufacturing steps.

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 viewpoint of thinning and / or lightening the glass substrate 20. When the thickness of the glass substrate 20 is 0.3 mm or less, good flexibility can be imparted to the glass substrate 20. The thickness of the glass substrate 20 is 0.15 mm or less In this case, the glass substrate 20 can be wound into a roll shape.

In addition, for reasons such as easy manufacturing of the glass substrate 20 and easy handling of the glass substrate 20, the thickness of the glass substrate 20 is preferably 0.03 mm or more.

Furthermore, the glass substrate 20 may include two or more layers. In this case, the materials forming each layer may be the same material or different materials. In this case, the "thickness of the glass substrate 20" means the total thickness of all layers.

(Glass laminate)

The glass laminated body 100 is a laminated body which has a support substrate 10, a glass substrate 20, and a silicone resin layer 16 existing between them. The silicone resin layer 16 is in contact with the first main surface of the support substrate 10 on one side and in contact with the first main surface 20 a of the glass substrate 20 on the other side.

This glass laminated body 100 is used in the following member formation steps. That is, the glass laminated body 100 is used until a member for electronic devices such as a liquid crystal display device is formed on the surface of the second main surface 20 b of the glass substrate 20. Thereafter, the glass laminated body on which the member for an electronic device is formed is separated into a supporting substrate 18 with a resin layer and an electronic device, and the supporting substrate 18 with a resin layer does not become a part constituting the electronic device. A new glass substrate 20 can be laminated on the support substrate 18 with a resin layer and reused as a new glass laminate 100.

The interface between the support substrate 10 and the polysiloxane layer 16 has a peeling strength (x). If a stress exceeding the peeling direction (x) in the peeling direction is applied to the interface between the support substrate 10 and the polysiloxane layer 16, the support substrate 10 has a peel strength (x). Delamination occurred at the interface between 10 and the polysiloxane layer 16. The interface between the silicone resin layer 16 and the glass substrate 20 has peeling strength (y). If a stress exceeding the peeling direction (y) in the peeling direction is applied to the interface between the silicone resin layer 16 and the glass substrate 20, then the silicon The interface between the oxyresin layer 16 and the glass substrate 20 is peeled.

As described above, in the glass laminated body 100 (also referred to as a laminated body with a member for an electronic device described below), the peel strength (x) is greater (higher) than the peel strength (y). Therefore, if a stress is applied to the glass laminate 100 in the direction in which the support substrate 10 and the glass substrate 20 are peeled off, the glass laminate 100 is produced at the interface between the polysiloxane resin layer 16 and the glass substrate 20. The glass substrate 20 is peeled off and separated into a support substrate 18 with a resin layer.

That is, the silicone resin layer 16 is fixed on the support substrate 10 to form a support substrate 18 with a resin layer, and the glass substrate 20 is adhered to the silicone resin layer 16 in a peelable manner.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the silicone resin layer 16 to the support substrate 10 can be improved, and a relatively high adhesion to the glass substrate 20 can be maintained after the heat treatment.

The improvement of the adhesion of the polysiloxane resin layer 16 to the support substrate 10 is achieved by crosslinking and hardening the curable polysiloxane composition layer 12 on the support substrate 10 as described above to form polysiloxane. Resin layer 16. The silicone resin layer 16 bonded to the supporting substrate 10 with a higher bonding force can be formed by using the adhesive force during the cross-linking curing.

On the other hand, the bonding force of the cured product of the curable polysiloxane composition layer 12 to the glass substrate 20 is generally lower than the bonding force generated during the above-mentioned crosslinking and curing.

The glass laminated body 100 can be used for various applications, and examples thereof include applications for manufacturing electronic components such as a panel for a display device described below, PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed on the surface. In addition, in this application, the glass laminate 100 is often exposed to high temperature conditions (for example, 360 ° C. or higher) (for example, 1 hour or longer).

Here, the so-called display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

<Surface Treatment Step>

The surface treatment step S106 is a step in which at least the second main surface of the supporting substrate (the surface opposite to the side having the silicone resin layer) is selected from the group consisting of corona treatment, plasma treatment, and UV ozone treatment. At least one treatment in the group. In the first aspect, the above-mentioned process is intentionally performed on the second main surface of the supporting substrate in the glass laminate formed in the above. More specifically, the above-mentioned processing is performed on the second main surface 10a of the support substrate 10 in FIG. 2 (C). Management. By implementing this step S106, the silicone resin or its raw material components which are volatilized and adhered to the second main surface 10a of the support substrate 10 during the heating step S102 described above are removed, so that the second main surface of the support substrate 10 is removed. 10a cleansing. That is, by performing the above-mentioned processing on the glass laminated body obtained in the above-mentioned laminating step S104, a processed glass laminated body can be obtained. In addition, as described below, in this step S106, the second main surface of the support substrate in the glass laminate and the exposed surface of the glass substrate in the glass laminate may be subjected to the above processing together.

As the corona treatment (corona cleaning) performed in this step S106, a known corona treatment is performed. In addition, the so-called corona treatment is a surface treatment technology for modifying the surface of a treated substrate such as a plastic film, paper, and metal foil by corona discharge irradiation. If the high-frequency power device will oscillate the high frequency. When a high voltage is applied between the high voltage electrode and the ground electrode, a corona discharge is generated.

The method of corona treatment is not particularly limited. For example, a method is preferred in which a corona discharge is performed by applying a high voltage between a transport roller supporting a glass laminate and an electrode disposed opposite to it, and during this period, The glass laminate is sequentially moved to perform surface treatment. Specific examples of the device 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 glass-laminated glass-conveying device is mounted in front and rear of the device. The frequency of the high-frequency oscillator is not particularly limited. For example, it is preferably 0.1 to 100 kHz, and preferably the maximum output is about 0.5 to 50 kW. The conveyance 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 lamination step S104, it is preferable to use a corona treatment device described below.

Fig. 4 is a side view showing an embodiment of the corona treatment device. The corona treatment device 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 opposed to each other at a specific interval to form a first electrode pair 70. The first high-voltage electrode 62 and the first ground electrode A discharge space is formed between 64. In addition, the second high-voltage electrode 66 and the second ground electrode 68 are arranged to face each other with a predetermined interval therebetween to form a second electrode pair 72, and a discharge space is formed between the second high-voltage electrode 66 and the second ground electrode 68. . As shown in FIG. 4, the first electrode pair 70 and the second electrode pair 72 are conveyed along the glass laminate X having a support substrate, a polysiloxane resin layer, and a glass substrate in the order obtained in the lamination step S104. The directions are adjacent to each other. Further, as shown in FIG. 4, the glass laminate X is conveyed by a conveying roller 74 and is between the first high-voltage electrode 62 and the first ground electrode 64, and the second high-voltage electrode 66 and the second ground electrode 68. Move between.

The first high-voltage electrode 62 is connected to the first high-frequency power source 76 and is applied with a high-frequency voltage. The second high-voltage electrode 66 is connected to the second high-frequency power source 78 and is applied with a high-frequency voltage. Moreover, in FIG. 4, both the first high-frequency power supply 76 and the second high-frequency power supply 78 are used, but the present invention is not limited to this aspect, and the first high-frequency power supply 76 and the second high-frequency power supply 78 may be used. Use (share) the same power source.

Further, the first high-voltage electrode 62 and the second high-voltage electrode 66 are respectively arranged on the upper side (one side) and the lower side (the other side) of the path (transport path) through which the glass laminate X is transported in FIG. 4. In other words, the first high-voltage electrodes 62 and the second high-voltage electrodes 66 are staggered along the transport direction of the glass laminate X.

When the glass laminate X is transferred to the corona processing device 60 using the transfer roller 74, the first high-voltage electrode 62 and the second high-voltage electrode 66 are respectively disposed on one side and the other of the conveyance path of the glass laminate X Side, so that both sides of the glass laminate X to be transported can be corona treated efficiently. That is, the second main surface of the support substrate in the glass laminate X (the surface opposite to the silicone resin layer side) and the exposed surface of the glass substrate (the surface opposite to the silicone resin layer side) can be applied. Corona treatment.

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

In FIG. 4, the first high-voltage electrode 62 is disposed on the upper side in the drawing, and the second high-voltage electrode 62 The electrode 66 is arranged on the lower side in the drawing, but it is not limited to this aspect, and the above-mentioned positional relationship may be reversed.

When the corona treatment is to be applied to only one side of the glass laminate X (the second main surface of the supporting substrate), the first high-voltage electrode 62 and the second high-voltage electrode 66 may be arranged together in the figure. In the formula, the upper side or the lower side.

Further, in FIG. 4, the corona treatment device including both the first electrode pair 70 and the second electrode pair 72 is described, but the number of electrode pairs is not limited to this aspect.

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 an electrode covered with a dielectric body may be used, but the corona treatment is performed in order to perform stably. The discharge is preferably at least one of the first high-voltage electrode 62 and the first ground electrode 64 arranged oppositely, and at least one of the second high-voltage electrode 66 and the second ground electrode 68 arranged oppositely. Covered. 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 body. Thereby, the gap between the high-voltage electrode and the ground electrode can be enlarged, and the glass laminated body X can be easily and stably transported.

The dielectric-coated electrode (dielectric-coated electrode) is preferably a ceramic electrode obtained by coating ceramics or the like on the surface of a conductive core material such as stainless steel or aluminum. Generally, when corona treatment is performed on a resin film, a rubber electrode formed by coating a rubber material on a metal core material can be used as a dielectric-coated electrode. However, due to the relationship between weight and rigidity, the diameter is relatively large. In the case where the corona treatment device 60 is enlarged, there is a gap between the transport rollers, and a problem occurs when the thin glass laminate X is transported. The ceramic electrode is light in weight and high in rigidity, so its diameter is smaller than that of a rubber electrode, so it is difficult to cause the above problems.

In addition, in the rubber electrode, the rubber film is easily damaged due to electric discharge, and it is difficult to fix and use the electrode. Therefore, a rotation mechanism is provided on the rubber electrode, and it is usually used while rotating, but there are problems that the device is complicated and large. Regarding the ceramic electrode, it is difficult to damage even if it is repeatedly discharged at the same position, so it is not necessary to install the above-mentioned rotating machine. 结构。 Structure.

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

In the treatment of ordinary piezoelectric plasma, the discharge energy is applied to the gas, and the plasma is released under normal pressure. As its characteristics, there is no need to set a vacuum due to the normal pressing process, and the equipment is simple and the productivity is high. As the method, there are mainly a rare gas system normal piezoelectric slurry and a pulse type normal piezoelectric slurry that controls the application of a voltage to perform a glow discharge, and any of the above methods can be used.

In the low-pressure and low-temperature plasma treatment, the glass laminate is passed through a pressure-reducing, low-temperature plasma treatment device, so that the inside of the device becomes an inorganic gas atmosphere, and the pressure is maintained at 0.001 to 10 Torr, preferably 0.01 to 1 Torr. Apply power between 50Hz to 13.6MHz between the electrodes. Glow discharge is performed by applying electric power of 0.1 to 50 kW, so that a low-temperature plasma of inorganic gas is generated. A glass laminate is disposed therein to process the support substrate. In the case where the glass laminated body is continuously processed, the glass laminated body is sequentially moved while facing the surface for plasma treatment. As the inorganic gas, rare gases such as helium, neon, and argon, and oxygen, nitrogen, air, carbon dioxide gas, ammonia gas, and the like can be used. These gases are not limited to one type, and may be a mixture of two or more types of gases.

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

The so-called UV-ozone treatment is a treatment in which UV (ultraviolet rays) is irradiated to change oxygen in the air into ozone, and the surface to be irradiated is cleaned 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. Examples of the UV light source include a low-pressure mercury lamp. Low-pressure mercury lamps produce UV light at 185nm and 254nm. The 185nm line turns oxygen into ozone. The illuminance at the time of irradiation differs depending on the light source used, and usually several tens to hundreds of mW / cm ² are used. It is also possible to change the illuminance by collecting or diffusing light. The irradiation time varies depending on the illuminance of the lamp and the type of the untreated layer, and is usually 1 minute to 24 hours. The processing temperature is usually 10 ~ 200 ℃. Further, the UV irradiation amount (i.e., an amount of ultraviolet rays) is generally 1mJ / cm ² or more, preferably 1 ~ 100000mJ / cm ^2, more preferably 10 ~ 100000mJ / cm ^2.

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

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

<< 2nd aspect >>

Fig. 5 is a flowchart showing manufacturing steps in the second aspect of the method for manufacturing a glass laminate according to the present invention. As shown in FIG. 5, the second aspect sequentially includes a heating step S102, a surface treatment step S106, and a lamination step S104.

Compared with the first aspect described above, except that the implementation order of the surface treatment step S106 is different, the steps of the first aspect described above are the same as the method of processing. More specifically, in the second aspect, the supporting substrate with a resin layer is manufactured in the heating step S102, and then the above-mentioned surface treatment is performed on the second main surface side of the supporting substrate in the supporting substrate with the resin layer ( For example, corona treatment), and thereafter, a glass substrate is laminated on a polysiloxane resin layer in a support substrate with a resin layer to obtain a glass laminate. The required glass laminate can also be obtained in this embodiment.

Furthermore, if the first aspect described above is compared with the second aspect, the first aspect is preferred. In the case of the first aspect, since the glass substrate is laminated after the polysiloxane resin layer is formed and before the surface treatment step S106, it is difficult for impurities to adhere to the polysiloxane resin layer, and the adhesion of the glass substrate is more excellent.

The glass laminates obtained in the first aspect and the second aspect described above are used to manufacture an electronic device (a glass substrate including a glass substrate and a member with a member for an electronic device). If necessary, the glass substrate of the glass laminate is subjected to a polishing treatment.

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

<Grinding step>

The polishing step is a step of polishing the second main surface 20 b of the glass substrate 20 in the obtained glass laminate 100. By providing this step, the minute unevenness and damage of the second main surface 20b of the glass substrate 20 can be removed, and the flatness of the surface on which the member for an electronic device is formed can be improved. Therefore, the reliability of the electronic device as a product can be improved. This effect is significant for a glass substrate having a thickness of 0.3 mm or less used in the present invention. The reason is that it is difficult to individually polish a glass substrate having a thickness of 0.3 mm or less, and it is difficult to perform polishing in advance before manufacturing 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. As the mechanical polishing, a sandblasting method in which ceramic abrasive particles are blown and polished, a polishing method using a polishing sheet or a grindstone, and a chemical mechanical polishing (CMP) method in which abrasive particles and a chemical solvent are used in combination can be used.

In addition, as chemical polishing (also referred to as wet etching), a method may be used in which the surface of the glass substrate is polished using a chemical solution.

Among them, chemical mechanical polishing is preferred in terms of higher flatness and cleanliness of the second main surface 20b of the glass substrate 20 after polishing. In addition, as the abrasive grains used in chemical mechanical polishing, known abrasive grains such as cerium oxide can be used.

<Electronic device (glass substrate with member) and manufacturing method thereof>

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

The manufacturing method of the electronic device is not particularly limited. In terms of excellent productivity of the electronic device, a method is preferred in which a member for an electronic device is formed on a glass substrate in the glass laminate described above to manufacture the electronic device. Polysilicon The glass substrate side interface of the resin layer is a peeling surface, and it is separated from the obtained laminated body with a member for an electronic device into a support substrate with an electronic device and a resin layer.

Hereinafter, the step of forming an electronic device member on the glass substrate in the above-mentioned glass laminated body to produce a laminated body with an electronic device member is referred to as a member forming step, and the glass substrate side interface of the silicone resin layer is peeled On the other hand, the step of separating the laminated body from a member for attaching an electronic device into an electronic device and a supporting substrate with a resin layer is called a separating step.

The materials and procedures used in each step are described in detail below.

(Member formation step)

The component formation step is a step of forming a component for an electronic device on the glass substrate 20 in the glass laminate 100 obtained in the above-mentioned lamination step. More specifically, as shown in FIG. 6 (A), a member 22 for an electronic device is formed on the second main surface 20b (exposed surface) of the glass substrate 20 to obtain a laminated body 24 with a member for an electronic device.

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

(Member (functional element) for electronic device)

The electronic device member 22 is a member formed on the glass substrate 20 in the glass laminate 100 and constitutes at least a part of the electronic device. More specifically, as the member 22 for an electronic device, members used in electronic parts such as a panel for a display device, a solar cell, a thin film secondary battery, or a semiconductor wafer with a circuit formed on the surface (for example, a member for a display device) , Solar battery components, thin film secondary battery components, and electronic component circuits).

For example, as the solar cell member, the silicon type includes transparent electrodes such as tin oxide of a positive electrode, a silicon layer represented by a p-layer / i-layer / n-layer, and a metal of a negative electrode. Various members corresponding to a compound type, a dye-sensitized type, a quantum dot type, and the like are listed.

Moreover, as a member for a thin film secondary battery, for a lithium ion type, a positive electrode can be mentioned In addition to the above, transparent electrodes such as metals and metal oxides, lithium compounds in the electrolyte layer, metals in the current collector layer, and resins used as sealing layers can be used in addition to the nickel-hydrogen, polymer, and ceramic electrolytes. Various components such as models.

In addition, as a circuit for an electronic component, for a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), a metal of a conductive portion, silicon oxide or nitride of an insulating portion can be cited. In addition to the above, silicon and the like may include various members corresponding to various sensors such as a pressure sensor and an acceleration sensor, or various components such as a rigid printed circuit board, a flexible printed circuit board, and a rigid flexible printed circuit board.

(Order of steps)

The manufacturing method of the above-mentioned laminated body 24 with a member for an electronic device is not particularly limited, and depending on the type of the constituent member of the electronic device member, the second principal surface of the glass substrate 20 of the glass laminated body 100 is previously known by a known method. An electronic device member 22 is formed on 20b.

Furthermore, the electronic device member 22 may not be all the members (hereinafter referred to as "all members") that are finally formed on the second main surface 20b of the glass substrate 20, but may be a part of all members (hereinafter referred to as "partial members" "). The glass substrate with a part of the components peeled from the silicone resin layer 16 may also be made into a glass substrate with all the components (equivalent to the electronic device described below) in a subsequent step.

In addition, for a glass substrate with all the members peeled from the silicone resin layer 16, other members for electronic devices may be formed on the peeling surface (first main surface 20 a). Alternatively, the laminated body with all the members may be combined, and then the support substrate 18 with the resin layer may be peeled off from the laminated body with all the members to manufacture an electronic device. Furthermore, an electronic device may be assembled using two laminated bodies with all components, and then the two supporting substrates 18 with resin layers may be peeled off from the laminated body with all components, and an electronic device having two glass substrates may be manufactured.

For example, if the case of manufacturing an OLED is taken as an example, An organic EL structure is formed on the surface of the glass substrate 20 opposite to the polysiloxane layer 16 side (equivalent to the second main surface 20b of the glass substrate 20), and the following various layers are formed or processed to form a transparent electrode; Further, a hole injection layer is evaporated on the surface where the transparent electrode is formed. Hole transmission layer. Light emitting layer. Electron transport layer, etc .; forming a back electrode; and sealing using a sealing plate. Specific examples of such layer formation or treatment include a film formation treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate.

In the case of manufacturing a TFT-LCD, for example, the manufacturing method includes various steps such as a TFT forming step, a CF forming step, and a bonding step. The TFT forming step is a second step of the glass substrate 20 of the glass laminate 100. A thin film is formed on the surface 20b by patterning a metal film, a metal oxide film, and the like formed by a common film forming method such as a CVD (Chemical Vapor Deposition) method and a sputtering method using a resist solution. Transistor (TFT); The above CF formation step is on the second main surface 20b of the glass substrate 20 of another glass laminate 100, and a resist is used for pattern formation to form a color filter (CF); The step is to laminate the laminated body with TFT obtained in the TFT formation step and the laminated body with CF obtained in the CF formation step.

In the TFT formation step or the CF formation step, a TFT or CF is formed on the second main surface 20 b of the glass substrate 20 using a well-known photolithography technique or an etching technique or the like. In this case, a resist liquid can be used as a coating liquid for pattern formation.

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

In the bonding step, the thin-film transistor-forming surface of the multilayer body with TFT and the color filter of the multilayer body with CF are faced, and a sealant (for example, a UV-curable sealant for cell formation) is used. ). Thereafter, a liquid crystal material is injected into a cell formed by the laminated body with the TFT and the laminated body with the CF. Examples of the method for injecting the liquid crystal material include a reduced-pressure injection method and a dropwise injection method.

(Separation step)

As shown in FIG. 6 (B), the separation step uses the interface between the polysiloxane resin layer 16 and the glass substrate 20 as a peeling surface, and separates from the laminated body 24 with a member for an electronic device obtained in the above-mentioned member forming step into A step of laminating a glass substrate 20 (electronic device) having a member 22 for electronic devices and a supporting substrate 18 with a resin layer to obtain an electronic device 26 including the member 22 for electronic devices and the glass substrate 20.

In the case where the electronic device member 22 on the glass substrate 20 at the time of peeling is a part of all necessary constituent members, the remaining constituent members may be formed on the glass substrate 20 after separation.

The method of peeling the glass substrate 20 and the support substrate 18 with a resin layer is not specifically limited. Specifically, for example, a sharp blade can be inserted into the interface between the glass substrate 20 and the silicone resin layer 16 to give a starting point for peeling, and then blow off a mixed fluid of water and compressed air. Preferably, the supporting substrate 10 of the laminated body 24 with the member for the electronic device is set on the upper side, and the side of the member for the electronic device 22 is set on the lower plate, and the side of the member 22 for the electronic device is vacuum-adsorbed on the platen. (Sequentially when the two-area layer has a supporting substrate), in this state, the cutting tool is first made to penetrate the interface of the glass substrate 20-polysiloxane layer 16. Then, the support substrate 10 side is adsorbed by a plurality of vacuum adsorption pads, and the vacuum adsorption pads are sequentially raised from the vicinity of the position where the cutting tool is inserted. Thereby, an air layer is formed at the interface between the silicone resin layer 16 and the glass substrate 20 or the condensation damage surface of the silicone resin layer 16, and the air layer extends to the entire surface of the interface or the condensation damage surface, and can be easily peeled and supported. Substrate 10.

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

Furthermore, when the electronic device 26 is separated from the laminated body 24 with the components for the electronic device, by controlling the blowing or humidity using the ionizer, it is possible to further suppress the electrostatic adsorption of the fragments of the silicone resin layer 16 on the electronic device. 26 case.

The manufacturing method of the electronic device 26 described above is preferably applied to a mobile terminal such as a mobile phone or a PDA (Personal Digital Assistant). Manufacturing of small display devices. Display devices mainly include LCDs or OLEDs. As LCDs, they include TN (Twisted Nematic), STN (Super Twisted Nematic), FE (Ferroelectric), and TFT (Thin-film). A transistor (thin film transistor) type, a MIM (Metal-Insulator-Metal) type, an IPS (In-Plane Switching) type, a VA (Vertical Aligned) type, and the like. Basically, it can also be applied in the case of any one of a passive driving type and an active driving type display device.

Examples of the electronic device 26 manufactured by the above method include a panel for a display device having a glass substrate and a member for a display device, a solar cell having a member for a glass substrate and a solar cell, and a member for a secondary battery having a glass substrate and a thin film. Thin-film secondary batteries, electronic components including glass substrates, and components for electronic devices. The display device panel includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

[Example]

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

In the following examples and comparative examples, a glass plate (length 880 mm, width 680 mm, plate thickness 0.2 mm, linear expansion coefficient 38 × 10 ^-7 / ° C) made of alkali-free borosilicate glass was used. "AN100") as a glass substrate. And, as a supporting substrate, formed of the same alkali-free glass, boron silicate glass plate (length 920mm, width 730mm, thickness 0.5mm, a linear expansion coefficient 38 × 10 ^-7 / ℃, Asahi Glass Co., trade name " AN100 ").

<Example 1>

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

Next, using a die coater (coating speed: 40 mm / s, discharge amount: 8 ml), the following solution S was coated on the first main surface of the support substrate to contain uncured cross-linked organic polysilicon An oxyalkane layer (curable polysiloxane composition layer) is provided on a support substrate, and a support substrate with a curable layer (a coating amount of 20 g / m ² ) is obtained.

(Solution S)

As a component (A), a linear vinyl methyl polysiloxane (manufactured by Azmax, trade name "VDT-127", viscosity at 25 ° C: 700-800 cP (centipoise), organic polysiloxane Mol% of vinyl group in 1 mol: 0.325), linear methyl hydride polysiloxane as component (B) (manufactured by Azmax, trade name "HMS-301", viscosity at 25 ° C: 25-35 cP (Centipoise), the number of hydrogen atoms bonded to silicon atoms in one molecule: 8) The molar ratio of all vinyl groups to all hydrogen atoms bonded to silicon atoms (hydrogen atom / vinyl group) becomes 0.9 The mixture was mixed in such a manner that 1 part by mass of a silicon compound having an acetylene-based unsaturated group (boiling point: 120 ° C.) represented by the following formula (1) as a component (C) was mixed with 100 parts by weight of the siloxane mixture. .

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

Next, a platinum-based catalyst (made by Shin-Etsu Silicones Co., Ltd., trade name) is added so that the platinum metal concentration becomes 100 ppm based on the total amount of the component (A), the component (B), and the component (C). "CAT-PL-56") to obtain a mixed solution of an organic polysiloxane composition. Furthermore, 150 parts by weight of IP solvent 2028 (initial boiling point: 200 ° C, manufactured by Idemitsu Kosan Co., Ltd.) was added to 100 parts by weight of the obtained mixed solution to obtain a mixed solution.

Then, the support substrate with a hardenable layer is placed on the top of a plurality of support pins provided at the bottom of the heat treatment device. In addition, the top end of the support pin is in contact with the surface on the second main surface side of the support substrate (the side opposite to the side with the curable polysiloxane composition layer) of the support substrate with a hardening layer, and is on the support substrate. There is a region not in contact with the support pin on the second main surface side.

In the heat treatment device, a heating plate is arranged on the upper part of the hardening polysilicone composition layer of the supporting substrate with a hardening layer, and the hardening is performed at 200 ° C with the heating plate. The support substrate of the layer was heated (pre-baking heating) for 3 minutes.

Next, for the support substrate with a hardening layer after the above-mentioned heat treatment, a heating treatment (post-baking treatment) was performed at 250 ° C. for 1450 seconds, and a polysilicon with a thickness of 8 μm was formed on the first main surface of the support substrate. Oxygen resin layer.

Thereafter, the glass substrate and the polysiloxane resin layer on the support substrate were bonded by atmospheric pressure at room temperature to obtain a glass laminate A.

In the obtained glass laminated body A, the support substrate and the glass substrate were adhered to each other without generating bubbles between them and the silicone resin layer, without deformation defects, and smoothness was also good. Furthermore, in the glass laminate A, the peel strength at the interface between the silicone resin layer and the layer supporting the substrate is greater than the peel strength at the interface between the glass substrate layer and the silicone layer.

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

The water contact angle before and after the corona treatment of the second main surface of the supporting substrate in the glass laminate A was measured, and it was 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 corona treatment.

(Peel evaluation)

The glass laminate A was placed on a table mat in such a manner that a supporting substrate in the glass laminate A subjected to corona treatment was brought into contact with a urethane-made table mat. Then, the glass laminated body A was crimped to the table mat at 100 g / cm ² for 120 seconds. After the crimping, air and water are blown between the support substrate and the pad, and the two are peeled off as a result.

Furthermore, even when the processing speed in the corona treatment is changed to 1 m / min and 6 m / min, the same results as described above can be obtained.

<Comparative example 1>

Except that no corona treatment was performed, a glass laminated body B was obtained according to the same procedure as in Example 1 described above.

When the above-mentioned (peel evaluation) is performed using the glass laminate B instead of the glass laminate A, the glass laminate B cannot be peeled.

<Example 2>

In this example, the corona-treated glass laminate A obtained in Example 1 was used to manufacture an OLED.

First, on the second main surface of the glass substrate of the glass laminate A, silicon nitride, silicon oxide, and amorphous silicon were sequentially formed into a film by a plasma CVD method. Then, a low-concentration boron is implanted into the amorphous silicon layer by an ion doping device, 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, by using a photolithography etching and ion doping device, a low concentration of phosphorus is implanted into the amorphous silicon layer to form N-type and P-type TFT regions. Next, on the second main surface side of the glass substrate, a silicon oxide film is formed by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by a sputtering method, and a photolithography method is used. The gate electrode is formed by etching. Then, a photolithography method and an ion doping device are used to inject a high concentration of boron and phosphorus into each of the N-type and P-type required regions to form a source region and a drain region. Next, on the second main surface side of the glass substrate, an interlayer insulating film is formed by the formation of silicon oxide using a plasma CVD method, and aluminum is formed by a sputtering method, and etching by a photolithography method is used. A TFT electrode is formed. Then, in a hydrogen environment, heat treatment and hydrogenation treatment are performed, and then a passivation layer is formed by forming a silicon nitride film by a plasma CVD method. Next, an ultraviolet curable resin was applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole were formed by a photolithography method. Then, indium tin oxide was formed into a film by a sputtering method, and a pixel electrode was formed by etching using a photolithography method.

Next, on the second main surface side of the glass substrate, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was sequentially injected as a hole injection layer by a vapor deposition method. , Bis [(N-naphthyl) -N-phenyl] benzidine as a hole transport layer, and 2,6-bis as a light emitting layer in 8-hydroxyquinoline aluminum complex (Alq ₃ ) [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-1,5-dinitrile (BSN-BCN) at 40% by volume, and as an electron transport layer Alq _{3 was} formed into a film. Then, aluminum was formed into a film by a sputtering method, and a counter electrode was formed by etching using a photolithography method. Then, on the second main surface side of the glass substrate, an ultraviolet curing type was interposed therebetween. Next, another glass substrate is laminated and sealed. The organic EL structure is formed on the glass substrate by the above procedure. The glass laminate A (hereinafter, referred to as a panel A) having the organic EL structure on the glass substrate is The laminated body with the member for electronic devices of this invention.

Next, after vacuum-sealing the sealing body side of the panel A to the platen, a 0.1 mm thick stainless steel cutting tool was inserted into the interface between the glass substrate and the resin layer at the corner of the panel A, and the interface between the glass substrate and the resin layer was applied. The beginning of the divestiture. Then, the first main surface of the support substrate of the panel A is adsorbed by the vacuum adsorption pad, and then the adsorption pad is raised. Here, the cutting tool is inserted together with a self-ionizer (manufactured by KEYENCE) to blow a static-eliminating fluid toward the interface between the glass substrate and the resin layer. Then, the self-ionizer continued to blow the static-eliminating fluid into the formed gap, and injected water into the peeling front, while lifting the vacuum adsorption pad. As a result, only the glass substrate on which the organic EL structure was formed remained on the platen, and the supporting substrate with a resin layer could be peeled off.

Next, the separated glass substrate is cut using a laser cutter or a scribe-break method, and after being divided into a plurality of units, the glass substrate on which the organic EL structure is formed is combined with a counter substrate, and a module forming step is performed. And make OLED. The OLED obtained in the above manner has no problem in characteristics.

Although the present invention has been described in detail and with reference to specific embodiments, it is clear to practitioners that various changes or modifications can be added without departing from the spirit and scope of the present invention.

This application is based on Japanese Patent Application No. 2013-260453 filed on Dec. 17, 2013, and the contents are incorporated herein by reference.

Claims (9)

A manufacturing method of a glass laminated body is a manufacturing method of a glass laminated body having a supporting substrate, a polysiloxane resin layer, and a glass substrate in this order, and includes a heating step, which includes a first main surface and a first A support substrate of 2 main surfaces and a support substrate with a hardening layer of a curable polysiloxane composition layer disposed on the first main surface of the support substrate use a plurality of support substrates from the second main surface side of the support substrate. The support pin supports and heat-processes the above-mentioned support substrate with a hardening layer to form a polysiloxane resin layer; a lamination step is a step of laminating a glass substrate on the polysiloxane resin layer after the above-mentioned heating step; and a surface The processing step is after the above lamination step, or after the heating step and before the lamination step, at least the second main surface of the support substrate is selected from the group consisting of corona treatment, plasma treatment, and UV ozone treatment. At least one treatment in the group. The method for manufacturing a glass laminate according to claim 1, wherein the hardening polysiloxane composition layer includes at least an organic alkenyl polysiloxane having an alkenyl group and an organic hydrogen polymer having a hydrogen atom bonded to a silicon atom. Siloxane. For example, the method for manufacturing a glass laminate according to claim 1, wherein the heating step includes a first heating step in which a heating treatment is performed at a first temperature, and a heating treatment in a second temperature which is higher than the first temperature. The second heating step. For example, the method for manufacturing a glass laminate according to claim 2, wherein the heating step includes a first heating step in which a heating treatment is performed at a first temperature, and a heating treatment in a second temperature which is higher than the first temperature. The second heating step. For example, the method for manufacturing a glass laminated body according to claim 3, wherein the support substrate with a hardening layer is formed by applying a hardening polysiloxane composition containing a hardening polysiloxane and a solvent to the first support substrate. 1 is formed on the main surface, and the first temperature satisfies the initial boiling point of the solvent—30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C. The method for manufacturing a glass laminated body according to claim 4, wherein the support substrate with a hardening layer is formed by applying a hardening polysiloxane composition containing a hardening polysiloxane and a solvent to the above-mentioned first support substrate. 1 is formed on the main surface, and the first temperature satisfies the initial boiling point of the solvent—30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C. The method for manufacturing a glass laminate according to any one of claims 1 to 6, wherein a surface treatment step is performed after the above-mentioned lamination step. For example, the method for manufacturing a glass laminated body according to claim 7, wherein in the above-mentioned surface treatment step, a plurality of pairs including the high-voltage electrode and the ground electrode which are opposed to each other through the conveying path of the glass laminated body obtained through the above-mentioned laminating step. The electrode pairs are arranged along the conveying direction of the glass laminate, and the high-voltage electrode of one of the adjacent electrode pairs is disposed on one side across the conveying path, and the other high-voltage electrode is disposed on the opposite side. The other side of the conveying path, while carrying the glass laminate along the conveying path, applies high-frequency voltage to the high-voltage electrode, and performs corona treatment on the glass laminate. An electronic device manufacturing method including a member forming step of forming a member for an electronic device on a surface of the above-mentioned glass substrate of a glass laminated body manufactured by the manufacturing method according to any one of claims 1 to 8, And obtaining a laminated body with a member for an electronic device; and a separation step of removing the supporting substrate having the polysiloxane resin layer and the resinous layer with the supporting substrate from the laminated body with an electronic device member, and obtaining An electronic device of the glass substrate and the member for an electronic device.