TW201536710A - 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

Method for manufacturing glass laminate and method for manufacturing electronic device

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

In recent years, thinner and lighter devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCDs), and organic EL (Electroluminescence) panels (OLEDs) have been developed, and the glass used in such devices has been progressing. The thinning of the substrate is constantly evolving. If the strength of the glass substrate is insufficient due to thinning, the handleability of the glass substrate is lowered in the manufacturing process of the device.

Recently, in order to cope with the above-mentioned problems, a glass laminate in which a glass substrate and a reinforcing plate are laminated is prepared, and a member for an electronic device such as a display device is formed on a glass substrate of a glass laminate, and then the reinforcing plate is made of glass. The substrate is separated (for example, refer to Patent Document 1). The reinforcing plate has a supporting substrate and a polyoxyalkylene resin layer fixed to the supporting substrate, and the polyoxyxylene resin layer and the glass substrate are adhered to each other in a peelable manner. The reinforcing plate is peeled off at the interface between the polyoxygen resin layer of the glass laminate and the glass substrate, and the reinforcing plate separated from the glass substrate can be laminated with a new glass substrate to be reused as a glass laminate.

Further, there is a case where the glass laminate formed is subjected to a polishing treatment for polishing the surface of the glass substrate (Patent Document 2).

[Previous 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 in which a support substrate having a coating film on its surface is placed on top of a plurality of support pins and heated and dried is known.

When the inventors of the present invention have produced a reinforcing plate according to the method described in Patent Document 1, the support substrate on which the coating film of the polyoxyxylene resin layer is heated by the surface is placed on top of a plurality of support pins. After heating and drying to form a polyoxyxylene resin layer, a glass substrate was laminated on the polyoxynitride resin layer to prepare a glass laminate. Then, the support substrate side of the obtained glass laminate is oriented toward a specific substrate side, and the glass laminate is placed on a specific substrate, and the glass in the glass laminate is as described in Patent Document 1 or 2. A member for an electronic device is formed on the substrate, or a surface of the glass substrate is polished. Thereafter, when the glass laminate is to be removed from the 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, the productivity is lowered due to the long-term processing time, or the manufacturing yield of the electronic device is lowered.

The present invention has been made in view of the above-described problems, and an object of the invention is to provide a method for producing a glass laminate which is capable of producing a glass laminate which can be easily peeled off from the substrate after the support substrate side is placed on various substrates.

Moreover, an object of the present invention is to provide a method of manufacturing an electronic device using a glass laminate produced by the method for producing a glass laminate.

The inventors of the present invention have diligently studied 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 producing a glass laminate, which is a method for producing a glass laminate having a support substrate, a polyoxyxylene resin layer, and a glass substrate. Further, the method includes a heating step of attaching a curable layer comprising a support substrate having a first main surface and a second main surface, and a curable polyoxynitride composition layer disposed on the first main surface of the support substrate. The support substrate is supported by a plurality of support pins on the second main surface side of the support substrate, and the support substrate with the curable layer is subjected to heat treatment to form a polyoxymethylene resin layer; and the layer stacking step is performed after the heating step. a layer of the glass substrate on the epoxy resin layer; and a surface treatment step, after the step of laminating, or after the heating step and before the step of laminating, at least the second main surface of the supporting substrate is selected from the group consisting of corona treatment and plasma treatment And at least one of a group consisting of UV (Ultra Violet) ozone treatment.

In the first aspect, it is preferred that the hardenable polyoxynitride composition layer contains at least an alkenyl group-containing organic alkenyl polyoxyalkylene and an organic hydrogen polyoxynitrene having a hydrogen atom bonded to a deuterium atom. alkyl.

In the first aspect, the heating step preferably includes a first heating step of performing heat treatment at the first temperature and a second heating step of performing heat treatment at a second temperature higher than the first temperature.

In the first aspect, the support substrate with the curable layer is formed by applying a curable polysulfonium oxide composition containing a curable polyfluorene oxide and a solvent to the first main surface of the support substrate, and The first temperature is preferably such that the initial boiling point of the solvent is -30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C.

In the first aspect, it is preferred to carry out the surface treatment step after the lamination step.

In the first aspect, preferably, in the surface treatment step, the pair of electrodes including the high-voltage electrode and the ground electrode facing the transport path through which the glass laminate obtained in the step of stacking is transported is along the glass. The transport direction of the laminated body is arranged, and one of the adjacent electrode pairs is placed on one side of the transport path, and the other high voltage electrode is placed on the other side of the transport path. The glass laminate is transported along the transport path, and a high-frequency voltage is applied to the high-voltage electrode, and the glass laminate is applied to the glass laminate. Corona treatment.

A second aspect of the present invention provides a method of manufacturing an electronic device, comprising: a member forming step of forming an electronic device on a surface of a glass substrate of a glass laminate produced by the manufacturing method of the first aspect; a laminate for obtaining a member for an electronic device; and a separating step of removing a support substrate having a resin layer of a polyoxyxylene resin layer and a support substrate from a laminate of the member for an electronic device, thereby obtaining a glass An electronic device for a member for a substrate and an electronic device.

According to the present invention, there is provided a method for producing a glass laminate which can produce a glass laminate which can be easily peeled off from the substrate after the support substrate side is placed on various substrates.

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

10‧‧‧Support substrate

10a‧‧‧Support the second main surface of the substrate

12‧‧‧ hardened polysiloxane composition layer

14‧‧‧Support substrate with hardened layer

16‧‧‧Polyoxy resin layer

16a‧‧‧ Surface of the polyoxyl resin layer opposite to the support substrate side

18‧‧‧Support substrate with resin layer

20‧‧‧ glass substrate

20a‧‧‧1st main surface of the glass substrate

20b‧‧‧2nd main surface of the glass substrate

22‧‧‧Members for electronic devices

24‧‧‧Laminated body of components for electronic devices

26‧‧‧Electronic devices

50‧‧‧Support desk

52‧‧‧Support pins

60‧‧‧Corona treatment device

62‧‧‧1st high voltage electrode

64‧‧‧1st grounding electrode

66‧‧‧2nd high voltage electrode

68‧‧‧2nd ground electrode

70‧‧‧1st electrode pair

72‧‧‧2nd electrode pair

74‧‧‧Transport roller

76‧‧‧1st high frequency power supply

78‧‧‧2nd high frequency power supply

100‧‧‧glass laminate

X‧‧‧glass laminate

Fig. 1 is a flow chart showing the manufacturing steps of the first aspect of the method for producing a glass laminate according to the present invention.

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

Fig. 3 is a schematic view showing an arrangement state of a supporting substrate with a hardenable layer in a heating step.

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

Fig. 5 is a flow chart showing the manufacturing steps of the second aspect of the method for producing a glass laminate according to the present invention.

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

In the following, the preferred embodiments of the present invention are described with reference to the drawings, but the present invention is not limited to the following embodiments, and various embodiments may be applied in the following embodiments without departing from the scope of the invention. Change and replacement.

The inventors of the present invention have studied the above problems and found that after the heating step or after the production of the glass laminate (after the lamination step), the polyoxyn resin adheres to the second main surface (back surface) side of the support substrate, which is the problem described above. One of the reasons.

More specifically, in the heating step, one of the polyoxyxylene resin or a raw material thereof is partially volatilized, and the polyoxyxylene 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 oriented toward a specific substrate side and the glass laminate is placed on a specific substrate, the polysiloxane is present between the specific substrate and the support substrate in the glass laminate. The resin increases the peel strength of the specific substrate and the support substrate, and the two become difficult to peel off. Therefore, it has been found that the above 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 and removing the polyoxymethylene resin.

The method for producing a glass laminate according to the present invention includes a heating step of heat-treating a support substrate with a curable layer, a lamination step of laminating a glass substrate, and a surface treatment step of performing surface treatment. Further, the surface treatment step is performed after the above-described lamination step, or after the heating step and before the lamination step. Hereinafter, the former aspect will be described as a first aspect, and the latter aspect will be described as a second aspect.

<<The first aspect>>

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

Hereinafter, the materials used in the respective steps and their procedures will be described in detail. First, the heating step S102 will be described in detail.

<heating step>

The heating step S102 is a step of including a support substrate having a first main surface and a second main surface and a hardenable polyoxynitride composition layer disposed on the first main surface of the support substrate by a plurality of support pins. The support substrate with the curable layer is supported from the second main surface of the support substrate (the surface opposite to the side having the curable polyoxynitride composition layer), and the support substrate with the curable layer is subjected to heat treatment to form Polyoxygenated resin layer. More specifically, the step S102 is performed for the support substrate 14 including the support substrate 10 and the hardenable layer of the curable polyoxynitride composition layer 12 in FIG. 2(A), whereby FIG. 2 can be obtained ( B) A support substrate 18 including a resin-attached layer supporting the substrate 10 and the polyoxy-oxygen resin layer 16 as shown.

Hereinafter, the members and materials (supporting substrate and curable polyoxynitride composition layer) used in the step S102 will be described in detail below, and then the procedure of the step S102 will be described in detail.

(support substrate)

The support substrate 10 has two main surfaces of the first main surface and the second main surface, and cooperates with the polyoxyxene resin layer 16 described below to support and reinforce the glass substrate 20 described below. (Manufacturing Procedure of Member for Electronic Device) The deformation, damage, breakage, and the like of the glass substrate 20 during the manufacture of the member for electronic device are prevented. Moreover, in the case of using a glass substrate having a thickness smaller than that of the prior art, a glass laminate having the same thickness as the previous glass substrate can be used, and a manufacturing method suitable for the glass substrate of the previous thickness can be used in the member forming step or The manufacturing equipment is also one of the purposes of using the support substrate 10.

As the support substrate 10, for example, a glass plate, a plastic plate, a metal plate such as a SUS (Steel Use Stainless) plate, a ceramic plate, or the like can be used. In the case where the member forming step is accompanied by 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 support 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 than the glass substrate 20 or thinner than the glass substrate. Board 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 member forming step is designed to treat 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 the usual case.

When the support substrate 10 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons of easy handling and difficulty in damage. In addition, when the thickness of the glass plate is peeled off after the member for electronic device is formed, it is preferably 1.0 mm or less for the reason that the rigidity is moderately bent without being damaged.

The difference between the 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, more preferably 300 × 10 ^-7 / ° C or less, further preferably 200 × 10 ^-7 / ° C or less. When the difference is too large, the glass laminate is strongly bent during the heating and cooling in the member forming step, or the glass substrate 20 may be peeled off from the support substrate 18 with the resin layer described below. When the material of the glass substrate 20 is the same as the material of the support substrate 10, the above problem can be suppressed.

(hardened polyoxyl composition layer)

The layer of the curable polyoxynitride composition can form a layer of the composition of the polyoxyxylene resin layer in this step S102.

The curable polyoxynitride composition layer contains a curable polyfluorene which is hardened to form a polyoxyxylene resin. Such a sclerosing polyfluorene is classified into a condensation reaction type polyoxane, an addition reaction type polyoxane, an ultraviolet curing type polyfluorene oxygen, and an electron beam hardening type polyoxane according to the hardening mechanism thereof, and the above may be used. Any of the hardened polyfluorene oxides. Among these, an addition reaction type polyoxane is preferred. The reason for this is that the hardening reaction proceeds easily, and the degree of peeling property when the polyoxynoxy resin layer is formed is good, and the heat resistance is also high.

The addition reaction type polyoxo oxygen-based composition contains a main component and a crosslinking agent, and is hardened by the presence of a catalyst such as a platinum-based catalyst. Addition reaction type polyoxyl Promoted by heat treatment. The main component in the addition reaction type polyoxo is preferably an organic polyoxyalkylene having an alkenyl group (vinyl group or the like) bonded to a halogen atom (i.e., an organic alkenyl polyoxyalkylene; further, preferably It is a linear chain), and an alkenyl group etc. become a crosslinking point. The crosslinking agent in the addition reaction type polyoxo is preferably an organic polyoxyalkylene having a hydrogen atom (hydrogenated alkylene group) bonded to a halogen atom (that is, an organic hydrogen polyoxyalkylene; further, preferably It is linear), and a hydrogenated alkylene group or the like becomes a crosslinking point.

The addition reaction type polyoxymethylene is hardened by an addition reaction of a crosslinking point of a main agent and a crosslinking agent. Further, in terms of the more excellent heat resistance derived from the crosslinked structure, the molar ratio of the hydrogen atom of the organohydrogenpolyoxyalkylene bonded to the hydrogen atom of the halogen atom relative to the alkenyl group of the organic alkenyl polyoxyalkylene is further compared. Good for 0.5~2.

In the case where the curable polyfluorene oxide contained in the layer of the curable polydecane oxide composition is an addition reaction type polyoxane, the layer of the curable polyoxynium composition may further contain a catalyst (especially a platinum group metal system). Catalyst), or a reaction inhibitor.

A platinum group metal catalyst (a platinum group metal catalyst for hydrogenation) is used to carry out and promote the hydrogenation of an alkenyl group in the above organic alkenyl polyoxyalkylene and a hydrogen atom in the above organic hydrogen polyoxyalkylene. Catalyst for reaction. Examples of the platinum group-based catalyst include platinum-based, palladium-based, and lanthanide-based catalysts. In terms of economy and reactivity, it is particularly preferable to use a platinum-based catalyst.

The reaction inhibitor (reaction inhibitor for hydrazine hydrogenation) suppresses the catalytic activity of the above-mentioned catalyst (especially a platinum group metal catalyst) at normal temperature, and the life of the hardenable polyfluorene composition becomes long. Applicable period extender (also known as retarder). Examples of the reaction inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, hydrazine compounds, and organic chlorine compounds. It is especially preferred to be an acetylene compound (for example, a decyl alcohol and a decyl alcohol of an acetylene alcohol).

The method of forming the layer of the curable polyoxynitride composition on the support substrate is not particularly limited, and a known method can be employed. For example, a method of applying the above-described curable polyfluorene-containing curable polydecane oxide composition to a support substrate can be mentioned. Furthermore, the side to be coated The method is not particularly limited, and a known method can be employed. 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 curable polyoxynoxy composition, a solvent may also be included as needed. The solvent is preferably one which can easily dissolve various components and can be easily removed by volatilization. Specifically, for example, butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF (Tetrahydrofuran, tetrahydrofuran), chloroform or the like can be listed. In particular, a saturated hydrocarbon is used, and one or two or more kinds of various saturated hydrocarbons (linear saturated hydrocarbons, branched saturated hydrocarbons, and alicyclic saturated hydrocarbons) can be used as practical various saturated hydrocarbon solvents. For example, Isopar G (manufactured by Exxon Mobil Co., Ltd.), Isopar L (manufactured by Exxon Mobil Co., Ltd.), Isopar H (manufactured by Exxon Mobil Co., Ltd.), Isopar M (manufactured by Exxon Mobil Co., Ltd.), NORPAR 13 (Exxon Mobil Co., Ltd.) Made by the company), NORPAR 15 (manufactured by Exxon Mobil Co., Ltd.), Exxsol D40 (manufactured by Exxon Mobil Co., Ltd.), Exxsol D60 (manufactured by Exxon Mobil Co., Ltd.), Exxsol D80 (manufactured by Exxon Mobil Co., Ltd.), Neothiosol (Centralized Chemicals Co., Ltd.) Made by the company), IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.).

In the case where the step S102 is carried out in two stages as described below, it is preferred to use a solvent having an initial boiling point (at atmospheric pressure) of 210 ° C or less from the viewpoint that the solvent is easily volatilized in the first heating stage.

Further, the thickness of the layer of the curable polydecane oxide composition is not particularly limited, and may be appropriately adjusted so as to obtain a polyoxynitride resin layer having a preferable thickness as described below.

(order of steps)

In the step S102, the support substrate with the curable layer is supported by the second main surface side of the support substrate by a plurality of support pins, and the heat treatment is performed. That is, heating is performed while supporting the support substrate with the curable layer on the support pin. More specifically, as shown in Figure 3. The support substrate 14 with the curable layer is disposed on the top (top) of the plurality of support pins 52 arranged at intervals on the support table 50. In this state, the support substrate 14 with the curable layer is subjected to heat treatment. Further, the support pin 52 supports the second main surface 10a of the support substrate 10 in the support substrate 14 with the curable layer as shown in FIG.

Only three support pins 52 are illustrated in FIG. 3, but the number of support pins is not particularly limited, and may be 10 or more. Further, the arrangement position of the support pins 52 is not particularly limited, and may be arranged at a specific interval or may be randomly arranged. Further, the shape of the support pin 52 is not particularly limited, and may be any of a columnar shape, a polygonal shape, and the like.

Further, as shown in FIG. 3, the support pin 52 is partially in contact with one of the second main surface 10a sides of the support substrate 10, so that there is an area on the second main surface 10a side of the support substrate 10 that is not in contact with the support pin 52. .

The method of heat-treating the support substrate with the hardenable layer is not particularly limited as long as it can be heated in a state in which the support substrate of the hardenable layer is supported by the support pin, and for example, a support pin can be provided in the heating chamber. A known heat treatment device such as an oven. More specifically, a method of using a heat treatment apparatus including a heating plate (for example, a layer of a hardening polysiloxane composition layer in a support substrate provided with a curable layer on a support pin) is provided. A method of heating in a heating treatment device of a heating plate).

The heating conditions for thermally hardening the curable polyoxynitride composition layer are appropriately selected depending on the type of the curable polyfluorene oxide to be used. Among them, in terms of the hardening rate of the hardening polyoxygen oxide and the heat resistance of the formed polyoxynoxy resin layer, it is preferably carried out at 150 to 300 ° C (preferably 180 to 250 ° C) for 10 to 120 Heat treatment in minutes (preferably 30 to 60 minutes).

As a preferred aspect of the present step S102, it is preferred to carry out the heat treatment in two stages under different temperature conditions. That is, it is more preferable to include a step of performing heat treatment at the first temperature and a step of performing heat treatment at a second temperature higher than the first temperature. borrow When the heat treatment is performed in two stages, the surface of the polyoxyxene resin layer 16 formed is more excellent in surface area, and the adhesion to the glass substrate 20 to be described later is further improved. Further, when the heat treatment is performed in two stages, the first heating step and the second heating step may be performed by using different heat treatment apparatuses.

In addition, when the support substrate having the curable layer is formed by applying a curable polyadenine composition containing a curable polyfluorene oxide and a solvent to a support substrate, the solvent is more excellent in removability. While the surface of the layer of the curable polydecane oxide composition is flat and the decomposition of the hardenable polyfluorene is further inhibited, the first temperature is preferably from the initial boiling point of the solvent to -30 ° C to the initial distillation of the solvent. Point +30 ° C range. In other words, the first temperature preferably satisfies the following relational expression.

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

Further, the initial boiling point of the 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, more preferably 70 ° C or lower.

Further, the first temperature is preferably 210 ° C or lower. That is, it is preferable to include a first heating step of performing heat treatment at 210 ° C or lower and a second heating step of performing heat treatment at a temperature exceeding 210 ° C. When it is 210 ° C or less, the boiling of the solvent or the volatilization of the polyoxymethylene resin is further suppressed, and the surface of the formed polyoxynitride resin layer 16 is more excellent. Hereinafter, the first heating step and the second heating step under the above temperature conditions will be described in detail.

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

The second heating step is a so-called post-baking step which mainly promotes the hardening of the curable polyoxynitride composition layer 12 to form the polyoxynoxy resin layer 16. The temperature condition of the second heating step is preferably more than 210 ° C, and more preferably more than 210 ° C and not more than 250 ° C in terms of more excellent solvent removal and hardening reaction of the curable polyoxynitride composition layer 12 . The heating time is appropriately selected depending on the materials to be used, and is preferably from 10 to 120 minutes, more preferably from 30 to 60 minutes, in terms of productivity and solvent removal.

The polyoxynoxy resin layer 16 formed in the step S102 is fixed to one surface of the support substrate 10 by the hardening reaction of the curable polyoxynitride composition layer 12 on the support substrate 10, and is also peelable. The method is in close contact with the glass substrate 20 described below. The polyoxygenated resin layer 16 prevents the misalignment of the glass substrate 20 until the operation of separating the glass substrate 20 from the support substrate 10 is performed, and is prevented from being easily peeled off from the glass substrate 20 due to the separation operation, and the glass substrate 20 or the like is separated by the operation. damaged. Further, the polyoxyxene resin layer 16 is fixed to the support substrate 10, and the polyoxynitride resin layer 16 is not peeled off from the support substrate 10 during the separation operation, and the support substrate 18 with the resin layer can be obtained by a separation operation.

The surface of the polyoxyxene resin layer 16 that is in contact with the glass substrate 20 is detachably adhered to the first main surface of the glass substrate 20. In the present invention, the property of easily peeling off the surface of the polyoxyalkylene resin layer 16 is referred to as easy peelability (peelability).

In the present invention, there is a difference in peel strength (i.e., stress required for peeling) in the above-mentioned fixation and peelable adhesion, and fixing means that the peel strength is large with respect to the adhesion. Further, the term "peelable" means that it can be peeled off and peeled off without causing peeling of the surface to be fixed. Specifically, in the case where the glass substrate 20 and the support substrate 10 are separated from each other in the glass laminate of the present invention, it means that the surface to be adhered is peeled off, and the surface to be fixed is not peeled off. Therefore, in the glass laminate, if the operation of separating the glass substrate 20 from the support substrate 10 is performed, the glass laminate The body is divided into both the glass substrate 20 and the support substrate 18 with the resin layer.

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

The thickness of the polyoxyxene resin layer 16 is not particularly limited, but is preferably 2 to 100 μm, more preferably 3 to 50 μm, still more preferably 7 to 20 μm. When the thickness of the polyoxyxene resin layer 16 is in the above range, even if air bubbles or foreign matter are present between the polyoxynoxy resin layer 16 and the glass substrate 20, the occurrence of deformation defects of the glass substrate 20 can be suppressed. Further, when the thickness of the polyoxyxene resin layer 16 is too thick, it takes time and material to form, which is uneconomical and the heat resistance is lowered. Further, when the thickness of the polyoxyxene resin layer 16 is too small, the adhesion between the polyoxynated resin layer 16 and the glass substrate 20 may be lowered.

<Lamination step>

The laminating step S104 is a step of laminating the glass substrate 20 on the surface of the polyoxynated resin layer 16 obtained in the above step S102, thereby obtaining the support substrate 10, the polyoxyxene resin layer 16, and the glass substrate 20 in this order. The glass laminate 100. More specifically, as shown in FIG. 2(C), the surface 16a of the polyoxynitride 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 are formed. The first main surface 20a of 20 is an accumulation layer, and the polyoxy-oxygen resin layer 16 and the glass substrate 20 are laminated to obtain a glass laminate 100. Further, as described below, the obtained glass laminate 100 is subjected to the pre-treatment glass laminate before the surface treatment step S106 described below, and is presumed to be the polyoxyxene resin layer 16 of the support substrate 10 of the glass laminate 100. The surface of the opposite side (the second main surface 10a of the support substrate 10) is adhered with a polyoxyxylene resin or a raw material thereof.

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

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

For example, a method of laminating the glass substrate 20 on the surface of the polyoxyxene resin layer 16 under a normal pressure environment can be mentioned. Furthermore, it is also possible to overlap on the surface of the polyoxyxene resin layer 16 as needed. After the glass substrate 20, the glass substrate 20 is pressure-bonded to the polyoxyalkylene resin layer 16 using a roll or pressurization. It is preferable to remove bubbles which are mixed between the polyoxynoxy resin layer 16 and the glass substrate 20 by pressure bonding by a roll or pressurization.

When the polyoxyxylene resin layer 16 and the glass substrate 20 are pressure-bonded by a vacuum lamination method or a vacuum press method, it is more preferable to suppress the incorporation of air bubbles or to ensure good adhesion. There is also an advantage that, by pressure bonding under vacuum, even when minute bubbles remain, there is no case where bubbles grow due to heating, and deformation defects of the glass substrate 20 are hard to occur.

In the case of laminating the glass substrate 20, it is preferable to sufficiently wash the surface of the glass substrate 20 which is in contact with the polyoxynoxy resin layer 16, and to laminate it in an environment having a high degree of cleanliness. The higher the degree of cleanliness, the better the flatness of the glass substrate 20 becomes, which is preferable.

Further, after the laminated glass substrate 20 is laminated, a pre-annealing treatment (heat treatment) may be performed as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 20 to the polyoxynoxy resin layer 16 is improved, and the peel strength can be suitably obtained, and it becomes difficult to produce an electronic device in the member forming step described below. The dislocation of the components, etc., and the productivity of the electronic device is improved.

The conditions of the pre-annealing treatment are appropriately selected according to the kind of the polyoxyxene resin layer 16 to be used, and the peeling strength between the glass substrate 20 and the polyoxyxene resin layer 16 is made more appropriate. In other words, it is preferred to carry out heat treatment at a temperature of 300 ° C or higher (preferably 300 to 400 ° C) for 5 minutes or longer (preferably 5 to 30 minutes).

(glass substrate)

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

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

When the linear expansion coefficient of the glass substrate 20 is large, since the member forming step described below is 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 case where the glass substrate 20 on which the TFT is formed is cooled under heating, and the TFT is displaced due to heat shrinkage of the glass substrate 20. Become too big.

The glass substrate 20 is obtained by melting a glass raw material and shaping the molten glass into a plate shape. Such a molding method may be a usual one, and for example, a float method, a melting method, a flow down method, a rich method, a Luber method, or the like may be used. Further, in particular, the glass substrate 20 having a small thickness can be formed by heating a glass which is temporarily formed into a plate shape to a temperature at which it can be formed, and stretching by a method such as stretching to thin the glass (re-drawing method). And get.

The type of the glass of the glass substrate 20 is not particularly limited, and is preferably an alkali-free borosilicate glass, a borosilicate glass, a soda lime glass, a high cerium oxide glass, or another oxide-based glass containing cerium oxide as a main component. The oxide-based glass is preferably a glass having a content of cerium oxide in an amount of 40 to 90% by mass in terms of oxide.

As the glass of the glass substrate 20, a glass suitable for the type of the member for an electronic device or a manufacturing step thereof is used. For example, a glass substrate for a liquid crystal panel is likely to have an influence on liquid crystals due to elution of an alkali metal component, and therefore is composed of glass (alkali-free glass) containing substantially no alkali metal component (including a normal alkaline earth metal component). As described above, the glass of the glass substrate 20 is appropriately selected depending on the type of the apparatus to be applied and the manufacturing steps 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 viewpoint of thickness reduction and/or weight reduction of the glass substrate 20. When the thickness of the glass substrate 20 is 0.3 mm or less, the glass substrate 20 can be provided with good flexibility. 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.

Moreover, the thickness of the glass substrate 20 is preferably 0.03 mm or more for the reason that the production of the glass substrate 20 is easy and the operation of the glass substrate 20 is easy.

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

(glass laminate)

The glass laminate 100 has a laminate of the support substrate 10, the glass substrate 20, and the polyoxynoxy resin layer 16 present between the layers. The polyoxyxene resin layer 16 is in contact with the first main surface of the support substrate 10 on one surface thereof, and the other surface thereof is in contact with the first main surface 20a of the glass substrate 20.

This glass laminate 100 is used in the member forming step described below. In other words, the glass laminate 100 is used until a member for an electronic device such as a liquid crystal display device is formed on the surface of the second main surface 20b of the glass substrate 20. Thereafter, the glass laminate in which the member for electronic device is formed is separated into the support substrate 18 with the resin layer and the electronic device, and the support substrate 18 with the 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 the resin layer to be reused as a new glass laminate 100.

The interface between the support substrate 10 and the polyoxyxene resin layer 16 has a peel strength (x), and when a stress exceeding the peeling strength (x) in the peeling direction is applied to the interface between the support substrate 10 and the polyoxyxene resin layer 16, the support substrate is applied to the support substrate. Peeling occurs at the interface between the layer 10 and the polyoxyxene resin layer 16. The interface between the polyoxyxene resin layer 16 and the glass substrate 20 has a peeling strength (y). When a stress exceeding the peeling strength (y) in the peeling direction is applied to the interface between the polyoxynoxy resin layer 16 and the glass substrate 20, Peeling occurs at the interface between the oxygen resin layer 16 and the glass substrate 20.

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

That is, the polyoxyxene resin layer 16 is fixed to the support substrate 10 to form a support substrate 18 with a resin layer, and the glass substrate 20 is detachably adhered to the polyoxynoxy resin layer 16.

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 the relatively high adhesion to the glass substrate 20 after the heat treatment can be maintained.

The improvement of the adhesion of the polyoxyxene resin layer 16 to the support substrate 10 is achieved by forming the curable polyoxyxene composition layer 12 on the support substrate 10 to form a polyfluorinated oxygen as described above. Resin layer 16. The polyoxynitride resin layer 16 bonded to the support substrate 10 with a high bonding force can be formed by the adhesion force at the time of cross-linking hardening.

On the other hand, the bonding strength of the cured product of the curable polyoxynitride composition layer 12 to the glass substrate 20 is generally lower than that at the time of crosslinking hardening described above.

The glass laminate 100 can be used for various purposes, and examples thereof include the use of a panel for a display device, a PV, a film secondary battery, and an electronic component such as a semiconductor wafer on which a circuit is formed. Further, 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 panel for a display device includes an LCD, an OLED, an electronic paper, a plasma display panel, a field emission 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 is a step of performing a treatment selected from the group consisting of corona treatment, plasma treatment, and UV ozone treatment on at least the second main surface of the support substrate (the surface opposite to the side having the polyoxynitride resin layer). At least one of the groups. In the first aspect, the above-described treatment is intentionally performed on the second main surface of the support substrate in the glass laminate formed above. More specifically, the above is performed on the second main surface 10a of the support substrate 10 of FIG. 2(C) Reason. By performing this step S106, the polyoxyxylene resin which is volatilized at the heating step S102 and adhered to the second main surface 10a of the support substrate 10 or a raw material component thereof is removed, and the second main surface of the support substrate 10 is removed. 10a is clean. That is, by performing the above-described treatment on the glass laminate obtained in the above-mentioned lamination step S104, a treated glass laminate can be obtained. Further, in the step S106 described above, the above-described treatment may be performed together with the second main surface of the support substrate in the glass laminate and the exposed surface of the glass substrate in the glass laminate.

As the corona treatment (corona cleaning) performed in this step S106, a known corona treatment is performed. Further, the corona treatment is a surface treatment technique in which the surface of a treated substrate such as a plastic film, paper, or metal foil is modified by corona discharge irradiation. If the high frequency power supply device will oscillate at high frequencies. A high voltage is applied between the high voltage electrode and the ground electrode to generate a corona discharge.

The method of the corona treatment is not particularly limited. For example, it is preferable to apply a high voltage to a transfer roller supporting the glass laminate and a counter electrode disposed therebetween, and to perform corona discharge during this period. The glass laminate is sequentially moved to perform surface treatment. Specific examples of the corona treatment device include a high-frequency power source (high-frequency oscillator), a high-voltage transformer, and a discharge electrode, and a device for transporting a glass laminate is attached to the front and rear sides thereof. The frequency of the high-frequency oscillator is not particularly limited, and is, for example, preferably 0.1 to 100 kHz, preferably about 0.5 to 50 kW. The conveying speed (treatment speed) of the glass laminate is not particularly limited, but is preferably 1 to 10 m/min.

Further, in the case where the surface treatment step S106 is performed after the step S104, it is preferable to use the corona treatment device described below.

Fig. 4 is a side view showing an embodiment of a 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 arranged to face each other with a predetermined interval therebetween, and the first electrode pair 70 is formed, and the first high voltage electrode 62 and the first ground electrode are formed. A discharge space is formed between 64. Further, the second high voltage electrode 66 and the second ground electrode 68 are disposed to face each other with a predetermined interval therebetween to form the 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 transported along the glass laminate X having the support substrate, the polyoxyn resin layer, and the glass substrate obtained in the step S104. The direction is adjacent to the configuration. Further, as shown in FIG. 4, the glass laminate X is transported by the transport roller 74, and between the first high voltage electrode 62 and the first ground electrode 64, and between the second high voltage electrode 66 and the second ground electrode 68. Move between.

Further, the first high voltage electrode 62 is connected to the first high frequency power source 76 to apply a high frequency voltage. Further, the second high voltage electrode 66 is connected to the second high frequency power source 78 to apply a high frequency voltage. Further, in FIG. 4, both the first high-frequency power source 76 and the second high-frequency power source 78 are used. However, the first high-frequency power source 76 and the second high-frequency power source 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 disposed on the upper side (one side) and the lower side (the other side) of the path (transport path) through which the glass laminated body X is conveyed in FIG. 4 . In other words, the first high voltage electrode 62 and the second high voltage electrode 66 are alternately arranged along the transport direction of the glass laminate X.

When the glass laminate X is transported to the corona treatment apparatus 60 by the transport roller 74, the first high voltage electrode 62 and the second high voltage electrode 66 are disposed on one side of the transport path of the glass laminate X and the other. On the side, it is possible to efficiently corona treat both sides of the glass laminate X to be conveyed. In other words, the second main surface of the support substrate in the glass laminate X (the surface opposite to the side of the polyoxymethylene resin layer) and the exposed surface of the glass substrate (the surface opposite to the side of the polyoxymethylene resin layer) can be used. Corona treatment is implemented.

Further, the preferable range of the conditions of the high-frequency power source or the conveying speed (processing speed) of the glass laminate X is as described above.

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

Further, when it is desired to strongly perform the corona treatment on only one side surface of the glass laminate X (the second main surface of the support substrate), the first high voltage electrode 62 and the second high voltage electrode 66 may be arranged together. The upper side or the lower side of the formula.

Further, in FIG. 4, a 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.

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 can be used, but in order to stably perform corona treatment Preferably, at least one of the first high voltage electrode 62 and the first ground electrode 64 disposed oppositely, and at least one of the second high voltage electrode 66 and the second ground electrode 68 disposed opposite each other are dielectric bodies. Covered. More preferably, both 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 are covered with a dielectric. Thereby, the distance between the high voltage electrode and the ground electrode can be increased, and the glass laminate X can be easily conveyed stably.

In addition, as the electrode (dielectric coated electrode) covered with the dielectric material, a ceramic electrode obtained by coating ceramic or the like on the surface of a conductive core material such as a metal such as stainless steel or aluminum is preferable. Usually, when a resin film is subjected to corona treatment, a rubber electrode obtained by coating a rubber material for a metal core material can be used as a dielectric coating electrode, but the diameter is relatively large due to the relationship between weight and rigidity. In the case where the corona treatment apparatus 60 is increased in size, there is a gap between the conveyance rollers, which causes a problem when the thin glass laminate X is conveyed. Since the ceramic electrode is light in weight and high in rigidity, the diameter is smaller than that of the rubber electrode, so that it is difficult to cause the above problem.

Further, in the rubber electrode, since the rubber film is easily damaged by the discharge, it is difficult to fix the electrode and use it. Therefore, a rotation mechanism is provided on the rubber electrode, and it is usually used while rotating, but there is a problem that the device is complicated and large. Regarding the ceramic electrode, it is difficult to damage even if the discharge is repeated at the same position, so it is not necessary to provide the above-described rotating machine. Structure.

The plasma treatment (plasma washing) has atmospheric pressure (or atmospheric pressure) plasma treatment and low pressure low temperature plasma treatment.

In the normal piezoelectric slurry treatment, discharge energy is applied to the gas, and it is released under normal pressure to generate plasma. As a feature thereof, it is not necessary to use a vacuum because of a normal pressing process, and the apparatus is simple and the productivity is also high. As a mode, there are mainly a normal gas slurry of a rare gas system and a pulse type normal piezoelectric slurry which performs a glow discharge by applying a voltage, and any of the above methods can be used.

In the low-pressure low-temperature plasma treatment, the glass laminate is passed through a decompressible low-temperature plasma processing apparatus to make the inside of the apparatus an inorganic gas atmosphere, and the pressure is maintained at 0.001 to 10 Torr, preferably 0.01 to 1 Torr. A power of 50 Hz to 13.6 MHz is applied between the lower electrodes. Glow discharge is performed by applying electric power of 0.1 to 50 kW, and low temperature plasma of inorganic gas is generated. A glass laminate is provided therein to process the support substrate. In the case where the glass laminate is continuously treated, the glass laminate is sequentially moved to face the surface for plasma treatment. As the inorganic gas, a rare gas such as helium, neon or argon, oxygen, nitrogen, air, carbon dioxide gas, ammonia or the like can be used. These gases are not limited to one type, and may be a mixture of two or more kinds of gases.

In any of the treatments of the normal piezoelectric slurry treatment and the low pressure low temperature plasma treatment, the plasma treatment time is preferably from 0.1 to 1,000 seconds, more preferably from 1 to 100 seconds.

The UV ozone treatment is a treatment in which UV (ultraviolet light) is irradiated to make oxygen in the air into ozone, and the irradiated surface is cleaned by the ozone and ultraviolet rays.

The UV light source is not particularly limited as long as it can turn oxygen into ozone by UV irradiation. As the UV light source, a low pressure mercury lamp can be cited. The low pressure mercury lamp produces UV light at 185 nm and 254 nm, and the 185 nm line converts oxygen into ozone. The illuminance at the time of irradiation differs depending on the light source used, and is usually tens to hundreds of mW/cm ² . Further, the illuminance can be changed by collecting or diffusing. The irradiation time varies depending on the illuminance of the lamp and the type of the untreated layer, and is usually from 1 minute to 24 hours. The treatment temperature is usually 10 to 200 °C. 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 the above-described step S106, the adhering matter adhering to the second main surface 10a side of the support substrate 10 is removed.

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

<<The second aspect>>

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

The steps of the first aspect described above are the same as those of the first aspect except that the order of the surface treatment step S106 is different from that of the first aspect described above. More specifically, in the second aspect, the support substrate with the resin layer is produced in the heating step S102, and then the surface treatment is performed on the second main surface side of the support substrate in the support substrate with the resin layer ( For example, corona treatment), thereafter, a glass substrate is laminated on the polyoxynitride resin layer in the support substrate with the resin layer to obtain a glass laminate. The desired glass laminate can also be obtained in this embodiment.

Further, when the first aspect is compared with the second aspect, the first aspect is preferable. In the case of the first aspect, since the glass substrate is laminated before the surface treatment step S106 after the formation of the polyoxynoxy resin layer, impurities are less likely to adhere to the polyoxymethylene resin layer, and the adhesion of the glass substrate is further improved.

An electronic device (a glass substrate including a glass substrate and an attached member of the member for an electronic device) is produced by using the glass laminate obtained in the first aspect and the second aspect described above. Further, the glass substrate of the glass laminate is subjected to a polishing treatment as needed.

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

<grinding step>

The polishing step is a step of polishing the second main surface 20b of the glass substrate 20 in the obtained glass laminate 100. By providing this step, minute irregularities and damage of the second main surface 20b of the glass substrate 20 can be removed, and the flatness of the surface for forming the electronic device member can be improved. Therefore, the reliability of the electronic device as a product can be improved. This effect is remarkable for the 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 separately, and it is difficult to perform polishing before the production of the glass laminate 100.

The method of grinding is not particularly limited, and a known method can be employed, and mechanical polishing (physical polishing) or chemical polishing (chemical polishing) can be used. As the mechanical polishing, a sandblasting method in which ceramic abrasive grains are blown and a polishing method, a polishing using a polishing sheet or a grindstone, and a chemical mechanical polishing (CMP) method in which abrasive grains and a chemical solvent are used in combination can be used.

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

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

<Electronic device (glass substrate with attached members) and method of manufacturing the same>

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 produced by using the above-described glass laminate.

The method of manufacturing the electronic device is not particularly limited, and in terms of excellent productivity of the electronic device, it is preferable to form an electronic device by forming a member for an electronic device on a glass substrate in the glass laminate. Multilayered oxygen The glass substrate side interface of the resin layer is a peeling surface, and is separated into a supporting substrate of an electronic device and a resin-attached layer from the laminated body of the obtained electronic device member.

In the following, a step of forming a laminate for a member for an electronic device on a glass substrate in the glass laminate is referred to as a member forming step, and the glass substrate side interface of the polyoxyxene resin layer is peeled off. The step of separating the laminated body of the member for electronic device into the supporting substrate of the electronic device and the resin-attached layer is referred to as a separating step.

Hereinafter, the materials and procedures used in the respective steps will be described in detail.

(component forming step)

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

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

(Mechanical components (functional components))

The electronic device member 22 is formed on the glass substrate 20 in the glass laminate 100 and is a member constituting at least a part of the electronic device. More specifically, the electronic device member 22 may be a member for use in 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, a member for a display device) , a member for a solar cell, a member for a film secondary battery, and a circuit for an electronic component).

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

Further, as a member for a film secondary battery, a positive electrode is exemplified for the lithium ion type. And a transparent electrode such as a metal or a metal oxide of a negative electrode, a lithium compound of an electrolyte layer, a metal of a collector layer, a resin as a sealing layer, and the like, in addition to the above, may also be a nickel-hydrogen type, a polymer type, or a ceramic electrolyte. Various types of components, etc.

Further, as a circuit for an electronic component, a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor) includes a metal of a conductive portion and yttrium oxide or nitridation of an insulating portion. In addition to the above, various members such as various sensors such as a pressure sensor and an acceleration sensor, or a rigid printed circuit board, a flexible printed circuit board, and a rigid flexible printed circuit board may be used.

(order of steps)

The manufacturing method of the laminated body 24 of the member for electronic devices described above is not particularly limited, and the second main surface of the glass substrate 20 of the glass laminate 100 is formed by a conventionally known method depending on the type of the constituent members of the electronic device member. A member 22 for an electronic device is formed on 20b.

In addition, the electronic device member 22 may not be the entire member (hereinafter referred to as "all members") of the second main surface 20b of the glass substrate 20, and may be one part of all members (hereinafter referred to as "partial member" "). The glass substrate with the member attached to the polyoxyxene resin layer 16 may be formed into a glass substrate (corresponding to an electronic device described below) with all the members in the subsequent step.

Moreover, the glass substrate with all the members which are peeled off from the polyoxynoxy resin layer 16 may be formed with other electronic device members on the peeling surface (first main surface 20a). Moreover, the laminated body with all the members may be combined, and thereafter, the laminated body with the resin layer may be peeled off from the laminated body of all the members to manufacture an electronic device. Further, an electronic device can be assembled by using two laminated bodies with all the members, and then the laminated body with the resin layers removed from the laminated body of all the members, and an electronic device having two glass substrates can be manufactured.

For example, if the case of manufacturing an OLED is taken as an example, for the glass laminate 100 An organic EL structure is formed on a surface of the glass substrate 20 opposite to the side of the polyoxyxene resin layer 16 (corresponding to the second main surface 20b of the glass substrate 20), and various layers are formed or processed to form a transparent electrode; Further, a hole injection layer is deposited on the surface on which the transparent electrode is formed. Hole transport layer. Luminous layer. An electron transport layer or the like; a back electrode; and a sealing plate for sealing or the like. Specific examples of the formation or treatment of the layers include a film formation treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate.

Further, for example, in the case of manufacturing a TFT-LCD, the manufacturing method has various steps such as a TFT forming step, a CF forming step, and a bonding step, and the TFT forming step is applied to the second main member of the glass substrate 20 of the glass laminate 100. On the surface 20b, a metal film and a metal oxide film formed by a usual film formation method such as a CVD (Chemical Vapor Deposition) method or a sputtering method are used to form a film by using a resist liquid. a TFT (TFT); the CF forming step is performed on the second main surface 20b of the glass substrate 20 of the other glass laminate 100, and the resist liquid is used for pattern formation to form a color filter (CF); In the step, the laminated body of the TFT obtained in the TFT forming step and the laminated body of the CF obtained in the CF forming step are laminated.

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

Further, before forming the TFT or the CF, the second main surface 20b of the glass substrate 20 may be washed as needed. As the washing method, a dry cleaning or a wet washing which is well known can be used.

In the bonding step, the thin film transistor forming surface of the laminated body with the TFT is formed to face the color filter of the laminated body with CF, and a sealing agent is used (for example, an ultraviolet curing type sealing agent for cell formation) ) to make a fit. Thereafter, a liquid crystal material is injected into a cell formed of a laminate body with TFTs and a laminate body with CF. As a method of injecting a liquid crystal material, for example, a pressure reduction injection method or a dropping injection method is available.

(separation step)

In the separation step, as shown in FIG. 6(B), the interface between the polyoxyxene resin layer 16 and the glass substrate 20 is a peeling surface, and the laminated body 24 of the member for electronic device obtained in the above-described member forming step is separated into The glass substrate 20 (electronic device) of the electronic device member 22 and the support substrate 18 with the resin layer are laminated to obtain the electronic device 26 including the electronic device member 22 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 polyoxyxene resin layer 16, and after the origin of the peeling is given, the mixed fluid of water and compressed air is blown and peeled off. It is preferable that the support substrate 10 of the laminated body 24 for the electronic device-attached member is placed on the upper side, the electronic device member 22 side is placed on the pressure plate, and the electronic device member 22 side is vacuum-adsorbed to the pressure plate. (In the case where the two-layer layer has a supporting substrate, it is sequentially performed), and in this state, the blade is first invaded into the interface of the glass substrate 20-polyoxyalkylene resin layer 16. Then, the support substrate 10 side is adsorbed by a plurality of vacuum adsorption pads, and the vacuum adsorption pad is sequentially raised from the vicinity of the insertion blade. Thereby, an air layer is formed at the interface between the polyoxyxene resin layer 16 and the glass substrate 20 or the agglomerated damaged surface of the polyoxyxene resin layer 16, and the air layer spreads to the entire surface of the interface or the agglomerated damaged surface, and can be easily peeled off and supported. Substrate 10.

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

Further, when the electronic device 26 is separated from the laminated body 24 of the self-contained electronic device member, it is possible to suppress the electrostatic adsorption of the fragments of the polyoxynoxy resin layer 16 to the electronic device by controlling the blowing or humidity by the ionizer. 26 cases.

The manufacturing method of the electronic device 26 described above is preferably used by a mobile terminal such as a mobile phone or a PDA (Personal Digital Assistant). Manufacturing of small display devices. Display devices mainly include LCD or OLED, and as LCD, including TN (Twisted Nematic), STN (Super Twisted Nematic), FE (Ferroelectric), TFT (Thin-film) Transistor, thin film transistor type, MIM (Metal-Insulator-Metal), IPS (In-Plane Switching) type, VA (Vertical Aligned) type, and the like. It can also be applied basically in the case of any of the passive driving type and the active driving type.

The electronic device 26 manufactured by the above method includes a panel for a display device having a member for a glass substrate and a display device, a solar cell having a member for a glass substrate and a solar cell, and a member for a glass substrate and a secondary battery. A film secondary battery, an electronic component having a glass substrate and a member for an electronic device, and the like. The panel for a display device 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 specifically described by way of examples, but the present invention is not limited by the examples.

In the following examples and comparative examples, a glass plate composed of an alkali-free borosilicate glass (length 880 mm, width 680 mm, thickness 0.2 mm, linear expansion coefficient 38×10 ^-7 /° C., manufactured by Asahi Glass Co., Ltd., was used. The name "AN100" is used as a glass substrate. Further, as the support substrate, the same glass plate (length 920 mm, width 730 mm, plate thickness 0.5 mm, linear expansion coefficient 38×10 ^-7 /° C., manufactured by Asahi Glass Co., Ltd., trade name) was used. AN100").

<Example 1>

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

Then, using a die coater (coating speed: 40 mm/s, discharge amount: 8 ml), the following solution S was applied to the first main surface of the support substrate to form an unhardened crosslinkable organic polyfluorene. The layer of the oxyalkylene (hardenable polyoxynitride composition layer) was provided on the support substrate to obtain a support substrate (coating amount: 20 g/m ² ) having a curable layer.

(solution S)

Linear linear methyl polysiloxane (component A), manufactured by Azmax Co., Ltd., trade name "VDT-127", viscosity at 25 ° C: 700-800 cP (centipoise), organic polyoxymethane The mol% of the vinyl group in 1 mol: 0.325), the linear methyl hydrogenated polyoxyalkylene as the component (B) (manufactured by Azmax, trade name "HMS-301", viscosity at 25 ° C: 25-35 cP (centipoise), the number of hydrogen atoms bonded to the deuterium atom in one molecule: 8) The molar ratio (hydrogen atom/vinyl group) of all the hydrogen atoms bonded to all the hydrogen atoms of the deuterium atom becomes 0.9. In this manner, 1 part by mass of the oxime compound having an acetylene-based unsaturated group (boiling point: 120 ° C) represented by the following formula (1) as the component (C) is mixed with 100 parts by weight of the mixture of the oxirane. .

HC≡CC(CH ₃ ) ₂ -O-Si(CH ₃ ) ₃ (1)

Then, a platinum-based catalyst (manufactured by Shin-Etsu Silicones Co., Ltd., trade name) was added to the total amount of the component (A) and the component (B) and the component (C) in a platinum equivalent of platinum. "CAT-PL-56") was obtained as a mixture of organopolyoxane compositions. 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 liquid to obtain a mixed solution.

Then, the support substrate with the curable layer is placed on the tip end of a plurality of support pins provided at the bottom of the heat treatment apparatus. Further, the tip end of the support pin is in contact with the surface of the second main surface side (the side opposite to the side having the curable polyoxynitride composition layer) of the support substrate in the support substrate with the curable layer, and is supported on the substrate. There is a region on the second main surface side that is not in contact with the support pin.

In the heat treatment apparatus, a heating plate is disposed on the upper portion of the curable polyoxynitride composition layer of the support substrate with the curable layer, and the curing plate is cured at 200 ° C. The support substrate of the layer was heated (prebake heating) for 3 minutes.

Then, the support substrate having the curable layer after the heat treatment was further subjected to a heat treatment (post-baking treatment) at 250 ° C for 1,450 seconds, and a polyethylene having 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 polyoxymethylene resin layer on the support substrate were bonded together by atmospheric pressure at room temperature to obtain a glass laminate A.

In the obtained glass laminate A, the support substrate and the glass substrate were adhered to each other without generating bubbles between the polyoxymethylene resin layer, and there was no deformation defect, and the smoothness was also good. Further, in the glass laminate A, the peel strength at the interface between the layer of the polyimide layer and the layer of the support substrate is larger than the peel strength at the interface between the layer of the glass substrate and the layer of the polyimide resin layer.

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

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

(peeling evaluation)

The glass laminate A was placed on a table mat in such a manner that the support substrate in the glass laminate A subjected to the corona treatment was brought into contact with the urethane-made mat. Then, the glass laminate A was pressure-bonded to the mat at 100 g/cm ² for 120 seconds. After the pressure bonding, air and water are blown between the support substrate and the table mat, and both are peeled off, and as a result, peeling can be performed.

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

<Comparative Example 1>

The glass laminate B was obtained in the same manner as in the above Example 1 except that the corona treatment was not carried out.

When the glass laminate B is used instead of the glass laminate A to perform the above (peel evaluation), the glass laminate B cannot be peeled off.

<Example 2>

In this example, an OLED was produced using the corona-treated glass laminate A obtained in Example 1.

First, on the second main surface of the glass substrate of the glass laminate A, tantalum nitride, ruthenium oxide, and amorphous ruthenium are sequentially formed by a plasma CVD method. Then, boron of a low concentration is injected into the amorphous germanium layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to carry out dehydrogenation treatment. Then, the crystallization treatment of the amorphous germanium layer is performed by a laser annealing device. Then, by using a photolithography etching and ion doping apparatus, a low concentration of phosphorus is implanted into the amorphous germanium layer to form N-type and P-type TFT regions. Then, on the second main surface side of the glass substrate, a ruthenium oxide film is formed by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by sputtering to form a film by using a photolithography method. The etching is performed to form a gate electrode. Then, by using a photolithography method and an ion doping apparatus, a high concentration of boron and phosphorus is implanted into a desired region of each of the N-type and the P-type to form a source region and a drain region. Then, on the second main surface side of the glass substrate, an interlayer insulating film is formed by film formation of cerium oxide by a plasma CVD method, and aluminum is formed by sputtering, and etching by photolithography is performed. And a TFT electrode is formed. Then, after performing a hydrogenation treatment in a hydrogen atmosphere, a passivation layer is formed by film formation of tantalum nitride by a plasma CVD method. Then, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Then, indium tin oxide is formed into a film by sputtering, and a pixel electrode is formed by etching using photolithography.

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

Then, after the sealing body side of the panel A is vacuum-adsorbed to the platen, a stainless steel blade having a thickness of 0.1 mm is 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 is imparted. The starting point of stripping. 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 insertion of the blade is performed by blowing an electrostatic fluid to the interface between the glass substrate and the resin layer from an ionizer (manufactured by KEYENCE Co., Ltd.). Then, the ionizer continues to blow the neutralizing fluid to the formed voids, and injects water into the stripping front while lifting the vacuum adsorbing pad. As a result, only the glass substrate on which the organic EL structure is formed remains on the platen, and the support substrate with the resin layer can be peeled off.

Then, the separated glass substrate is cut by a laser cutting or scribing-breaking method, and divided into a plurality of units, and then the glass substrate on which the organic EL structure is formed is combined with the counter substrate, and the module forming step is performed. And making OLED. The OLED obtained in the above manner has no problem in characteristics.

The present invention has been described in detail with reference to the specific embodiments thereof.

The present application is based on Japanese Patent Application No. 2013-260453 filed on Dec.

Claims (7)

A method for producing a glass laminate, which comprises a method for producing a glass laminate comprising a support substrate, a polyoxyxene resin layer and a glass substrate, and comprising: a heating step comprising: having a first main surface and a first The supporting substrate of the main surface and the supporting substrate of the curable layer disposed on the first main surface of the supporting substrate on the first main surface are used from the second main surface side of the supporting substrate Supporting the support of the pin, heat-treating the support substrate with the hardenable layer to form a polyoxyxylene resin layer; and stacking the layer, after the heating step, laminating the glass substrate on the polyoxyxylene resin layer; and surface The processing step is performed after the step of laminating, or after the heating step and before the laminating 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 of the constituent groups. The method for producing a glass laminate according to claim 1, wherein the hardenable polyoxynitride composition layer contains at least an alkenyl group-containing organic alkenyl polysiloxane and an organic hydrogen group having a hydrogen atom bonded to a germanium atom. Oxane. The method for producing a glass laminate according to claim 1 or 2, wherein the heating step sequentially includes a first heating step of performing heat treatment at a first temperature, and heating at a second temperature higher than the first temperature. The second heating step of the treatment. The method for producing a glass laminate according to claim 3, wherein the support substrate with the curable layer is coated on the support substrate by a curable polyoxyl composition comprising a curable polyfluorene oxide and a solvent. 1 is formed on the main surface, and the first temperature satisfies the initial boiling point of the solvent -30 ° C ≦ first temperature 初 the initial boiling point of the solvent + 30 ° C. The method for producing a glass laminate according to any one of claims 1 to 4, wherein the surface treatment step is carried out after the step of laminating. The method for producing a glass laminate according to claim 5, wherein in the surface treatment step, the plurality of pairs are provided with a high-pressure electrode and a ground electrode which are opposed to each other by a transport path through which the glass laminate obtained in the stacking step is transported The electrode pairs are arranged along the transport direction of the glass laminate, and the high voltage electrode of one of the adjacent electrode pairs is disposed on one side of the transport path, and the other high voltage electrode is placed on the other side. On the other side of the transport path, the glass laminate is transported along the transport path, and a high-frequency voltage is applied to the high-voltage electrode, and the glass laminate is subjected to corona treatment. A method of manufacturing an electronic device, comprising: a member forming step of forming a member for an electronic device on a surface of the glass substrate of the glass laminate produced by the manufacturing method according to any one of claims 1 to 6, And obtaining a laminate of the member for an electronic device; and a separating step of removing the support substrate having the resin layer of the polyoxynoxy resin layer and the support substrate from the laminate of the member for an electronic device; The glass substrate and the electronic device of the above-described electronic device member.