TWI580566B - A manufacturing method of an electronic device, and a method for manufacturing a glass laminate - Google Patents

Description

Method for manufacturing electronic device and method for manufacturing glass laminate

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

In recent years, devices such as solar cells (PV, photovoltaic), liquid crystal panels (LCD), organic EL (Electro Luminescence) panels (OLED, Organic Light Emitting Diode) The thinner and lighter (electronic devices) are progressing, and the thinning of the glass substrates used in these devices is progressing. If the strength of the glass substrate is insufficient due to thinning, the glass substrate is rationally lowered in the manufacturing process of the device.

Therefore, a method of thinning a glass substrate by a chemical etching treatment after forming a device member (for example, a thin film transistor) on a glass substrate having a thicker final thickness has been widely used. However, in this method, for example, when the thickness of one glass substrate is thinned from 0.7 mm to 0.2 mm or 0.1 mm, since most of the material of the original glass substrate is etched by the etching liquid, the production is performed. The viewpoint of the efficiency of use of sex or raw materials is not good.

Further, in the thinning method of the glass substrate by chemical etching, there is a case where there is a slight damage on the surface of the glass substrate, and a fine pit (etching hole) is formed as a starting point from the damage by the etching treatment to become an optical defect. Happening.

Recently, in order to cope with the above problems, it has been proposed to laminate a thin-plate glass substrate and a reinforcing plate, and to form a display device on a thin-plate glass substrate of a laminate, and then strengthen it. A method of separating a plate from a thin glass substrate (for example, refer to Patent Document 1). The reinforcing plate has a supporting substrate and a resin layer fixed to the supporting substrate, and the resin layer and the thin glass substrate are detachably adhered. The reinforcing plate from which the interface between the resin layer of the laminate and the thin glass substrate is separated from the thin glass substrate can be laminated with a new thin glass substrate to be reused in the form of a laminate.

On the other hand, as described in paragraph [0084] of Patent Document 2, if the surface of the glass has an undulation of more than 0.100 μm, it is difficult to accurately pattern the circuit electrode or the like formed on the surface thereof, and as a result, the circuit The probability of electrode disconnection and short circuit increases, the yield of electronic devices such as liquid crystal displays decreases, and it is difficult to ensure reliability.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 07/018028

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-13049

When the inventors of the present invention have studied the invention described in Patent Document 1, it has been found that when a member for an electronic device such as a display member is formed into a specific pattern on a thin glass substrate of a laminate, the pattern is shifted and displayed. The production yield of the panel is reduced.

As a result of the investigation, as described in Patent Document 2, the surface unevenness such as the undulation of the surface of the laminated thin plate glass causes the production yield to decrease as described above.

Therefore, the inventors of the present invention polished the surface of the thin glass substrate in the laminate described in Patent Document 1 to form a flat surface, and formed a member for an electronic device or the like thereon. However, when the thin glass substrate on which the electronic device member is formed is peeled off from the laminate, the surface of the thin glass substrate on which the electronic device member is formed after peeling is again undulated. As described above, such surface undulations may be a cause of a decrease in productivity.

The present invention has been made in view of the above problems, and an object thereof is to provide an electronic device. In the case of forming the electronic device member and peeling off the glass substrate on which the electronic device member is formed, the flatness of the surface of the glass substrate is excellent, and as a result, the production yield of the electronic device can be suppressed. reduce. Still another object of the present invention is to provide a method for producing a glass laminate for use in the manufacture of the electronic device.

The inventors of the present invention have studied the problems of the prior art and found that the surface undulation of the surface of the resin layer on which the glass substrate is laminated is related to the above problem. Based on this insight, it was found that the above problems can be solved by the following configuration, and the present invention has been completed.

That is, in order to achieve the above object, a first aspect of the invention is a method of manufacturing an electronic device, comprising the steps of: a laminating step of a resin layer having a support substrate and a single side fixed to the support substrate; and the resin layer The exposed surface of the resin layer of the support substrate with the resin layer exposed on the exposed surface, and the first main surface of the glass substrate having the first main surface and the second main surface having a thickness of 0.3 mm or less as a laminate a surface of the support substrate with the resin layer and the glass substrate are laminated to obtain a glass laminate; the polishing step is to polish the second main surface of the glass substrate in the glass laminate; and the member forming step is performed on the glass substrate a member for forming an electronic device on the second main surface to be polished; and a separating step of separating the glass substrate on which the member for the electronic device is laminated and the support substrate with the resin layer, thereby obtaining the glass substrate and the substrate An electronic device for the member for an electronic device; and the surface undulation on the exposed surface of the resin layer is 0.100 μm or less in terms of filter center line undulation (W _CA ).

In the first aspect, the resin of the resin layer is preferably an fluorenone resin.

In the first aspect, the fluorenone resin is preferably a reaction hardened product of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene.

In the first aspect, the polishing is preferably CMP (Chemical Mechanical Polishing).

In the first aspect, the glass substrate preferably comprises an alkali-free glass containing the following components in terms of an oxide-based mass percentage: SiO ₂ : 50 to 66%, and Al ₂ O ₃ : 10.5 to 24%, B. ₂ O ₃ : 0~12%, MgO: 0~8%, CaO: 0~14.5%, SrO: 0~24%, BaO: 0~13.5%, MgO+CaO+SrO+BaO: 9~29.5%, And ZrO ₂ : 0 to 5%.

In the first aspect, the glass substrate preferably comprises an alkali-free glass containing the following components in terms of an oxide-based mass percentage: SiO ₂ : 58 to 66%, and Al ₂ O ₃ : 15 to 22%, B. ₂ O ₃ : 5~12%, MgO: 0~8%, CaO: 0~9%, SrO: 3~12.5%, BaO: 0~2%, and MgO+CaO+SrO+BaO: 9~18% .

A second aspect of the present invention provides a method for producing a glass laminate, wherein the glass laminate comprises a ground glass substrate, and the method comprises the steps of: a step of laminating a resin having a support substrate and a single surface fixed to the support substrate The exposed surface of the resin layer of the support substrate with the resin layer on the exposed surface of the resin layer and the glass substrate having a thickness of 0.3 mm or less of the first main surface and the second main surface The first main surface serves as an accumulation layer, and the support substrate of the resin layer and the glass substrate are laminated to each other to obtain a glass laminate; and the polishing step of polishing the second main surface of the glass substrate in the glass laminate; and The surface undulation of the surface of the resin layer was 0.100 μm or less in terms of filter center line undulation (W _CA ).

In the second aspect, the resin of the resin layer is preferably an fluorenone resin.

In the second aspect, the fluorenone resin is preferably a reaction hardened product of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene.

In the second aspect, the polishing is preferably chemical mechanical polishing (CMP).

According to the present invention, it is possible to provide a method for producing an electronic device which is excellent in flatness of a surface of a glass substrate even when a member for an electronic device is formed and a glass substrate on which an electronic device member is formed is peeled off. Suppressing the reduction in production yield of electronic devices. Moreover, the present invention can also provide a method of manufacturing a glass laminate for use in the manufacture of the electronic device.

10, 100‧‧ ‧ glass laminate

12, 112‧‧‧ Support substrate

14, 114‧‧‧ resin layer

14a‧‧‧Resin layer surface

16, 116‧‧‧ glass substrate

16a, 116a‧‧‧ the first main surface of the glass substrate

16b, 116b‧‧‧ the second main surface of the glass substrate

18‧‧‧Support substrate with resin layer

20‧‧‧Laminated body of components for electronic devices

22‧‧‧Members for electronic devices

24‧‧‧Electronic devices

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the steps of a method of manufacturing an electronic device of the present invention.

Fig. 2 is a schematic cross-sectional view showing an embodiment of a glass laminate of the present invention.

Fig. 3 is a schematic cross-sectional view showing an embodiment of a laminate of members for an electronic device according to the present invention.

4(a) to 4(c) are schematic cross-sectional views showing a grinding step and a separating step of the prior art glass laminate.

The present invention is not limited by the following embodiments, and various modifications and substitutions may be made to the embodiments described below without departing from the scope of the invention.

Furthermore, in the present invention, the case where the peeling strength of the interface between the layer of the substrate and the resin layer is higher than the peeling strength of the interface between the layer of the resin layer and the layer of the glass substrate is hereinafter referred to as a resin. The layer and the glass substrate are detachably adhered to each other, and the support substrate and the resin layer are fixed.

The inventors of the present invention have found that the surface of the glass substrate in the laminate used in the prior art (the invention of Patent Document 1) has undulations, and the surface of the glass substrate itself is undulated and the resin is in contact with the glass substrate. The undulations of the surface of the layer, especially the latter, are greater. Therefore, first, the correlation between the fluctuation of the surface of the resin layer and the problems of the prior art will be described using FIG.

As shown in FIG. 4(a), in the case of the glass laminate 100 of the prior art, when the surface of the resin layer 114 on the support substrate 112 has surface irregularities such as undulations, the glass substrate 116 disposed in contact with the surface is provided. Since the thickness of the plate is thin, the glass substrate 116 is deformed in such a manner as to follow the surface undulation of the surface of the resin layer 114 (see FIG. 4(a)). Thereafter, by exposing the polishing step, the exposed first main surface 116a of the glass substrate 116 is temporarily flattened. However, when the glass substrate 116 and the resin layer 114 are peeled off, the original flat second main surface 116b of the glass substrate 116 returns to a flat force and acts to flatten. However, the stress is applied to the polishing step to be flat. The surface undulation occurs again on the first main surface 116a. That is, the surface of the resin layer 114 is undulated and transferred to the surface of the glass substrate. The surface undulation after peeling of the glass substrate 116 is also generated after the electronic device member is formed on the first main surface 116a of the glass substrate 116. Therefore, if only the grinding step is set, the desired effect cannot be obtained.

Therefore, the inventors of the present invention have found that the above problem can be solved by setting the undulation of the surface of the resin layer to a specific value or less and providing a polishing step. By reducing the undulation of the surface of the resin layer, the deformation of the glass substrate laminated thereon can be reduced, and even after the separation step described below, the undulation of the surface of the resin layer can be suppressed from being transferred to the surface of the glass substrate. Further, by the grinding step, the surface undulation of the glass substrate itself or the minute flaw of the surface can be removed. In particular, if the surface undulation on the exposed surface of the resin layer is 0.100 μm or less in terms of the filter center line undulation (W _CA ), the surface undulation of the glass substrate laminated thereon is also equal to or less than the above, and Patent Document 2 can be achieved. The suppression of the reduction in the yield of the electronic device or the assurance of the reliability.

Hereinafter, the electronic device and the method of manufacturing the laminated body will be described in the order of the respective steps.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the manufacturing steps in an embodiment of a method of manufacturing an electronic device according to the present invention. As shown in FIG. 1, the manufacturing method of the electronic device includes a laminating step (S102), a grinding step (S104), a member forming step (S106), and a separating step (S108).

The materials used in each step and their procedures are described in detail below. First, the lamination step (S102) will be described in detail.

[Lamination step]

In the laminating step S102, the exposed surface of the resin layer of the support substrate with the resin layer and the first main surface of the glass substrate having the specific thickness of the first main surface and the second main surface are used as a layer, and the resin layer is attached. The step of obtaining a glass laminate by supporting the resin layer of the substrate and the glass substrate in close contact with each other. By performing this step S102, the glass laminate which is used in the following polishing step S104 and member forming step S106 can be obtained.

Fig. 2 is a schematic cross-sectional view showing an example of a glass laminate of the present invention.

As shown in FIG. 2, the glass laminate 10 supports a layer of the substrate 12, a layer of the glass substrate 16, and a laminate of the resin layer 14 present between the layers. One surface of the resin layer 14 is fixed to the layer of the support substrate 12, and the other surface thereof is in contact with the first main surface 16a of the glass substrate 16, and the interface between the resin layer 14 and the glass substrate 16 is detachably adhered. In other words, the resin layer 14 has easy peelability to the first main surface 16a of the glass substrate 16.

The glass substrate 16 is reinforced in a member forming step S106 in which a layer of the support substrate 12 and the resin layer 14 are formed in a member for manufacturing an electronic device member such as a liquid crystal panel. In addition, the two layers of the glass laminate 10 including the support substrate 12 and the resin layer 14 are referred to as the support substrate 18 with the resin layer independently of the glass laminate 10 . In the support substrate 18 with the resin layer attached, the resin layer 14 is fixed to the support substrate 12.

This glass laminate 10 is used up to the member forming step S106. In other words, the glass laminate 10 is formed by forming a member for an electronic device such as a liquid crystal display device on the surface of the second main surface 16b of the glass substrate 16. Thereafter, the layer of the support substrate 18 with the resin layer is The interface between the layers of the glass substrate 16 is peeled off, and the layer of the support substrate 18 with the resin layer is not part of the electronic device. The support substrate 18 with the separated resin layer can be laminated with the new glass substrate 16 to be reused as the glass laminate 10.

Hereinafter, each layer (support substrate, resin layer, glass substrate) constituting the glass laminate will be described in detail first, and then the procedure of step S102 will be described in detail.

(support substrate)

The support substrate 12 and the resin layer 14 cooperate to support the glass substrate 16 and enhance the deformation of the glass substrate 16 during the manufacture of the electronic device member in the following member forming step S106 (manufacturing step of the electronic device member). Damage, damage, etc. Further, when a glass substrate having a thickness smaller than that of the prior art is used, by using the glass laminate 10 having the same thickness as the previous glass substrate, the manufacturing process of the glass substrate suitable for the previous thickness can be used in the member forming step S106 or Manufacturing equipment, which is also one of the purposes of using the support substrate 12.

As the support substrate 12, for example, a glass plate, a plastic plate, a SUS plate, a ceramic plate, a metal plate, or the like can be used. In the case where the member forming step S106 is accompanied by the heat treatment, the support substrate 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16, more preferably formed of the same material as the glass substrate 16, and the support substrate. 12 is preferably a glass plate. The support substrate 12 is particularly preferably a glass plate containing the same glass material as the glass substrate 16.

The surface undulation of the surface of the support substrate 12 having the resin layer 14 described below is preferably 0.100 μm or less in terms of the filter center line undulation (W _CA ). Here, the "surface undulation" is a value obtained by measuring a W _CA (filter center line undulation) described in JIS B-0610 (1987) using a known stylus type surface shape measuring device. Further, in the present invention, the cutoff value of the filter fluctuation curve is set to 0.8 mm, and the measurement length is set to 40 mm. When the surface undulation is within the above range, the surface of the resin layer 14 which is in contact with the glass substrate 16 (the easily peelable surface) 14a has a small surface undulation, and as a result, the electronic device is formed even after the separation step S108 described below. The surface of the second main surface of the glass substrate 16 of the member is also undulated, and the occurrence of positional displacement of the member for electronic device can be suppressed. Among them, in terms of the above-described effects being more excellent, the filter center line undulation is preferably 0.070 μm or less, more preferably 0.030 μm or less. Further, the lower limit is not particularly limited, and is preferably 0 μm.

Further, as a method of reducing the surface undulation of the surface of the support substrate 12, a known polishing method (for example, known physical polishing or chemical polishing; more specifically, CMP or the like) can be used.

The thickness of the support substrate 12 may be thicker than the glass substrate 16, or may be thinner than the glass substrate 16. The thickness of the support substrate 12 is preferably selected based on the thickness of the glass substrate 16, the thickness of the resin layer 14, and the thickness of the glass laminate 10. For example, the current member forming step is designed to handle a substrate having a thickness of 0.5 mm. When the sum of the thickness of the glass substrate 16 and the thickness of the resin layer 14 is 0.1 mm, the thickness of the support substrate 12 is set to 0.4 mm. . The thickness of the support substrate 12 is preferably 0.2 to 5.0 mm in the usual case.

When the support substrate 12 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 cracking. In addition, it is expected that the thickness of the glass plate is preferably 1.0 mm or less for the reason that the member for an electronic device is formed and the rigidity is appropriately flexed without being broken at the time of peeling.

The difference between the average linear expansion coefficient (hereinafter simply referred to as "average linear expansion coefficient") of the glass substrate 16 and the support substrate 12 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, there is a possibility that the glass laminate 10 is rapidly warped or the glass substrate 16 and the support substrate 18 with the resin layer are peeled off during the heating and cooling in the member forming step S106. When the material of the glass substrate 16 is the same as that of the support substrate 12, the occurrence of such a problem can be suppressed.

(resin layer)

The resin layer 14 is fixed to at least one surface of the support substrate 12, and is detachably adhered to the glass substrate 16. The resin layer 14 prevents the position of the glass substrate 16 from being displaced before the operation of separating the glass substrate 16 from the support substrate 12, and is easily peeled off from the glass substrate 16 by a separation operation, thereby preventing the glass substrate 16 and the like from being broken due to the separation operation. . Tree The grease layer 14 is fixed to the support substrate 12, and the resin layer 14 and the support substrate 12 are not peeled off during the separation operation, and the support substrate 18 with the resin layer can be obtained by a separation operation. Further, in order to facilitate the separation of the interface between the resin layer 14 and the glass substrate 16 by the separation operation, it is preferable to provide a peeling starting point at the interface at the time of starting the separation operation and peeling off.

The surface 14a of the resin layer 14 that is in contact with the glass substrate 16 is detachably adhered to the first main surface 16a of the glass substrate 16. In the present invention, the property of easily peeling the surface of the resin layer 14a is referred to as easy peelability (peelability).

In the present invention, the fixing is indistinguishable from the peeling strength (i.e., the stress required for peeling), and the fixing means that the peeling strength is large with respect to the adhesion.

Further, the term "peelable" means peeling, and means peeling without peeling off the surface to be fixed. Specifically, in the case where the operation of separating the glass substrate 16 from the support substrate 12 is performed in the glass laminate 10 of the present invention, the surface is adhered to the surface to be adhered, and the surface is not peeled off from the fixed surface. Therefore, when the operation of separating the glass laminate 10 into the glass substrate 16 and the support substrate 12 is performed, the glass laminate 10 is separated into both the glass substrate 16 and the support substrate 18 with the resin layer.

The resin layer 14 is preferably fixed to the surface of the support substrate 12 by a strong bonding force such as an adhesive force or an adhesive force. For example, the cured resin is bonded to the surface of the support substrate 12 by reactively curing the reaction curable resin on the surface of the support substrate 12. Further, a process of generating a strong bonding force (for example, a treatment using a coupling agent) between the surface of the support substrate 12 and the resin layer 14 can be performed to improve the bonding force between the surface of the support substrate 12 and the resin layer 14.

On the other hand, it is preferable to bond the resin layer 14 to the first main surface 16a of the glass substrate 16 with a weak bonding force, for example, by a bonding force generated by the van der Waals force between the solid molecules. The surface of the resin layer 14a before the glass substrate 16 is in contact with the glass substrate 16 is preferably a surface which is easily peelable, and the surface of the resin layer 14a which is easily peelable is brought into contact with the first main surface 16a of the glass substrate 16 to be weakly bonded. Force combines the two surfaces. In other words, when the resin layer surface 14a is easily peelable, the peeling property at the interface with the first main surface 16a of the glass substrate 16 is further improved. The two surfaces are in contact with each other without a gap, and this state is referred to as a close contact in the present invention.

Further, the surface of the resin layer can be easily peeled off by imparting a surface treatment to the surface of the resin layer which is not easily peelable in a usual sense. In addition, the resin layer which is not easily peelable in the usual sense is a resin which can be intimately bonded to the bonding force which is sufficiently low in the above-mentioned fixation (and as long as the glass substrate or the support substrate is not damaged) Alternatively, if it is peeled off, it may be used as a material of the resin layer without performing surface treatment.

In particular, when the surface of the resin layer that is in contact with the glass substrate is easily peelable, a part of the surface of the resin layer remains on the surface of the glass substrate due to breakage of the surface of the resin layer during peeling.

As described above, the bonding force of the resin layer 14 to the surface of the support substrate 12 is relatively higher than the bonding force of the resin layer 14 to the first main surface 16a of the glass substrate. Therefore, the peeling strength between the resin layer 14 and the support substrate 12 is higher than the peel strength between the resin layer 14 and the glass substrate 16. Preferably, the resin layer 14 and the support substrate 12 are bonded by adhesion or adhesion. However, the present invention is not limited thereto, and the resin layer 14 and the support substrate 12 may be bonded by a force generated by another bonding force as long as the bonding strength of the resin layer 14 to the glass substrate 16 is relatively higher.

The surface undulation on the surface 14a of the resin layer 14 (the surface in contact with the glass substrate 16) is 0.100 μm or less in terms of the filter center line undulation (W _CA ). The "surface undulation" is a value obtained by measuring a W _CA (filter center line undulation) described in JIS B-0610 (1987) using a known stylus type surface shape measuring device. Further, in the present invention, the cutoff value of the filter fluctuation curve is set to 0.8 mm, and the measurement length is set to 40 mm. When the surface undulation is within the above range, surface undulation of the second main surface of the glass substrate 16 on which the electronic device member is formed can be suppressed even after the separation step S108 described below. As a result, the occurrence of the positional shift of the member for the electronic device can be suppressed. In view of the fact that the effect is more excellent, it is preferably 0.070 μm or less, more preferably 0.030 μm or less. The lower limit is not particularly limited, and is preferably 0 μm.

Further, as a method of reducing the surface undulation of the surface of the resin layer 14, a method of using the support substrate 12 having a small surface relief is used, and a composition for forming a resin layer used for forming the resin layer 14 is used for the support substrate 12 a method in which a layer of a composition for forming a resin layer (hereinafter also referred to as a layer for forming a resin layer) is formed, and a support substrate 12 having a composition layer for forming a resin layer is left to stand before curing; (a method of transferring flatness to a surface of a resin layer 14 (preferably in a heating environment) with a filter center line undulation (W _CA ) of 0.100 μm or less); etching the resin layer 14 Surface method, etc.

The size of the resin layer 14 is not particularly limited. The resin layer 14 may be larger than the glass substrate 16 or the support substrate 12, or may be smaller than the glass substrate 16 or the support substrate 12.

The thickness of the resin layer 14 is not particularly limited, and is preferably 15 μm or less, more preferably 2 to 15 μm, still more preferably 2 to 10 μm, in terms of surface undulation. The reason for this is that when the thickness of the resin layer 14 is within such a range, the adhesion between the resin layer 14 and the glass substrate 16 becomes sufficient. Moreover, the reason is that even if bubbles or foreign matter are interposed between the resin layer 14 and the glass substrate 16, the occurrence of deformation defects of the glass substrate 16 can be suppressed. Further, if the thickness of the resin layer 14 is too thick, it takes time and material to form, which is uneconomical and the surface undulation tends to become large.

Further, the resin layer 14 may include two or more layers. In this case, "the thickness of the resin layer 14" means the total thickness of all the layers.

Further, when the resin layer 14 contains two or more layers, the types of the resins forming the respective layers may be different.

Preferably, the resin layer 14 comprises a material having a glass transition point lower than room temperature (about 25 ° C) or having no glass transition point. This is because the glass substrate 16 can be more easily peeled off and the adhesion to the glass substrate 16 is also sufficient.

Moreover, since the resin layer 14 is heat-processed in the member formation process S106 in many cases, it is preferable to have heat resistance.

Moreover, if the elastic modulus of the resin layer 14 is too high, there is adhesion to the glass substrate 16. Reduce the tendency. On the other hand, if the elastic modulus of the resin layer 14 is too low, the peelability is lowered.

The kind of the resin forming the resin layer 14 is not particularly limited. For example, an acrylic resin, a polyolefin resin, a polyurethane resin, or an anthrone resin can be mentioned. It can also be used by mixing several kinds of resins. Among them, an anthrone resin is preferred. The reason for this is that the fluorenone resin is excellent in heat resistance or peelability. Further, the reason is that when the support substrate 12 is a glass plate, it is easily fixed to the glass plate by a condensation reaction with a stanol group on the surface of the glass plate. The fluorenone resin layer is preferably treated in a state of, for example, about 200 ° C in the air for about 1 hour in a state of being inserted between the support substrate 12 and the glass substrate 16 , and the peeling property is hardly deteriorated.

The resin layer 14 is preferably an fluorenone resin (cured product) for separating paper in an anthrone resin. The fluorenone resin of the release layer of the release paper is formed by curing a layer of the curable fluorenone resin composition applied on the release paper. A resin layer comprising a hardenable ketone resin formed by curing the surface of the support substrate 12 by using the curable fluorenone resin composition, and a surface of the support substrate 12, and having a free surface thereof It is excellent in easy peelability. Moreover, since the flexibility is high, even if foreign matter such as bubbles or dust is mixed between the resin layer 14 and the glass substrate 16, the occurrence of deformation defects of the glass substrate 16 can be suppressed.

The curable fluorenone resin composition for forming such a resin layer 14 is classified into a condensation reaction type fluorenone resin composition, an addition reaction type fluorene ketone resin composition, and an ultraviolet curing type fluorenone resin composition according to the curing mechanism thereof. And an electron beam hardening type fluorenone resin composition, either can be used. Among these, an addition reaction type fluorenone resin composition is preferred. This is because the curing reaction is easy, and the degree of easy peelability of the surface 14a of the resin layer after curing is good, and the heat resistance is also high.

The addition reaction type fluorenone resin composition is a composition containing a main component and a crosslinking agent, and is hardenable in the presence of a catalyst such as a platinum-based catalyst. Addition reaction type fluorenone resin composition The hardening is promoted by heat treatment. The main component in the addition reaction type fluorenone resin composition is preferably an organic polyoxyalkylene having an alkenyl group (vinyl group or the like) bonded to a ruthenium atom (i.e., an organic alkenyl polyoxy siloxane; Preferably, it is a linear chain, and an alkenyl group becomes a crosslinking point. The crosslinking agent in the addition reaction type fluorene ketone resin composition is preferably an organic polyoxy siloxane having a hydrogen atom (hydroalkylene group) bonded to a ruthenium atom (ie, an organic hydrogen polyoxy siloxane); Preferably, it is a linear chain), and a hydroquinone group or the like becomes a crosslinking point.

The addition reaction type fluorenone resin composition is hardened by an addition reaction of a crosslinking point of a main agent and a crosslinking agent.

Further, the curable fluorenone resin composition includes a solvent type, an emulsion type, and a solventless type, and any type may be used. These are preferably solventless. The reason is excellent in productivity, safety, and environmental characteristics. The reason for this is that since the solvent which is foamed at the time of curing in the formation of the resin layer 14, that is, heat curing, ultraviolet curing, or electron beam curing, is not contained, bubbles are not easily left in the resin layer 14.

In addition, as a curable fluorene ketone resin composition, specifically, a commercially available product name or model, KNS-320A, KS-847 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and TPR6700 (Momentive Performance Materials Japan) are mentioned. Co., Ltd., a combination of vinyl ketone "8500" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogen polyoxyalkylene "12031" (manufactured by Arakawa Chemical Industries, Ltd.), vinyl ketone "11364" (Arakawa Chemical Co., Ltd.) (manufactured by Industrial Co., Ltd.) in combination with methyl hydrogen polyoxyalkylene "12031" (manufactured by Arakawa Chemical Industries Co., Ltd.), vinyl ketone "11365" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogen polyoxyalkylene "12031" (a combination of Arakawa Chemical Industry Co., Ltd.) and the like.

Further, KNS-320A, KS-847, and TPR6700 are sclerosing fluorenone resin compositions containing a main component and a crosslinking agent in advance.

Moreover, it is preferable that the fluorenone resin (the cured product of the curable fluorene ketone resin composition) which forms the resin layer 14 has a property that the components such as fluorenone having a low molecular weight in the fluorenone resin layer are less likely to be transferred to the glass substrate 16, that is, Low fluorenone transferability.

(Method of Manufacturing Resin Layer)

The method of fixing the resin layer 14 to the support substrate 12 is not particularly limited.

For example, a resin layer forming step of forming the resin layer 14 having easy peelability on the support substrate 12 and fixing it may be performed before the laminating step S102. For example, a resin layer forming step of forming a resin layer 14 by applying a resin layer forming composition (curable resin composition) onto the support substrate 12 may be performed. More specifically, it is preferable to form a resin layer forming composition layer as the resin layer 14 on the surface of the support substrate 12, and then to cure the resin layer forming composition to form a resin layer fixed on the support substrate 12. 14 method.

Further, for example, the resin layer 14 may be formed by a method of fixing a film-like resin to the surface of the support substrate 12. Specifically, the surface of the support substrate 12 is subjected to surface modification treatment (primer treatment) in order to impart a high fixing force (high peel strength) to the surface of the support substrate 12 to the surface of the support substrate 12, and is fixed to the support. The method on the substrate 12. For example, a chemical method for chemically increasing the fixing force such as a decane coupling agent (primer treatment), a physical method for increasing the surface active group such as a flame treatment, and a surface roughness by, for example, sand blasting, can be exemplified. Increase the mechanical treatment of the gripping force, etc.

A resin layer forming composition layer to be the resin layer 14 is formed on the surface of the support substrate 12, and then the resin layer forming composition layer is cured to form the resin layer 14, and a resin layer is formed on the surface of the support substrate 12. The method of forming the composition layer may, for example, be a method of applying a composition for forming a resin layer onto the support substrate 12. 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. It can be suitably selected from such a method depending on the kind of the resin composition.

In the case where the resin layer forming composition of the resin layer 14 is applied onto the support substrate 12, the coating amount thereof is preferably from 1 to 100 g/m ² , more preferably from 5 to 20 g/m ² .

When the solvent layer and the resin are contained in the resin layer-forming composition, in order to produce the resin layer 14 having the surface exhibiting the specific surface relief, the resin layer is preferably used. The content of the solvent in the composition for formation is 70% by mass or less based on the total amount of the composition, more preferably 60% by mass or less, and still more preferably 50% by mass or less. By adjusting the amount of the solvent within the above range, the amount of evaporation of the solvent from the layer of the formed composition can be suppressed, and as a result, the resin layer 14 having less surface undulation can be obtained. In addition, the lower limit of the amount of the solvent is not particularly limited as long as the resin layer-forming composition can be applied, and is preferably 30% by mass or more in terms of handleability and the like.

The type of the solvent to be used for the composition for forming a resin layer is not particularly limited, and it is preferable to use a solvent having a boiling point of 100 ° C or less in terms of suppressing the occurrence of surface undulation of the obtained resin layer 14 .

Further, the resin layer-forming composition preferably has a viscosity of 40 mPa ̇s or less, more preferably 20 mPa ̇s or less, in terms of forming the resin layer 14 having less surface undulation. Further, the lower limit is not particularly limited, and is preferably 3 mPa ̇s or more in terms of film formability of the composition.

In addition, as the resin contained in the resin layer-forming composition, a resin which can form the above resin layer is exemplified, and a curable fluorenone is preferably used.

For example, when the resin layer 14 is formed from the addition reaction type fluorenone resin composition, the organic alkenyl polysiloxane, the organic hydrogen polyoxyalkylene and the catalyst are contained by a known method such as the above-described spraying method. The resin layer forming composition X of the mixture is applied onto the support substrate 12, and then heat-hardened.

The heat curing conditions vary depending on the amount of the catalyst to be mixed, and the reaction is carried out in the air at 50 ° C to 250 ° C, preferably at 100 ° C to 200 ° C. Further, the reaction time in this case is set to 5 to 60 minutes, preferably 10 to 30 minutes.

By heat-hardening the composition for forming a resin layer X, the fluorenone resin is chemically bonded to the support substrate 12 during the curing reaction, and the fluorenone resin layer is bonded to the support substrate 12 by the anchoring effect. By the action of these, the fluorenone resin layer is firmly fixed to the support substrate 12. Further, the formation of the composition for forming a resin layer includes an fluorenone resin In the case of a resin layer other than the resin, the resin layer 14 fixed to the support substrate 12 may be formed in the same manner as described above.

Further, a resin layer forming composition layer to be the resin layer 14 is formed on the surface of the support substrate 12, and then the resin layer forming composition layer is cured to form a resin layer 14 fixed to the support substrate 12, In view of the fact that the flatness of the resin layer 14 to be formed is more excellent, it is preferable to leave the support substrate 12 including the resin layer-forming composition layer after the formation of the resin layer-forming composition layer and before curing. By allowing to stand for a specific period of time, the flatness of the surface of the composition layer for forming a resin layer can be improved, and the volatile component contained in the composition layer for forming a resin layer can be removed, and the surface roughness of the resin layer 14 at the time of curing can be further suppressed.

The temperature at the time of standing is not particularly limited, and it may be left at a temperature lower than the temperature of the heating condition at the time of hardening, preferably from 0 ° C to 100 ° C, more preferably from 0 ° C to room temperature (about 25 ° C). ).

The standing time is not particularly limited, and is preferably from 30 seconds to 1 hour, more preferably from 1 minute to 10 minutes, in terms of the balance between the flatness and the productivity of the resin layer 14.

Further, it may be allowed to stand under reduced pressure as needed. The condition of the pressure reduction is not particularly limited, and is preferably from 1 to 1,000 Pa, more preferably from 10 to 1,000 Pa, in terms of the balance between the flatness of the resin layer 14 and the efficiency of the operation.

(glass substrate)

The first main surface 16a of the glass substrate 16 is in close contact with the resin layer, and the electronic device member is provided on the second main surface 16b on the side opposite to the resin layer 14 side.

The type of the glass substrate 16 may be a normal one, and examples thereof include a glass substrate for a display device such as an LCD or an OLED. The glass substrate 16 is excellent in chemical resistance and moisture permeability resistance, and has a low heat shrinkage rate. As an index of the heat shrinkage rate, the coefficient of linear expansion prescribed by JIS R 3102 (1995 Revision) is used.

If the linear expansion coefficient of the glass substrate 16 is large, since the member forming step S106 is large In some cases, there is a heat treatment, so that various disadvantages are likely to occur. For example, when a TFT (Thin Film Transistor) is formed on the glass substrate 16, when the glass substrate 16 on which the TFT is formed under heating is cooled, the position of the TFT is caused by thermal contraction of the glass substrate 16. The offset is too large.

The glass substrate 16 is obtained by melting a glass raw material and molding the molten glass into a plate shape. Such a molding method may be a 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 16 having a small thickness can be formed by heating a glass which is temporarily formed into a plate shape to a moldable temperature, and stretching it by means of stretching or the like to be thinned (re-draw method). And get.

The glass of the glass substrate 16 is not particularly limited, and is preferably an alkali-free borosilicate glass, a borosilicate glass, a soda lime glass, a sorghum 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 of 40 to 90% by mass in terms of oxide.

As the glass of the glass substrate 16, a glass suitable for the type of the member for an electronic device or a manufacturing step thereof can be used. For example, since the elution of the alkali metal component is likely to affect the liquid crystal, the glass substrate for a liquid crystal panel contains glass (alkali-free glass) which does not substantially contain an alkali metal component (but usually contains an alkaline earth metal component). As described above, the glass of the glass substrate can be appropriately selected depending on the kind of the apparatus to be applied and the manufacturing steps thereof.

As the glass of the glass substrate 16, in terms of a small thermal expansion coefficient, an alkali-free glass containing SiO ₂ : 50 to 66%, Al ₂ represented by a mass percentage based on an oxide is preferably used. O ₃ : 10.5~24%, B ₂ O ₃ : 0~12%, MgO: 0~8%, CaO: 0~14.5%, SrO: 0~24%, BaO: 0~13.5%, MgO+CaO+ SrO+BaO: 9~29.5%, and ZrO ₂ : 0~5%.

Further, as the glass of the glass substrate 16, in terms of a small thermal expansion coefficient, an alkali-free glass containing the following components, which is represented by a mass percentage based on an oxide, is preferably used: SiO ₂ : 58 to 66% , Al ₂ O ₃ : 15 to 22%, B ₂ O ₃ : 5 to 12%, MgO: 0 to 8%, CaO: 0 to 9%, SrO: 3 to 12.5%, BaO: 0 to 2%, and MgO+CaO+SrO+BaO: 9~18%.

The thickness of the glass substrate 16 is 0.3 mm or less, and more preferably 0.15 mm or less from the viewpoint of thinning and/or weight reduction of the glass substrate 16. When it exceeds 0.3 mm, the requirements for thinning and/or weight reduction of the glass substrate 16 are not satisfied. When it is 0.3 mm or less, the glass substrate 16 can be provided with good softness. In the case of 0.15 mm or less, the glass substrate 16 can be wound into a roll shape.

Further, the thickness of the glass substrate 16 is preferably 0.03 mm or more for the reason that the production of the glass substrate 16 is easy and the operation of the glass substrate 16 is easy.

Furthermore, the glass substrate 16 may also comprise two or more layers. In this case, the materials forming the layers may be the same material or different types of materials. Moreover, in this case, "the thickness of the glass substrate 16" means the total thickness of all the layers.

(procedure of steps)

In the step S102, the support substrate 18 with the resin layer and the glass substrate are prepared. 16. The resin layer surface 14a of the support substrate 18 with the resin layer and the first main surface 16a of the glass substrate 16 are laminated as a layer. The layer of the resin layer 14 has an easy peeling property, and can be easily adhered in a peelable manner by usual overlapping and pressurization.

Specifically, for example, a method in which the resin substrate 14 and the glass substrate 16 are pressure-bonded by a roll or a press after the glass substrate 16 is superposed on the surface 14a of the easily peelable resin layer 14 in a normal pressure environment. It is preferable to bond the resin layer 14 to the glass substrate 16 by pressure bonding using a roll or a press. Moreover, the air bubbles mixed between the resin layer 14 and the glass substrate 16 can be relatively easily removed by pressure bonding using a roll or a press.

When the pressure bonding is carried out by a vacuum lamination method or a vacuum press method, it is more preferable because the incorporation of air bubbles can be suppressed or a good adhesion can be ensured. By the pressure bonding under vacuum, even when minute bubbles are left, the bubbles are not grown by heating, and the strain defects of the glass substrate 16 are less likely to occur.

When the resin layer 14 is detachably adhered to the first main surface 16a of the glass substrate 16, it is preferable to sufficiently clean the side of the resin layer 14 and the glass substrate 16 which are in contact with each other, and the degree of cleanliness is high. Layering under the environment. That is, it is easy to mix foreign matter between the resin layer 14 and the glass substrate 16, and since the resin layer 14 is deformed, there is no possibility of affecting the flatness of the surface of the glass substrate 16, but the higher the cleanliness, the more flatness is. Good, so it is better.

The glass laminate 10 formed by the laminating step S102 can be used for various purposes, and examples thereof include the use of a panel for a display device, a PV, a thin film secondary battery, and an electronic component such as a semiconductor wafer having a circuit formed thereon. . Further, in this application, the glass laminate 10 is often exposed to high temperature conditions (for example, 320 ° 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.

[grinding step]

The polishing step S104 is a step of polishing the second main surface 16b of the glass substrate 16 in the glass laminate 10 obtained in the step S102. By providing this step S104, minute irregularities and flaws of the second main surface 16b of the glass substrate 16 can be removed, and the flatness of the surface on which the electronic device member is formed can be improved. Thereby, the reliability of the electronic device as a product can be improved. This effect is apparent 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 alone, and it is difficult to perform pre-polishing before the glass laminate 10 is formed.

The method of polishing 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 sand blasting method in which ceramic abrasive grains are blown, a polishing using a polishing sheet or a grindstone, and a chemical mechanical polishing (CMP) method using abrasive grains and a chemical solvent can be used.

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

Among them, chemical mechanical polishing is preferred in terms of higher flatness and cleanliness of the second main surface 16b of the polished glass substrate 16. Further, as the abrasive grains used for chemical mechanical polishing, known abrasive grains such as cerium oxide can be used.

By the above-described lamination step S102 and polishing step S104, a glass laminate including a polished glass substrate can be produced.

[Component forming step]

The member forming step S106 is a step of forming a member for an electronic device on the second main surface 16b of the glass substrate 16 polished in the polishing step S104.

Fig. 3 is a schematic cross-sectional view showing an example of a laminate of members for an electronic device obtained in the step S106. The laminated body 20 of the member for electronic devices includes the glass laminate 10 and the electronic device member 22.

First, the electronic device member used in the step S106 will be described in detail, and then the procedure of the step S106 will be described in detail.

(Mechanical components (functional components))

The electronic device member 22 is formed on the second main surface 16b of the glass substrate 16 in the glass laminate 10, and constitutes at least a part of the electronic device. More specifically, the electronic device member 22 includes members such as a display device panel, a solar cell, a thin film secondary battery, and an electronic component such as a semiconductor wafer on which a circuit is formed. The panel for a display device includes an organic EL panel, a plasma display panel, a field emission panel, and the like.

For example, as a member for a solar cell, a transparent electrode such as a tin oxide of a positive electrode, a ruthenium layer represented by a p layer/i layer/n layer, a metal of a negative electrode, and the like may be mentioned. It is used in various types such as compound type, dye sensitization type, and quantum dot type.

Further, examples of the lithium ion type include a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a collector layer, a resin as a sealing layer, and the like. Further, various members such as a nickel hydride type, a polymer type, and a ceramic electrolyte type may be mentioned.

Further, as a member for an electronic component, in a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), a metal of a conductive portion, yttrium oxide or nitridation of an insulating portion may be mentioned. In addition, 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 can be cited.

(procedure of steps)

The method for producing the laminated body 20 of the member for an electronic device is not particularly limited, and may be a conventionally known method depending on the type of the constituent member of the member for an electronic device. The electronic device member 22 is formed on the surface of the second main surface 16b of the glass substrate 16 of the laminated body 10.

In addition, the electronic device member 22 may not be all the members (hereinafter referred to as "all members") finally formed on the second main surface 16b of the glass substrate 16, but may be one part of all members (hereinafter referred to as "partial members" "). In the subsequent step, the glass substrate with the part of the member peeled off from the resin layer 14 may be formed into a glass substrate (corresponding to the following electronic device) with all the members.

Further, other electronic device members can be formed on the peeling surface (first main surface 16a) of the glass substrate with all the members peeled off from the resin layer 14. Further, a laminate having all the members may be assembled, and thereafter, the laminate of the resin layer is peeled off from the laminate of all the members to manufacture an electronic device. Further, the electronic device can be assembled by using two laminated bodies with all the members, and thereafter, the laminated substrate with the resin layers is peeled off from the laminated body of all the members to manufacture an electronic device.

For example, in the case of manufacturing an OLED, an organic EL structure is formed on the surface opposite to the resin layer 14 side of the glass substrate 16 of the glass laminate 10 (corresponding to the second main surface 16b of the glass substrate 16). The body is subjected to various layer forming operations or processes of forming a transparent electrode, and further depositing a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and the like on the surface on which the transparent electrode is formed to form a back electrode, using a seal Plate sealing, etc. Specific examples of the layer forming operation or treatment include a film forming treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate.

Further, for example, a method of manufacturing a TFT-LCD includes a TFT forming step of using a resist solution on the second main surface 16b of the glass substrate 16 of the planarized glass laminate 10 by CVD (Chemical Vapor Deposition) a thin film transistor (TFT) is formed on a metal film or a metal oxide film formed by a usual film formation method such as a chemical vapor deposition method or a sputtering method; and CF (Color Filter) is formed. Step, on the second main surface 16b of the glass substrate 16 of the other planarized glass laminate 10, a resist solution is used for pattern formation to form a color filter (CF); and a bonding step is attached TFT device substrate and Various steps such as lamination of the device substrate of CF are attached.

In the TFT forming step or the CF forming step, TFT or CF is formed on the second main surface 16b of the glass substrate 16 by a known photolithography technique or etching technique. At this time, a resist solution is used as a coating liquid for pattern formation.

Further, before forming the TFT or CF, the second main surface 16b of the glass substrate 16 may be cleaned as needed. As the cleaning method, a well-known dry cleaning or wet cleaning can be used.

In the bonding step, a liquid crystal material is injected between the laminated body with the TFT and the laminated body with the CF to laminate. 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 S108, the glass substrate 16 on which the electronic device member 22 is laminated is separated from the support substrate 18 on which the resin layer is laminated, from the laminate 20 of the member for electronic device obtained in the above-described member forming step S106, and the member for electronic device is obtained. 22 and the steps of the electronic device 24 of the glass substrate 16 (the glass substrate with the member for the electronic device).

In the case where the electronic device member 22 on the glass substrate 16 at the time of peeling is a part of all the constituent members required, the remaining constituent members may be formed on the glass substrate 16 after separation.

The method of peeling the first main surface 16a of the glass substrate 16 from the surface 14a of the resin layer 14 is not specifically limited. Specifically, for example, a sharp blade can be inserted at the interface between the glass substrate 16 and the resin layer 14 to add a starting point of peeling, and then a mixed fluid of water and compressed air is blown and peeled off. It is preferable that the support substrate 12 of the laminated body 20 for the electronic device-attached member is placed on the upper side and 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 double-layer layer has a supporting substrate, it is sequentially performed), and in this state, the cutter is first inserted into the interface of the glass substrate 16 - the resin layer 14. Then, the side of the support substrate 12 is adsorbed by a plurality of vacuum chucks, and the vacuum chuck is sequentially raised from the vicinity of the portion where the cutter is inserted. Thus, the interface between the resin layer 14 and the glass substrate 16 An air layer is formed which diffuses toward the entire surface of the interface, and the support substrate 12 can be easily peeled off.

The above manufacturing method is preferably a small display device used for a mobile terminal such as a mobile phone or a PDA (Personal Digital Assistant). The display device is mainly LCD or OLED, and as LCD, including TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, FE (Field Emission) type, TFT type, MIM (Metal-Insulator-Metal, metal-insulator-metal) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, and the like. Basically, it can be applied to any of the passive driving type and the active driving type.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples.

<Example 1>

A glass substrate ("AN100", an alkali-free glass plate with a linear expansion coefficient of 38 × 10 ^-7 /°C, manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, and a thickness of 0.5 mm was prepared as a support substrate and cleaned with pure water. UV (Ultraviolet) cleaning to purify the surface, and obtain a support substrate with a clean surface.

Then, as a component (A), a linear vinyl methyl polyoxyalkylene ("VDT-127", a viscosity at 25 ° C of 700-800 cP (centipoise), manufactured by Azmax, 1 mol of organopolyoxane The mol% of the vinyl group in the middle: 0.325) and the linear methyl hydrogen polyoxyalkylene as the component (B) ("HMS-301", the viscosity at 25 ° C is 25-35 cP (centipoise), manufactured by Azmax , the number of hydrogen atoms bonded to the ruthenium atom in one molecule: 8) is mixed in such a manner that the molar ratio (hydrogen atom/vinyl group) of all the vinyl groups bonded to the hydrogen atom bonded to the ruthenium atom is 0.9. One part by weight of the oxime compound having an acetylene-based unsaturated group represented by the following formula (1) as the component (C) is mixed with 100 parts by weight of the oxirane mixture.

HC≡CC(CH ₃ ) ₂ -O-Si(CH ₃ ) ₃ (1)

Then, a platinum-based catalyst (manufactured by Shin-Etsu Silicone Co., Ltd., CAT) is added to the total amount of the component (A), the component (B), and the component (C) so that the platinum metal concentration is 100 ppm in terms of platinum. -PL-56), a mixture of organopolyoxane compositions is obtained.

The obtained mixed liquid was applied onto the first main surface of the previously cleaned support substrate by a die coater (speed: 5 mm/s, gap: 150 μm, coating pressure: 95 kPa). Thereafter, the mixture (the resin layer-forming composition layer) applied on the support substrate was allowed to stand at room temperature for 10 minutes, and then heat-hardened at 180 ° C for 60 minutes in the air to form a length of 350 mm on the support substrate. A hardened fluorenone resin layer having a width of 300 mm and a thickness of 15 μm was obtained to obtain a support A (a support substrate with a resin layer). Further, the filter center line undulation (W _CA ) of the exposed surface of the hardened fluorenone resin layer was 0.090 μm.

On the other hand, a glass substrate ("AN100", an alkali-free glass plate having a linear expansion coefficient of 38 × 10 ^-7 / ° C, manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was subjected to pure water cleaning. UV cleaning cleans the surface of the glass substrate.

Thereafter, after the support A and the glass substrate were aligned, the first main surface of the glass substrate and the peeling surface of the cured fluorenone resin layer of the support A were adhered to each other at room temperature using a vacuum press device to obtain a glass. Laminated body.

Then, the second main surface (exposed surface) of the glass substrate of the obtained glass laminate was polished using an Oscar type grinder. As the polishing liquid, a colloidal cerium oxide polishing solution having an average particle diameter of cerium oxide particles of 0.08 μm and a content of cerium oxide particles of 10% by mass was used. As the polishing pad, suede material is used. Regarding the polishing conditions, the supply amount of the polishing liquid was 30 ml/min, the polishing pressure was 20000 Pa, the rotation speed of the lower platen was 80 rpm, and the polishing time was 600 seconds.

After the completion of the polishing, the second main surface of the glass substrate in the glass laminate subjected to the polishing treatment is vacuum-adsorbed on the platen, and then the glass substrate on one of the four corners of the glass substrate is The interface of the fluorenone resin layer was inserted into a stainless steel cutter having a thickness of 0.1 mm, and the starting point of the peeling was added to the interface between the glass substrate and the fluorenone resin layer. Then, after the support substrate was suctioned by the 24 vacuum chucks, the chucks were sequentially raised from the chucks near the corners of the inserted cutter. Here, the inserting of the cutter is performed while blowing an electrostatic fluid from the ionizer (manufactured by KEYENCE Co., Ltd.) to the interface. Then, while the electrostaticizer is continuously blown from the ionizer toward the space formed, the vacuum chuck is pulled up. As a result, the glass substrate subjected to the polishing treatment can be separated from the glass laminate on the platen. The filter center line undulation (W _CA ) of the second main surface of the obtained glass substrate was 0.090 μm. According to the results, it was confirmed that the glass substrate separated by the polishing treatment on the glass substrate of the glass laminate has excellent surface flatness. The results are summarized in Table 1.

<Example 2>

A mixed solution was prepared by adding 43 parts by weight of heptane to 100 parts by weight of the mixed liquid of the organopolyoxane composition obtained in the same procedure as in Example 1, using a die coater (coating speed: 40 mm/s, The obtained mixed solution was applied onto a support substrate with a gap of 140 μm and a coating pressure of 50 kPa. The mixture was allowed to stand at room temperature for 10 minutes, and then heat-hardened at 180 ° C for 60 minutes in the atmosphere to form a 15 μm hardened fluorenone resin layer. In the same manner as in Example 1, a glass laminate was produced and subjected to a polishing treatment to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 3>

After the mixed solution was applied onto a support substrate by a die coater, it was allowed to stand at room temperature for 30 minutes, and then heat-hardened at 180 ° C for 60 minutes in the atmosphere to form a 15 μm hardened fluorenone resin layer. In the same procedure as in Example 2, a glass laminate was produced and subjected to a polishing treatment to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 4>

100 parts by weight of heptane was added to 100 parts by weight of the mixed liquid of the organopolyoxane composition obtained in the same procedure as in Example 1, to prepare a mixed solution, using a die coater (coating speed: 40 mm/s, The obtained mixed solution was applied onto a support substrate with a gap of 100 μm and a coating pressure of 28 kPa. The mixture was allowed to stand at room temperature for 30 seconds, and then heat-hardened at 180 ° C for 60 minutes in the atmosphere to form a 15 μm hardened ketone resin layer. In the same manner as in Example 1, a glass laminate was produced and subjected to a polishing treatment to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 5>

After the mixed solution was applied onto a support substrate by a die coater, it was allowed to stand at room temperature for 10 minutes, and then heat-hardened at 180 ° C for 60 minutes in the atmosphere to form a 15 μm hardened fluorenone resin layer. According to the same procedure as in Example 4, a glass laminate was produced and subjected to a polishing treatment to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 6>

A glass laminate was produced and polished in the same manner as in Example 4 except that the coating speed of the die coater was changed from 40 mm/s to 80 mm/s to form a hardened fluorenone resin layer of 8 μm. Separation of the glass substrate subjected to the grinding treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 7>

After the mixed solution was applied onto a support substrate by a die coater, it was allowed to stand at room temperature for 10 minutes, and then heat-hardened at 180 ° C for 60 minutes in the atmosphere to form a hardened fluorenone resin layer of 8 μm. In the same procedure as in Example 6, a glass laminate was produced and subjected to a polishing treatment to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 8>

A mixed solution was prepared by adding 150 parts by weight of heptane to 100 parts by weight of the mixed solution of the organopolyoxane composition obtained in the same procedure as in Example 1, using a die coater (coating speed: 40 mm/s, The obtained mixed solution was applied to a support substrate at a gap of 100 μm and a coating pressure of 20 kPa. After standing at room temperature for 30 seconds, it was heat-hardened at 180 ° C for 60 minutes in the atmosphere to form a 15 μm hardened ketone resin. In the same manner as in Example 1, a glass laminate was produced and subjected to a polishing treatment to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 9>

After the mixed solution was applied onto a support substrate by a die coater, it was allowed to stand at room temperature for 10 minutes, and then heat-hardened at 180 ° C for 60 minutes in the air to form a hardened fluorenone resin layer of 8 μm. A glass laminate was produced and subjected to a polishing treatment in the same manner as in Example 8 to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 10>

A mixed solution was prepared by adding 233 parts by weight of heptane to 100 parts by weight of the mixed liquid of the organopolyoxane composition obtained in the same procedure as in Example 1, using a die coater (coating speed: 40 mm/s, The obtained mixed solution was applied onto a support substrate at a gap of 70 μm and a coating pressure of 15 kPa. After standing at room temperature for 30 seconds, it was heat-hardened at 180 ° C for 60 minutes in the atmosphere to form a 15 μm hardened ketone resin layer. In the same manner as in Example 1, a glass laminate was produced and subjected to a polishing treatment to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 11>

After the mixed solution was applied onto a support substrate by a die coater, it was allowed to stand at room temperature for 10 minutes, and then heat-hardened at 180 ° C for 60 minutes in the atmosphere to form a 15 μm hardened fluorenone resin layer. According to the same procedure as in Example 10, a glass laminate was produced and subjected to a polishing treatment to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Example 12>

After the mixed solution was applied onto a support substrate by a die coater, it was allowed to stand at room temperature for 30 minutes, and then heat-hardened at 180 ° C for 60 minutes in the atmosphere to form a 15 μm hardened fluorenone resin layer. According to the same procedure as in Example 10, a glass laminate was produced and subjected to a polishing treatment to separate the glass substrate subjected to the polishing treatment. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and is 0.100 μm or less.

<Comparative Example 1>

After the mixed solution was applied onto a support substrate by a die coater, it was heat-hardened at 180 ° C for 60 minutes in the air without standing, and a hardened fluorenone resin layer of 15 μm was formed without being left in the same manner as in Example 1. In the procedure, a glass laminate is produced and polished, and the glass substrate subjected to the polishing treatment is separated. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and exceeds 0.100 μm.

<Comparative Example 2>

After the mixed solution was applied onto a support substrate by a die coater, it was heat-hardened at 180 ° C for 60 minutes in the air without standing, and a hardened fluorenone resin layer of 15 μm was formed without being left in the same manner as in Example 2. In the procedure, a glass laminate is produced and polished, and the glass substrate subjected to the polishing treatment is separated. The various results are summarized in Table 1. Further, the filter center line undulation (W _CA ) of the second main surface of the glass substrate separated from the glass laminate is approximately the same as the filter center line of the resin layer, and exceeds 0.100 μm.

In the following Table 1, the solid content concentration refers to the solid content concentration (concentration other than the solvent) in the mixed liquid of the organopolyoxane composition, and the resin layer W _CA refers to the resin layer before the laminated glass substrate. The filter center line of the exposed surface of the resin layer in the support substrate is undulated. Further, the filter center line undulation is measured in accordance with JIS B-0610 (1987). Further, the cutoff value of the filter fluctuation curve was set to 0.8 mm, and the measurement length was set to 40 mm.

As shown in the above Table 1, in the embodiment in which the filter center line of the resin layer has an undulation of 0.100 μm or less, the filter center line undulation of the polished surface of the obtained glass substrate is substantially the same as the value of the resin layer, which is 0.100. Below μm. According to the results, it was confirmed that the surface of the glass substrate obtained by the present production method has a small fluctuation, and when a device such as a circuit electrode is formed on the glass substrate, the circuit electrode can be further suppressed as described in Patent Document 2. Problems such as lines and short circuits.

Moreover, it can be confirmed from the comparison of Examples 2 and 3 that the flatness of the resin layer is more excellent as the rest time is longer.

On the other hand, in Comparative Examples 1 and 2, as described in Patent Document 1, the resin layer was produced without a standing time. In these comparative examples, it was confirmed that the filter center line of the resin layer fluctuated by more than 0.100 μm, and as a result, the filter center line of the obtained glass substrate obtained had a fluctuation of the center line of the filter of more than 0.100 μm, which is not suitable as a glass substrate for electronic device manufacturing.

<Example 13>

In this example, an OLED was produced using the glass laminate produced by the polishing method produced in Example 1.

More specifically, molybdenum is formed on the second main surface of the glass substrate subjected to the rubbing treatment in the glass laminate by sputtering, and the gate electrode is formed by etching by photolithography. Then, by the plasma CVD method, tantalum nitride, intrinsic amorphous germanium, and n-type amorphous germanium are sequentially formed on the second main surface side of the glass substrate provided with the gate electrode, and then by sputtering. The molybdenum is formed into a film, and the gate insulating film, the semiconductor element portion, and the source/drain electrodes are formed by etching by photolithography. Then, by the plasma CVD method, the second main glass substrate After the surface layer is further formed into a film of tantalum nitride to form a passivation layer, indium tin oxide is formed into a film by sputtering, and the pixel electrode is formed by etching by photolithography.

Then, on the second main surface side of the glass substrate, 4,4',4"-tris(3-methylphenylphenylamino)triphenyl which is a hole injection layer is sequentially formed by a vapor deposition method. The base amine, bis[(N-naphthyl)-N-phenyl]benzidine as a hole transport layer, and 40% by volume of the 8-hydroxyquinoline aluminum complex (Alq ₃ ) as a light-emitting layer 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyryl]naphthalene-1,5-dicarbonitrile (BSN-BCN) Alq _{3 of the} electron transport layer. Then, aluminum is formed on the second main surface side of the glass substrate by sputtering, and the counter electrode is formed by etching by photolithography. Then, the counter electrode is formed. The second main surface of the glass substrate is sealed by laminating another glass substrate via an ultraviolet curing type. The glass laminate having the organic EL structure on the glass substrate obtained by the above procedure corresponds to an electronic device. A laminate of components.

Then, after the sealed body side of the obtained glass laminate was vacuum-adsorbed on the platen, a stainless steel cutter having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the fluorene-ketone resin layer at the corner of the glass laminate, and the resin was attached. The support substrate of the layer is separated from the glass laminate to obtain an OLED panel (corresponding to an electronic device; hereinafter referred to as panel A). The manufactured panel A connection IC (Integrated Circuit) driver was driven at normal temperature and normal pressure, and as a result, no display unevenness was observed in the driving region. Further, no display unevenness was observed in the case of driving in a high-temperature and high-humidity environment (80 ° C, 80% RH).

<Example 14>

In this example, an LCD was produced using the glass laminate produced by the polishing method manufactured in Example 1.

Two sheets of the glass laminate are prepared. First, molybdenum is formed on the second main surface of the glass substrate subjected to the polishing treatment in one of the glass laminates by sputtering, and is formed by etching by photolithography. Gate electrode. Then, by the plasma CVD method, a tantalum nitride, an intrinsic amorphous germanium, and an n-type non-crystalline film are sequentially formed on the second main surface side of the glass substrate provided with the gate electrode. The wafer is then formed into a film by sputtering, and a gate insulating film, a semiconductor element portion, and a source/drain electrode are formed by etching by photolithography. Then, a passivation layer is formed by forming a passivation layer on the second main surface side of the glass substrate by a plasma CVD method, and then indium tin oxide is formed by sputtering, and by photolithography. The etching forms a pixel electrode. Then, the polyimide film was applied onto the second main surface of the glass substrate on which the pixel electrode was formed by a roll coating method, and an alignment layer was formed by thermal curing and polished. The obtained glass laminate is referred to as a glass laminate A1.

Then, chromium is formed on the second main surface of the glass substrate subjected to the polishing treatment in the other glass laminate by sputtering, and the light shielding layer is formed by etching by photolithography. Then, a color filter is applied by a die coating method on the second main surface side of the glass substrate provided with the light shielding layer, and a color filter layer is formed by photolithography and thermal curing. Then, indium tin oxide is further formed on the second main surface side of the glass substrate by sputtering to form a counter electrode. Then, an ultraviolet curable resin liquid is applied onto the second main surface of the glass substrate provided with the counter electrode by a die coating method, and a columnar spacer is formed by photolithography and thermal hardening. Then, the polyimide film was applied onto the second main surface of the glass substrate on which the columnar spacers were formed by a roll coating method, and the alignment layer was formed by thermal curing and polished. Then, the sealing resin liquid is drawn into a frame shape on the second main surface side of the glass substrate by a dispensing method, and liquid crystal is dropped in the frame by a dispensing method, and then the glass laminated body A1 is used to form two sheets. The second main surface side of the glass substrate of the glass laminate is bonded to each other, and a laminate having an LCD panel is obtained by ultraviolet curing and thermal curing. Hereinafter, the laminated body having the LCD panel will be referred to as a laminated body B2 of the attached panel.

Then, in the same manner as in the first embodiment, the support substrate of the resin layer on both sides is peeled off from the laminated body B2 of the attached panel, and the LCD panel B including the substrate on which the TFT array is formed and the substrate on which the color filter is formed is obtained ( Equivalent to electronic devices).

The manufactured LCD panel B was connected to the IC driver and driven under normal temperature and normal pressure, and as a result, no display unevenness was observed in the driving region. Also, in a high temperature and high humidity environment (80 ° C, 80% No display unevenness was observed in the case of driving under RH).

<Comparative Example 3>

The glass laminate subjected to the grinding treatment was produced in accordance with the procedure of Comparative Example 1.

Then, using the obtained glass laminate, an OLED panel was produced in the same manner as in Example 13.

The panel-connected IC driver was driven at normal temperature and normal pressure. As a result, no unevenness was observed in the driving area, but if it was continuously connected for a long time in a high-temperature and high-humidity environment (80 ° C, 80% RH), A partial display is uneven.

The present application is based on Japanese Patent Application No. 2012-007927, filed on Jan.

Claims (12)

A method of manufacturing an electronic device comprising the steps of: a laminating step of supporting a substrate having a resin layer having a supporting substrate and a resin layer fixed on one surface of the supporting substrate and exposing the exposed surface of the resin layer The exposed surface of the resin layer and the first main surface of the glass substrate having a thickness of 0.3 mm or less of the first main surface and the second main surface are used as an accumulation layer, and the support substrate with the resin layer and the glass substrate are laminated in a layer. a glass laminate; a polishing step of polishing the second main surface of the glass substrate in the glass laminate; and a member forming step of forming a member for the electronic device on the polished second main surface of the glass substrate a separation step of separating the glass substrate and the support substrate with the resin layer of the member for the electronic device, and obtaining an electronic device including the glass substrate and the member for the electronic device; and the exposed surface of the resin layer The surface undulation is 0.100 μm or less with a filter center line undulation (W _CA ). The method of producing an electronic device according to claim 1, wherein the resin of the resin layer is an fluorenone resin. The method of producing an electronic device according to claim 2, wherein the fluorenone resin is a reaction hardened product of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene. The method of manufacturing an electronic device according to any one of claims 1 to 3, wherein the grinding is chemical mechanical polishing (CMP). The method of manufacturing an electronic device according to any one of claims 1 to 3, wherein the glass substrate comprises an alkali-free glass containing a composition based on an oxide based on an oxide content: SiO ₂ : 50 to 66%, Al ₂ O ₃ : 10.5~24%, B ₂ O ₃ : 0~12%, MgO: 0~8%, CaO: 0~14.5%, SrO: 0~24%, BaO: 0~13.5%, MgO+CaO+ SrO+BaO: 9~29.5%, and ZrO ₂ : 0~5%. The method of manufacturing an electronic device according to claim 4, wherein the glass substrate comprises an alkali-free glass containing a composition based on an oxide standard: SiO ₂ : 50 to 66%, and Al ₂ O ₃ : 10.5 to 24 %, B ₂ O ₃ : 0~12%, MgO: 0~8%, CaO: 0~14.5%, SrO: 0~24%, BaO: 0~13.5%, MgO+CaO+SrO+BaO: 9~ 29.5%, and ZrO ₂ : 0 to 5%. The method of manufacturing an electronic device according to any one of claims 1 to 3, wherein the glass substrate comprises an alkali-free glass containing a composition of the following composition, which is represented by a mass percentage based on an oxide: SiO ₂ : 58 to 66%, Al ₂ O ₃ : 15 to 22%, B ₂ O ₃ : 5 to 12%, MgO: 0 to 8%, CaO: 0 to 9%, SrO: 3 to 12.5%, BaO: 0 to 2%, and MgO + CaO +SrO+BaO: 9~18%. The method for producing an electronic device according to claim 4, wherein the glass substrate comprises an alkali-free glass containing a composition based on an oxide standard: SiO ₂ : 58 to 66%, and Al ₂ O ₃ : 15 to 22 %, B ₂ O ₃ : 5 to 12%, MgO: 0 to 8%, CaO: 0 to 9%, SrO: 3 to 12.5%, BaO: 0 to 2%, and MgO + CaO + SrO + BaO: 9 ~18%. A method for producing a glass laminate, wherein the glass laminate comprises a ground glass substrate, and the method comprises the steps of: forming a resin layer having a support substrate and a single surface fixed to the support substrate and exposing the resin layer The exposed surface of the resin layer of the support substrate with a resin layer having a peelable surface, and the first main surface of the glass substrate having a thickness of 0.3 mm or less of the first main surface and the second main surface are used as an integrated layer. And the glass substrate is obtained by laminating the support substrate with the resin layer and the glass substrate; and a polishing step of polishing the second main surface of the glass substrate in the glass laminate; and the surface of the resin layer is undulated on the surface The filter center line undulation (W _CA ) is calculated to be 0.100 μm or less. The method for producing a glass laminate according to claim 9, wherein the resin of the resin layer is an fluorenone resin. The method for producing a glass laminate according to claim 10, wherein the fluorenone resin is a reaction hardened product of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene. The method for producing a glass laminate according to any one of claims 9 to 11, wherein the polishing is chemical mechanical polishing (CMP).