JP5887946B2 - Method for manufacturing electronic device and method for manufacturing glass laminate - Google Patents

Description

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

  In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and the glass substrates used in these devices have been made thinner. Progressing. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the device manufacturing process.

  Therefore, conventionally, a method of forming a device member (for example, a thin film transistor) on a glass substrate thicker than the final thickness and then thinning the glass substrate by chemical etching is widely used. However, in this method, for example, when the thickness of one glass substrate is reduced from 0.7 mm to 0.2 mm or 0.1 mm, most of the original glass substrate material is scraped off with an etching solution. Therefore, it is not preferable from the viewpoint of productivity and use efficiency of raw materials.

  In addition, in the method of thinning a glass substrate by the above chemical etching, if a fine scratch exists on the surface of the glass substrate, a fine recess (etch pit) is formed from the scratch by the etching process, resulting in an optical defect. There was a case.

Recently, in order to cope with the above problems, a laminate in which a thin glass substrate and a reinforcing plate are laminated is prepared, a display device is formed on the thin glass substrate of the laminated body, and then the reinforcing plate is separated from the thin glass substrate. A method has been proposed (see, for example, Patent Document 1). The reinforcing plate has a support substrate and a resin layer fixed on the support substrate, and the resin layer and the thin glass substrate are in close contact with each other in a peelable manner. The interface between the resin layer of the laminate and the thin glass substrate is peeled off, and the reinforcing plate separated from the thin glass substrate can be laminated with a new thin glass substrate and reused as a laminate.
On the other hand, as described in paragraph [0084] of Patent Document 2, if there is a undulation larger than 0.100 μm on the surface of glass, it becomes difficult to accurately pattern circuit electrodes and the like formed on the surface. As a result, it is known that the probability that the circuit electrode is disconnected or short-circuited is increased, the yield of electronic devices such as a liquid crystal display is decreased, and the reliability is difficult to ensure.

International Publication No. 07/018028 Pamphlet JP 2009-13049 A

The present inventors have examined the invention described in Patent Document 1, and when forming a member for an electronic device such as a display member on a thin glass substrate of a laminate in a predetermined pattern, It has been found that the production yield of the display panel may be lowered due to the deviation.
When the cause was examined, as described in Patent Document 2, surface irregularities such as waviness on the surface of the laminated thin glass were the cause of the decrease in the production yield as described above.

  Therefore, the present inventors polished the surface of the thin glass substrate in the laminate described in Patent Document 1 to form a flat surface, and formed an electronic device member and the like thereon. However, when the thin glass substrate on which the electronic device member is formed is peeled off from the laminate, undulation is generated again on the surface of the thin glass substrate on which the electronic device member is formed after peeling. Such surface waviness causes a decrease in productivity yield as described above.

  The present invention has been made in view of the above-described problems, and the flatness of the glass substrate surface can be achieved even when the electronic device member is formed and after the glass substrate on which the electronic device member is formed is peeled off. An object of the present invention is to provide a method for manufacturing an electronic device that is excellent and as a result can suppress a decrease in production yield of the electronic device. Another object of the present invention is to provide a method for producing a glass laminate used for producing the electronic device.

  The inventor examined the problems of the prior art and found that the surface waviness on the surface of the resin layer on which the glass substrate is laminated is related to the above problem. As a result of intensive studies based on the findings, the inventors have found that the above-described problems can be solved by the following configuration, and have completed the present invention.

That is, in order to achieve the above-mentioned object, the first aspect of the present invention is a support with a resin layer having a support substrate and a resin layer fixed to one surface thereof, and the exposed surface of the resin layer exhibits easy peelability. Using the exposed surface of the resin layer of the substrate and the first main surface of a glass substrate having a first main surface and a second main surface and having a thickness of 0.3 mm or less as a laminated surface, the support substrate with a resin layer and glass A laminating step of closely laminating a substrate to obtain a glass laminate, a polishing step of polishing the second main surface of the glass substrate in the glass laminate, and the polished second main surface of the glass substrate A member forming step for forming an electronic device member, the glass substrate on which the electronic device member is laminated, and the support substrate with a resin layer are separated to include the glass substrate and the electronic device member. A separation step of obtaining an electronic device, and an exposed surface of the resin layer Definitive surface waviness is 0.100μm or less filtered centerline waviness (W _CA), is a manufacturing method of an electronic device.

In the first aspect, the resin of the resin layer is preferably a silicone resin.
In the first aspect, the silicone resin is preferably a reaction cured product of an organoalkenylpolysiloxane and an organohydrogenpolysiloxane.
In the first aspect, the polishing is preferably chemical mechanical polishing (CMP).

1st aspect WHEREIN: It is preferable that a glass substrate consists of an alkali free glass containing the following in the mass percentage display of an oxide basis.
SiO ₂ : 50 to 66%
Al ₂ O _3: 10.5~24%
B ₂ O _3: 0~12%
MgO: 0 to 8%
CaO: 0 to 14.5%
SrO: 0 to 24%
BaO: 0 to 13.5%
MgO + CaO + SrO + BaO: 9 to 29.5%
ZrO ₂ : 0 to 5%

1st aspect WHEREIN: It is preferable that a glass substrate consists of an alkali free glass containing the following in the mass percentage display of an oxide basis.
SiO _2: 58~66%
Al ₂ O ₃ : 15-22%
B ₂ O _3: 5~12%
MgO: 0 to 8%
CaO: 0 to 9%
SrO: 3 to 12.5%
BaO: 0 to 2%
MgO + CaO + SrO + BaO: 9 to 18%

According to a second aspect of the present invention, there is provided a support substrate and a resin layer fixed to one surface thereof, and the exposed surface of the resin layer of the support substrate with a resin layer in which the exposed surface of the resin layer exhibits easy peelability; A glass substrate having a first main surface and a second main surface and having a thickness of 0.3 mm or less as a laminated surface, the support substrate with a resin layer and the glass substrate are adhered and laminated, 0 and laminated to obtain a laminate, a polishing step of polishing the second main surface of the glass substrate of the glass laminate in surface waviness of the resin layer surface is in filtered centerline waviness (W _CA). It is a manufacturing method of the glass laminated body containing the grind | polished glass substrate which is 100 micrometers or less.

In the second aspect, the resin of the resin layer is preferably a silicone resin.
In the second embodiment, the silicone resin is preferably a reaction cured product of an organoalkenylpolysiloxane and an organohydrogenpolysiloxane.
In the second embodiment, the polishing is preferably chemical mechanical polishing (CMP).

  According to the present invention, the flatness of the surface of the glass substrate is excellent during the formation of the electronic device member and after the glass substrate on which the electronic device member is formed, and as a result, the production yield of the electronic device is reduced. It is possible to provide a method for manufacturing an electronic device that can suppress the above. Moreover, this invention can also provide the manufacturing method of the glass laminated body used for manufacture of this electronic device.

It is process drawing of the manufacturing method of the electronic device of this invention. It is typical sectional drawing of one Embodiment of the glass laminated body which concerns on this invention. It is typical sectional drawing of one Embodiment of the laminated body with the member for electronic devices which concerns on this invention. It is typical sectional drawing of the grinding | polishing process and isolation | separation process which use the glass laminated body of a prior art.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not deviated from the scope of the present invention. Various modifications and substitutions can be made.
In the present invention, the resin layer and the glass substrate are in close contact with each other so that the peel strength at the interface between the support substrate layer and the resin layer is higher than the peel strength at the interface between the resin layer and the glass substrate. The support substrate and the resin layer are fixed.

As a cause of undulations on the surface of the glass substrate in the laminate used in the prior art (invention of Patent Document 1), the inventors of the present invention have a surface of the resin layer in contact with the undulation of the surface of the glass substrate itself. We found that the latter factor was particularly significant. First, the relationship between the undulation on the surface of the resin layer and the problems of the prior art will be described with reference to FIG.
As shown in FIG. 4A, in the conventional glass laminate 100, when the surface of the resin layer 114 on the support substrate 112 has surface irregularities such as waviness, the glass substrate 116 disposed in contact with the surface is provided. Therefore, the glass substrate 116 is deformed so as to follow the surface waviness on the surface of the resin layer 114 (see FIG. 4A). After that, by performing a polishing process, the exposed first main surface 116a of the glass substrate 116 is temporarily planarized. However, if the glass substrate 116 and the resin layer 114 are peeled off, the second main surface 116b of the glass substrate 116 that has been originally flat acts as a flattening force, and is flattened during the polishing process. The first main surface 116a is stressed and surface undulation appears again. That is, the surface waviness of the resin layer 114 is transferred to the surface of the glass substrate. Such surface waviness after the glass substrate 116 is peeled off occurs even after the electronic device member is formed on the first main surface 116 a of the glass substrate 116. Therefore, a desired effect cannot be obtained simply by providing a polishing step.

Therefore, the present inventors have found that the above problem can be solved by setting the waviness on the surface of the resin layer to a predetermined value or less and providing a polishing step. By reducing the waviness on the surface of the resin layer, the deformation of the glass substrate laminated thereon can be reduced, and the waviness on the surface of the resin layer can be transferred to the surface of the glass substrate even after the separation step described later. Can be suppressed. Furthermore, the surface waviness and minute wrinkles on the surface of the glass substrate itself can be removed by the polishing process. In particular, if the surface waviness on the exposed surface of the resin layer is 0.100 μm or less in the filtered center line waviness (W _CA ), the surface waviness of the glass substrate laminated thereon is also less than that. The reduction in the yield of electronic devices and the securing of reliability are achieved as described above.
Below, the manufacturing method of an electronic device and a laminated body is demonstrated in order of each process.

FIG. 1 is a flowchart showing a manufacturing process in an embodiment of a method for manufacturing an electronic device of the present invention. As shown in FIG. 1, the electronic device manufacturing method includes a stacking step (S102), a polishing step (S104), a member forming step (S106), and a separation step (S108).
Below, the material used in each process and its procedure are explained in full detail. First, the lamination step (S102) will be described in detail.

[Lamination process]
The laminating step S102 includes a resin layer with 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 a predetermined plate thickness having the first main surface and the second main surface. In this step, the resin layer of the support substrate and the glass substrate are adhered and laminated to obtain a glass laminate. By carrying out the step S102, a glass laminate used in the polishing step S104 and the member forming step S106 described later is obtained.

FIG. 2 is a schematic cross-sectional view of an example of a glass laminate according to the present invention.
As shown in FIG. 2, the glass laminate 10 is a laminate in which a support substrate 12 layer, a glass substrate 16 layer, and a resin layer 14 exist therebetween. One surface of the resin layer 14 is fixed to the layer of the support substrate 12, the other surface is in contact with the first main surface 16 a of the glass substrate 16, and the interface between the resin layer 14 and the glass substrate 16 is peeled off. Close contact is possible. In other words, the resin layer 14 is easily peelable from the first main surface 16 a of the glass substrate 16.
The two-layer portion including the layer of the support substrate 12 and the resin layer 14 reinforces the glass substrate 16 in the member forming step S106 for manufacturing an electronic device member such as a liquid crystal panel. In addition, what the 2 layer part which consists of the layer of the support substrate 12 of the glass laminated body 10 and the resin layer 14 became independent from the glass laminated body 10 is called the support substrate 18 with a resin layer. In the support substrate 18 with the resin layer, the resin layer 14 is fixed to the support substrate 12.

  This glass laminated body 10 is used until member formation process S106. That is, the glass laminate 10 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 16b of the glass substrate 16. Thereafter, the layer of the support substrate 18 with the resin layer is peeled off at the interface with the layer of the glass substrate 16, and the layer of the support substrate 18 with the resin layer does not become a part constituting the electronic device. The separated support substrate 18 with the resin layer is laminated with a new glass substrate 16 and can be reused as the glass laminate 10.

  Below, each layer (a support substrate, a resin layer, a glass substrate) which comprises a glass laminated body is explained in full detail first, and the procedure of this process S102 is explained in full detail after that.

(Support substrate)
The support substrate 12 cooperates with the resin layer 14 to support and reinforce the glass substrate 16, and in manufacturing the electronic device member in the member forming step S <b> 106 (electronic device member manufacturing step) described later. The substrate 16 is prevented from being deformed, scratched or damaged. In addition, when a glass substrate having a thickness smaller than that of the conventional glass substrate is used, the glass laminate 10 having the same thickness as that of the conventional glass substrate is adapted to the glass substrate having the conventional thickness in the member forming step S106. One of the purposes of using the support substrate 12 is to make it possible to use manufacturing technology and manufacturing equipment.

  As the support substrate 12, for example, a metal plate such as a glass plate, a plastic plate, a SUS plate, or a ceramic plate is used. When the member forming step S106 involves 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, and more preferably formed of the same material as the glass substrate 16. The support substrate 12 is preferably a glass plate. In particular, the support substrate 12 is preferably a glass plate made of the same glass material as the glass substrate 16.

It is preferable that the surface waviness of the support substrate 12 on which a resin layer 14 to be described later is laminated is 0.100 μm or less in terms of filtered center line waviness (W _CA ). Here, “surface waviness” is a value obtained by measuring W _CA (filtered centerline waviness) described in JIS B-0610 (1987) using a known stylus type surface shape measuring device. In the present invention, the cutoff value of the filtered waviness curve is 0.8 mm, and the measurement length is 40 mm. If the surface waviness is within the above range, the surface waviness of the surface (easy peelable surface) 14a that contacts the glass substrate 16 of the resin layer 14 to be described later becomes small, and as a result, even after the separation step S108 described later, the electronic device The surface waviness of the second main surface of the glass substrate 16 on which the member for use is formed is small, and the occurrence of displacement of the electronic device member is suppressed. Of these, the filtered center line undulation is preferably 0.070 μm or less, and more preferably 0.030 μm or less, in that the above effect is more excellent. The lower limit is not particularly limited, but is preferably 0 μm.
In addition, as a method for reducing the surface waviness on the surface of the support substrate 12, a known polishing method (for example, a known physical polishing or chemical polishing, more specifically, CMP or the like) can be used.

  The support substrate 12 may be thicker than the glass substrate 16 or thinner. Preferably, the thickness of the support substrate 12 is 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, when the current member forming process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the glass substrate 16 and the thickness of the resin layer 14 is 0.1 mm, the support is provided. The thickness of the substrate 12 is 0.4 mm. In general, the thickness of the support substrate 12 is preferably 0.2 to 5.0 mm.

  When the support substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more because it is easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.

The difference in average linear expansion coefficient between glass substrate 16 and support substrate 12 at 25 to 300 ° C. (hereinafter simply referred to as “average linear expansion coefficient”) is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably It is 300 × 10 ⁻⁷ / ° C. or less, more preferably 200 × 10 ⁻⁷ / ° C. or less. If the difference is too large, the glass laminate 10 may be severely warped or the glass substrate 16 and the support substrate 18 with a resin layer may be peeled off during heating and cooling in the member forming step S106. When the material of the glass substrate 16 and the material of the support substrate 12 are the same, it can suppress that such a problem arises.

(Resin layer)
The resin layer 14 is fixed on at least one surface of the support substrate 12 and is in close contact with the glass substrate 16 so as to be peeled off. The resin layer 14 prevents displacement of the glass substrate 16 until the operation of separating the glass substrate 16 and the support substrate 12 is performed, and is easily separated from the glass substrate 16 by the separation operation, so that the glass substrate 16 and the like are separated. Prevent damage by operation. Further, the resin layer 14 is fixed to the support substrate 12, and the resin layer 14 and the support substrate 12 are not separated in the separation operation, and the support substrate 18 with the resin layer is obtained by the separation operation. 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 perform separation by providing a separation starting point at the interface.
The surface 14a of the resin layer 14 that contacts the glass substrate 16 is in close contact with the first main surface 16a of the glass substrate 16 in a peelable manner. In this invention, the property which can peel this resin layer surface 14a easily is called easy peelability (peelability).

  In the present invention, the above-mentioned fixing and (separable) adhesion have a difference in peeling strength (that is, stress required for peeling), and fixing means that the peeling strength is larger than the adhesion. Further, the peelable adhesion means that it can be peeled at the same time that it can be peeled without causing peeling of the fixed surface. Specifically, in the glass laminate 10 of the present invention, when the operation of separating the glass substrate 16 and the support substrate 12 is performed, it means that the peeled surface is peeled off and the fixed surface is not peeled off. . 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 two, the glass substrate 16 and the support substrate 18 with a resin layer.

The resin layer 14 is preferably fixed to the surface of the support substrate 12 with a strong bonding force such as an adhesive force or an adhesive force. For example, the reaction-curable resin is reacted and cured on the surface of the support substrate 12 so that the cured resin adheres to the surface of the support substrate 12. In addition, the bonding force between the surface of the support substrate 12 and the resin layer 14 can be increased by applying a treatment (for example, treatment using a coupling agent) that generates a strong bonding force between the surface of the support substrate 12 and the resin layer 14. .
On the other hand, the resin layer 14 is preferably bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, for example, with a bonding force caused by van der Waals force between solid molecules. The resin layer surface 14a before being in contact with the glass substrate 16 is preferably an easily peelable surface, and by contacting the easily peelable resin layer surface 14a with the first main surface 16a of the glass substrate 16, Both surfaces can be bonded with a weak bonding force. That is, if the resin layer surface 14a is easily peelable, the peelability at the interface with the first main surface 16a of the glass substrate 16 becomes better. Both surfaces are in contact with each other without any gap, and this state is referred to as close contact in the present invention.

In addition, the resin layer surface can be made easily peelable also by the surface treatment which gives easy peelability to the surface of the resin layer which is not easily peelable in a normal meaning. In addition, even a resin layer that is not easily peelable in a normal sense is a resin that can be adhered with a sufficiently low bonding force with respect to the above-described fixing force (and breakage of a glass substrate or a support substrate, etc.) Can be used as a material for the resin layer without surface treatment.
In particular, when the surface of the resin layer in contact with the glass substrate is easily peelable, a part of the surface of the resin layer is hardly left due to breakage of the resin layer surface 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. For this reason, the peel 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. It is preferable that the resin layer 14 and the support substrate 12 are bonded together by adhesion or adhesion. However, the present invention is not limited to this, and the resin layer 14 and the support substrate 12 are bonded by a force due to another bonding force as long as the bonding force is relatively higher than the bonding force of the resin layer 14 to the glass substrate 16. It may be.

The surface waviness on the surface 14a of the resin layer 14 (the surface in contact with the glass substrate 16) is 0.100 μm or less as a filtered center line waviness (W _CA ). The “surface waviness” is a value obtained by measuring W _CA (filtered center line waviness) described in JIS B-0610 (1987) using a known stylus type surface shape measuring device. In the present invention, the cutoff value of the filtered waviness curve is 0.8 mm, and the measurement length is 40 mm. If the surface waviness is within the above range, the occurrence of surface waviness on the second main surface of the glass substrate 16 on which the electronic device member is formed is suppressed even after the separation step S108 described later. As a result, occurrence of displacement of the electronic device member is suppressed. In the point which this effect is more excellent, 0.070 micrometer or less is preferable and 0.030 micrometer or less is more preferable. The lower limit is not particularly limited, but is preferably 0 μm.
In addition, as a method of reducing the surface waviness on the surface of the resin layer 14, a resin using a method using the support substrate 12 with a small surface waviness or a resin layer forming composition used when forming the resin layer 14 is used. A method of allowing the support substrate 12 provided with the resin layer forming composition layer to stand after forming a layer of the layer forming composition (hereinafter also referred to as a resin layer forming composition layer) on the support substrate 12 and before curing. The flatness is transferred by pressing a flat member (preferably in a heating environment) having a flat surface (surface having a filtered center line waviness (W _CA ) of 0.100 μm or less) on the surface of the resin layer 14. And a method of etching the surface of the resin layer 14.

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

  The thickness of the resin layer 14 is not particularly limited, but is preferably 15 μm or less, more preferably 2 to 15 μm, and even more preferably 2 to 10 μm in that the surface waviness can be reduced. This is because if the thickness of the resin layer 14 is within such a range, the resin layer 14 and the glass substrate 16 are sufficiently adhered. In addition, even if bubbles or foreign substances may be present between the resin layer 14 and the glass substrate 16, the occurrence of distortion defects in the glass substrate 16 can be suppressed. On the other hand, if the resin layer 14 is too thick, it takes time and materials to form the resin layer 14, which is not economical and the surface undulation tends to increase.

The resin layer 14 may be composed of two or more layers. In this case, “the thickness of the resin layer 14” means the total thickness of all the layers.
Moreover, when the resin layer 14 consists of two or more layers, the kind of resin which forms each layer may differ.

  The resin layer 14 is preferably made of a material having a glass transition point lower than room temperature (about 25 ° C.) or having no glass transition point. This is because it can be more easily peeled off from the glass substrate 16 and at the same time the adhesion to the glass substrate 16 becomes sufficient.

  Moreover, since the resin layer 14 is often heat-treated in the member forming step S106, the resin layer 14 preferably has heat resistance.

  Moreover, when the elasticity modulus of the resin layer 14 is too high, it exists in the tendency for adhesiveness with the glass substrate 16 to become low. On the other hand, if the elastic modulus of the resin layer 14 is too low, the peelability is lowered.

  The kind of resin which forms the resin layer 14 is not specifically limited. For example, acrylic resin, polyolefin resin, polyurethane resin, or silicone resin can be used. Several types of resins can be mixed and used. Of these, silicone resins are preferred. This is because the silicone resin is excellent in heat resistance and peelability. Moreover, when the support substrate 12 is a glass plate, it is because it is easy to fix to a glass plate by the condensation reaction with the silanol group of the glass plate surface. In the state where the silicone resin layer is interposed between the support substrate 12 and the glass substrate 16, for example, it is preferable that the peelability does not substantially deteriorate even if the silicone resin layer is processed in the atmosphere at about 200 ° C. for about 1 hour.

  The resin layer 14 is preferably made of a silicone resin (cured product) used for release paper among silicone resins. The silicone resin of the release layer of the release paper is formed by curing a layer of the curable silicone resin composition coated on the release paper. Using this curable silicone resin composition, a resin layer made of a cured silicone resin formed by curing the curable silicone resin composition on the surface of the support substrate 12 adheres to the surface of the support substrate 12 and its free surface. Is preferable because it has excellent 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, it is possible to suppress the occurrence of distortion defects of the glass substrate 16.

  The curable silicone resin composition used to form such a resin layer 14 has a condensation reaction type silicone resin composition, an addition reaction type silicone resin composition, an ultraviolet curable type silicone resin composition, and a curing mechanism. Although classified into the electron beam curable silicone resin composition, any of them can be used. Among these, addition reaction type silicone resin compositions are preferred. This is because the curing reaction is easy, the degree of easy peeling of the resin layer surface 14a after curing is good, and the heat resistance is also high.

The addition reaction type silicone resin composition is a curable composition that contains a main agent and a crosslinking agent and cures in the presence of a catalyst such as a platinum-based catalyst. Curing of the addition reaction type silicone resin composition is accelerated by heat treatment. The main component in the addition reaction type silicone resin composition is preferably an organopolysiloxane having an alkenyl group (such as a vinyl group) bonded to a silicon atom (that is, an organoalkenylpolysiloxane, preferably a straight chain). An alkenyl group or the like serves as a crosslinking point. The crosslinking agent in the addition reaction type silicone resin composition is an organopolysiloxane having a hydrogen atom (hydrosilyl group) bonded to a silicon atom (that is, an organohydrogenpolysiloxane, preferably a straight chain). Is preferred, and a hydrosilyl group or the like serves as a crosslinking point.
The addition reaction type silicone resin composition is cured by an addition reaction between the crosslinking points of the main agent and the crosslinking agent.

  Moreover, the curable silicone resin composition has a solvent type, an emulsion type, and a solventless type in terms of form, and any type can be used. Among these, a solventless type is preferable. This is because productivity, safety, and environmental characteristics are excellent. Further, it does not contain a solvent that causes foaming at the time of curing when forming the resin layer 14, that is, at the time of heat curing, ultraviolet curing, or electron beam curing, so that bubbles are unlikely to remain in the resin layer 14.

  Moreover, as a curable silicone resin composition, specifically, as a trade name or a model number that is commercially available, KNS-320A, KS-847 (both manufactured by Shin-Etsu Silicone), TPR6700 (Momentive Performance Materials Japan Joint) Company), a combination of vinyl silicone “8500” (Arakawa Chemical Industries) and methylhydrogenpolysiloxane “12031” (Arakawa Chemical Industries), vinyl silicone “11364” (Arakawa Chemical Industries) and methyl Combination with hydrogenpolysiloxane "12031" (Arakawa Chemical Industries), combination of vinyl silicone "11365" (Arakawa Chemical Industries) and methylhydrogenpolysiloxane "12031" (Arakawa Chemical Industries), etc. Is mentioned.

  KNS-320A, KS-847, and TPR6700 are curable silicone resin compositions that contain a main agent and a crosslinking agent in advance.

  Further, the silicone resin forming the resin layer 14 (cured product of the curable silicone resin composition) has a property that components such as low molecular weight silicone in the silicone resin layer are difficult to migrate to the glass substrate 16, that is, low silicone migration. It is preferable to have properties.

(Method for producing resin layer)
The method for fixing the resin layer 14 on the support substrate 12 is not particularly limited.
For example, a resin layer forming step of forming and fixing the easily peelable resin layer 14 on the support substrate 12 may be performed before the stacking 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) on the support substrate 12 may be performed. More specifically, a resin layer forming composition layer that becomes the resin layer 14 is formed on the surface of the support substrate 12, and then the resin layer forming composition is cured and fixed on the support substrate 12. A method of forming layer 14 is preferred.
In addition, for example, the resin layer 14 can be formed by a method of fixing a film-like resin to the surface of the support substrate 12. Specifically, in order to impart a high fixing force (high peel strength) to the surface of the film on the surface of the support substrate 12, a surface modification process (priming process) is performed on the surface of the support substrate 12, and the support substrate 12 The method of fixing on top is mentioned. For example, chemical methods (primer treatment) that improve the fixing force chemically such as silane coupling agents, physical methods that increase surface active groups such as flame (flame) treatment, surface treatments such as sandblast treatment Examples thereof include a mechanical processing method for increasing the catch by increasing the roughness.

  In the method of forming a resin layer forming composition layer to be the resin layer 14 on the surface of the supporting substrate 12 and then curing the resin layer forming composition layer to form the resin layer 14, Examples of the method of forming the resin layer forming composition layer include a method of coating the resin layer forming composition on the support substrate 12. Examples of the coating method include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. From such a method, it can select suitably according to the kind of resin composition.

In the case of coating a resin layer forming composition comprising a resin layer 14 on the supporting substrate 12, and more is that the coating amount is preferably from 1 to 100 g / m ^2, is 5 to 20 g / m ² preferable.

  When a resin and a resin are contained in the resin layer forming composition, in order to produce the resin layer 14 having a surface exhibiting the predetermined surface waviness described above, the content of the solvent in the resin layer forming composition is: It is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less with respect to the total amount of the composition. By adjusting the amount of the solvent within the above range, the amount of the solvent volatilized from the formed composition layer can be suppressed, and as a result, the resin layer 14 with less surface waviness can be obtained. The lower limit of the amount of the solvent is not particularly limited as long as the resin layer forming composition can be applied, but is preferably 30% by mass or more from the viewpoint of handleability.

The type of the solvent used in the resin layer forming composition is not particularly limited, but it is preferable to use a solvent having a boiling point of 100 ° C. or lower in terms of further suppressing the occurrence of surface waviness of the resulting resin layer 14. .
The viscosity of the resin layer forming composition is preferably 40 mPas or less, and more preferably 20 mPas or less, from the viewpoint that the resin layer 14 with less surface waviness can be formed. In addition, although a minimum in particular is not restrict | limited, From the point of the film formability of a composition, it is preferable that it is 3 mPas or more.

  In addition, as resin contained in the composition for resin layer formation, resin which can form the resin layer mentioned above is mentioned, Especially, curable silicone is mentioned preferably.

For example, when the resin layer 14 is formed from an addition reaction type silicone resin composition, the resin layer forming composition X composed of a mixture of an organoalkenylpolysiloxane, an organohydrogenpolysiloxane, and a catalyst is used as the spray coating method described above. Is applied onto the support substrate 12 by a known method, and then cured by heating.
The heat curing conditions vary depending on the amount of the catalyst, but the reaction is carried out at 50 ° C. to 250 ° C., preferably 100 ° C. to 200 ° C. in the atmosphere. In this case, the reaction time is 5 to 60 minutes, preferably 10 to 30 minutes.

  By thermally curing the resin layer forming composition X, the silicone resin is chemically bonded to the support substrate 12 during the curing reaction, and the silicone resin layer is bonded to the support substrate 12 by the anchor effect, thereby being bonded. To do. By these actions, the silicone resin layer is firmly fixed to the support substrate 12. In addition, also when forming the resin layer which consists of resin other than a silicone resin from the composition for resin layer formation, the resin layer 14 fixed to the support substrate 12 by the method similar to the above can be formed.

A resin layer forming composition layer that becomes the resin layer 14 is formed on the surface of the support substrate 12, and then the resin layer 14 fixed on the support substrate 12 is cured by curing the resin layer forming composition layer. In the method of forming, the support substrate 12 provided with the resin layer forming composition layer is allowed to stand after the resin layer forming composition layer is formed and before curing, in that the flatness of the formed resin layer 14 is more excellent. It is preferable to do. By allowing to stand for a predetermined time, the flatness of the surface of the resin layer forming composition layer is improved, and the volatile components contained in the resin layer forming composition layer are removed so that the surface of the resin layer 14 is cured during curing. Roughening can be further suppressed.
The temperature at the time of leaving still is not restrict | limited, What is necessary is just to leave still at the temperature lower than the temperature of the heating conditions in the case of hardening, It is preferable that it is 0-100 degreeC, 0-room temperature (about 25 degreeC) Is more preferable.
The standing time is not particularly limited, and is preferably 30 seconds to 1 hour, more preferably 1 minute to 10 minutes, in that the balance between the flatness and productivity of the resin layer 14 is more excellent.
Moreover, you may stand still under reduced pressure as needed. The conditions for reducing the pressure are not particularly limited, but 1 to 1000 Pa is preferable and 10 to 1000 Pa is more preferable in that the balance between the flatness of the resin layer 14 and the operational efficiency is more excellent.

(Glass substrate)
As for the glass substrate 16, the 1st main surface 16a is closely_contact | adhered with a resin layer, and the member for electronic devices is provided in the 2nd main surface 16b on the opposite side to the resin layer 14 side.
The glass substrate 16 may be of a general type, 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 and has a low heat shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.

  When the linear expansion coefficient of the glass substrate 16 is large, the member forming step S106 is often accompanied by heat treatment, and various inconveniences are likely to occur. For example, when a TFT is formed on the glass substrate 16, if the glass substrate 16 on which the TFT is formed is cooled under heating, the TFT may be displaced excessively due to thermal contraction of the glass substrate 16.

  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 general one, and for example, a float method, a fusion method, a slot down draw method, a full call method, a rubber method, or the like is used. The glass substrate 16 having a particularly small thickness can be obtained by heating a glass once formed into a plate shape to a moldable temperature and then stretching it by means of stretching or the like to make it thin (redraw method).

  The glass of the glass substrate 16 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses mainly composed of silicon oxide are preferable. As the oxide glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.

  As the glass of the glass substrate 16, glass suitable for the type of electronic device member and its manufacturing process is employed. For example, a glass substrate for a liquid crystal panel is made of glass (non-alkali glass) that does not substantially contain an alkali metal component because the elution of an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) Ingredients are included). Thus, the glass of the glass substrate is appropriately selected based on the type of device to be applied and its manufacturing process.

The glass of the glass substrate 16 is preferably an alkali-free glass containing the following in terms of the oxide-based mass percentage because the coefficient of thermal expansion is small.
SiO ₂ : 50 to 66%
Al ₂ O _3: 10.5~24%
B ₂ O _3: 0~12%
MgO: 0 to 8%
CaO: 0 to 14.5%
SrO: 0 to 24%
BaO: 0 to 13.5%
MgO + CaO + SrO + BaO: 9 to 29.5%
ZrO ₂ : 0 to 5%

Moreover, as a glass of the glass substrate 16, the alkali free glass containing the following is preferably mentioned in the mass percentage display of an oxide basis at a point with a small thermal expansion coefficient.
SiO _2: 58~66%
Al ₂ O ₃ : 15-22%
B ₂ O _3: 5~12%
MgO: 0 to 8%
CaO: 0 to 9%
SrO: 3 to 12.5%
BaO: 0 to 2%
MgO + CaO + SrO + BaO: 9 to 18%

The thickness of the glass substrate 16 is 0.3 mm or less, more preferably 0.15 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 16. In the case of more than 0.3 mm, the glass substrate 16 cannot satisfy the demand for thickness reduction and / or weight reduction. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 16. In the case of 0.15 mm or less, the glass substrate 16 can be rolled up.
Further, the thickness of the glass substrate 16 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 16 and easy handling of the glass substrate 16.

  The glass substrate 16 may be composed of two or more layers. In this case, the material for forming each layer may be the same material or different materials. In this case, “the thickness of the glass substrate 16” means the total thickness of all the layers.

(Process procedure)
In this step S102, the support substrate 18 with a resin layer and the glass substrate 16 described above are prepared, and both 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 surfaces. Are stuck together. The laminated surface of the resin layer 14 has easy peelability, and can be easily and peelably adhered by normal superposition and pressurization.
Specifically, for example, after the glass substrate 16 is stacked on the surface 14a of the easily peelable resin layer 14 in a normal pressure environment, the resin layer 14 and the glass substrate 16 are pressure-bonded using a roll or a press. Can be mentioned. It is preferable because the resin layer 14 and the glass substrate 16 are more closely adhered by pressure bonding with a roll or a press. Further, it is preferable because bubbles mixed between the resin layer 14 and the glass substrate 16 are relatively easily removed by pressure bonding with a roll or a press.

  When pressure bonding is performed by a vacuum laminating method or a vacuum pressing method, it is more preferable because it suppresses mixing of bubbles and secures good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are not likely to lead to a distortion defect of the glass substrate 16.

  When the resin layer 14 is detachably adhered to the first main surface 16a of the glass substrate 16, the surfaces of the resin layer 14 and the glass substrate 16 that are in contact with each other are sufficiently washed and laminated in a clean environment. It is preferable to do. Even if a foreign substance is mixed between the resin layer 14 and the glass substrate 16, the resin layer 14 is deformed and thus does not affect the flatness of the surface of the glass substrate 16. Is preferable because it becomes favorable.

The glass laminate 10 formed by the lamination step S102 can be used for various applications, such as a display device panel, PV, a thin film secondary battery, a semiconductor wafer having a circuit formed on the surface, and the like. The use which manufactures these electronic components is mentioned. In this application, the glass laminate 10 is often exposed (for example, 1 hour or longer) under high temperature conditions (for example, 320 ° C. or higher).
Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

[Polishing process]
Polishing process S104 is a process of grind | polishing the 2nd main surface 16b of the glass substrate 16 in the glass laminated body 10 obtained by lamination process S102. By providing this step S104, minute irregularities and wrinkles on 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. Therefore, the reliability of the electronic device which is a product can be improved. This effect is remarkable for a glass substrate having a thickness of 0.3 mm or less used in the present invention. This is because it is difficult to polish a glass substrate having a thickness of 0.3 mm or less alone, and it is difficult to polish it in advance before forming the glass laminate 10.

The polishing method is not particularly limited, and a known method can be adopted, and mechanical polishing (physical polishing) or chemical polishing (chemical polishing) can be used. As mechanical polishing, use a sand blasting method in which ceramic abrasive grains are sprayed to grind, polishing using a lapping sheet or a grindstone, a chemical mechanical polishing (CMP) method in which abrasive grains and a chemical solvent are used in combination. Can do.
As chemical polishing (sometimes referred to as wet etching), a method of polishing the surface of a glass substrate using a chemical solution can be used.
Among these, chemical mechanical polishing is preferable in that the flatness and cleanliness of the second main surface 16b of the glass substrate 16 after polishing are higher. In addition, as abrasive grains used in chemical mechanical polishing, known abrasive grains such as cerium oxide can be used.

  By passing through the lamination step S102 and the polishing step S104, a glass laminate including a polished glass substrate can be produced.

[Member forming process]
The member forming step S106 is a step of forming an electronic device member 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 of an example of a laminated body with an electronic device member obtained in this step S106. The laminated body 20 with a member for electronic devices is comprised from the said glass laminated body 10 and the member 22 for electronic devices.
First, the electronic device member used in this step S106 will be described in detail, and then the procedure of step S106 will be described in detail.

(Electronic device components (functional elements))
The electronic device member 22 is a member that 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, examples of the electronic device member 22 include a member used for a display device panel, a solar cell, a thin film secondary battery, and an electronic component such as a semiconductor wafer having a circuit formed on the surface. Examples of the display device panel include 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 silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
Further, as a member for a thin film secondary battery, in the lithium ion type, 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 current collecting layer, a resin as a sealing layer, etc. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
In addition, as a member for electronic components, in CCD and CMOS, metal of conductive part, silicon oxide and silicon nitride of insulating part, etc., other various sensors such as pressure sensor and acceleration sensor, rigid printed board, flexible printed board And various members corresponding to a rigid flexible printed circuit board.

(Process procedure)
The manufacturing method of the laminated body 20 with the member for electronic devices mentioned above is not specifically limited, The 2nd main surface of the glass substrate 16 of the laminated body 10 by a conventionally well-known method according to the kind of structural member of the member for electronic devices. An electronic device member 22 is formed on the surface of 16b.
The electronic device member 22 is not all of the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter referred to as “all members”), but a part of all the members (hereinafter referred to as “parts”). May be referred to as a member. The glass substrate with a partial member peeled from the resin layer 14 can be used as a glass substrate with all members (corresponding to an electronic device described later) in the subsequent steps.
Moreover, the other electronic device member may be formed in the peeling surface (1st main surface 16a) in the glass substrate with all the members peeled from the resin layer 14. FIG. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the support substrate with a resin layer from the laminate with all members. Furthermore, an electronic device can also be manufactured by assembling an electronic device using two laminates with all members, and then peeling the two support substrates with resin layers from the laminate with all members.

  For example, taking the case of manufacturing an OLED as an example, an organic EL structure on the surface of the glass laminate 10 opposite to the resin layer 14 side of the glass substrate 16 (corresponding to the second main surface 16b of the glass substrate 16). In order to form a body, a transparent electrode is formed, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and a sealing plate Various layers are formed and processed, such as sealing with the use of. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.

  In addition, for example, the TFT-LCD manufacturing method uses a resist solution on the second main surface 16b of the glass substrate 16 of the planarized glass laminate 10 using a resist solution, such as a CVD method and a sputtering method. TFT forming step of forming a thin film transistor (TFT) by patterning a metal film and a metal oxide film formed by a film method, and a second main surface 16b of the glass substrate 16 of the glass laminate 10 after another planarization On top of this, there are various processes such as a CF forming process for forming a color filter (CF) using a resist solution for pattern formation, and a bonding process for laminating a device substrate with TFT and a device substrate with CF.

In the TFT formation process and the CF formation process, the TFT and the CF are formed on the second main surface 16b of the glass substrate 16 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist solution is used as a coating solution for pattern formation.
In addition, before forming TFT and CF, you may wash | clean the 2nd main surface 16b of the glass substrate 16 as needed. As a cleaning method, known dry cleaning or wet cleaning can be used.

  In the bonding step, a liquid crystal material is injected and laminated between the laminated body with TFT and the laminated body with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.

[Separation process]
In the separation step S108, the glass substrate 16 on which the electronic device member 22 is laminated and the support substrate 18 with the resin layer are separated from the laminate 20 with the electronic device member obtained in the member forming step S106, and an electronic This is a step of obtaining an electronic device 24 (a glass substrate with a member for electronic devices) including the device member 22 and the glass substrate 16.
When the electronic device member 22 on the glass substrate 16 at the time of peeling is a part of the formation of all the necessary constituent members, the remaining constituent members can be formed on the glass substrate 16 after separation.

  The method of peeling the 1st main surface 16a of the glass substrate 16 and the surface 14a of the resin layer 14 is not specifically limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate 16 and the resin layer 14 and given a trigger for peeling, and then the peeling is performed by spraying a mixed fluid of water and compressed air. can do. Preferably, the laminate 20 with electronic device members is placed on a surface plate so that the support substrate 12 is on the upper side and the electronic device member 22 side is on the lower side, and the electronic device member 22 side is vacuum-adsorbed on the surface plate. (In the case where support substrates are laminated on both surfaces, the steps are sequentially performed). In this state, the blade is first inserted into the glass substrate 16-resin layer 14 interface. Then, the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. Then, an air layer is formed at the interface between the resin layer 14 and the glass substrate 16, and the air layer spreads over the entire interface, and the support substrate 12 can be easily peeled off.

  The manufacturing method described above is suitable for manufacturing a small display device used for a mobile terminal such as a mobile phone or a PDA. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type, and the like. Basically, the present invention can be applied to both passive drive type and active drive type display devices.

  EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples.

<Example 1>
Prepare a glass substrate (“AN100”, linear expansion coefficient 38 × 10 ⁻⁷ / ° C. non-alkali glass plate: manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, and a thickness of 0.5 mm as a support substrate and washed with pure water The substrate was cleaned by UV cleaning to obtain a support substrate with a cleaned surface.
Next, as a component (A), linear vinylmethylpolysiloxane (“VDT-127”, viscosity at 25 ° C. 700-800 cP (centipoise): manufactured by Azumax, mol% of vinyl group in 1 mol of organopolysiloxane: 0.325 ) And linear methylhydropolysiloxane (“HMS-301” as component (B), viscosity 25-35 cP (centipoise) at 25 ° C .: manufactured by Asmax, the number of hydrogen atoms bonded to silicon atoms in one molecule: 8) are mixed so that the molar ratio of all vinyl groups to hydrogen atoms bonded to all silicon atoms (hydrogen atoms / vinyl groups) is 0.9, with respect to 100 parts by weight of this siloxane mixture, As a component (C), 1 part by mass of a silicon compound having an acetylenically unsaturated group represented by the following formula (1) was mixed.
HC≡C—C (CH ₃ ) ₂ —O—Si (CH ₃ ) ₃ Formula (1)
Next, a platinum-based catalyst (CAT-PL-56 manufactured by Shin-Etsu Silicone Co., Ltd.) such that the platinum metal concentration is 100 ppm in terms of platinum with respect to the total amount of component (A), component (B), and component (C). ) Was added to obtain a mixed liquid of the organopolysiloxane composition.
The obtained mixed liquid was coated on 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 (composition layer for resin layer formation) coated on the support substrate was allowed to stand at room temperature for 10 minutes, and then heat-cured at 180 ° C. for 60 minutes in the atmosphere, and 350 mm long × 300 mm wide on the support substrate. Then, a cured silicone resin layer having a thickness of 15 μm was formed to obtain a support A (support substrate with a resin layer). The filtered center line waviness (W _CA ) of the exposed surface of the cured silicone resin layer was 0.090 μm.

On the other hand, a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm (“AN100”, an alkali-free glass plate having a linear expansion coefficient of 38 × 10 ⁻⁷ / ° C .: manufactured by Asahi Glass Co., Ltd.) is washed with pure water and UV washed. The surface of the glass substrate was cleaned.
Then, after aligning the support A and the glass substrate, using a vacuum press apparatus, the first main surface of the glass substrate and the peelable surface of the cured silicone resin layer of the support A are used at room temperature. It was made to adhere and the glass laminated body was obtained.
Next, the 2nd main surface (exposed surface) of the glass substrate of the obtained glass laminated body was grind | polished using the Oscar type | mold grinder. As the polishing liquid, a colloidal silica polishing solution having an average particle diameter of silica particles of 0.08 μm and a silica particle content of 10% by mass was used. A suede material was used as the polishing pad. The polishing conditions were a polishing liquid supply amount of 30 ml / min, a polishing pressure of 20000 Pa, a rotation speed of the lower platen of 80 rpm, and a polishing time of 600 seconds.
After the polishing is completed, the second main surface of the glass substrate in the glass laminate subjected to the polishing treatment is vacuum-adsorbed on the surface plate, and then the glass substrate at one corner portion of the four corner portions of the glass substrate. A stainless steel knife having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the silicone resin layer, and an interface for peeling was applied to the interface between the glass substrate and the silicone resin layer. And after adsorbing a support substrate with 24 vacuum suction pads, it raised in order from the suction pad near the corner part which inserted the blade. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad was pulled up while spraying a static eliminating fluid continuously from the ionizer toward the formed gap. As a result, it was possible to separate the glass substrate whose surface was polished on the surface plate from the glass laminate. The filtered center line waviness (W _CA ) of the second main surface of the obtained glass substrate was 0.090 μm. From the results, it was confirmed that the glass substrate separated after the glass substrate of the glass laminate was polished had 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 solution of the organopolysiloxane composition obtained by the same procedure as in Example 1, and the resulting mixed solution was mixed with a die coater (coating speed 40 mm / s, GAP 140 μm, coating pressure 50 kPa), applied to a support substrate, allowed to stand at room temperature for 10 minutes, and then heated and cured in air at 180 ° C. for 60 minutes to form a 15 μm cured silicone resin layer. In accordance with the same procedure as in Example 1, a glass laminate was prepared and subjected to polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 0.100 μm or less.

<Example 3>
The mixed solution was applied on a support substrate with a die coater, allowed to stand at room temperature for 30 minutes, and then heated and cured in the atmosphere at 180 ° C. for 60 minutes to form a 15 μm cured silicone resin layer. According to the same procedure, a glass laminate was prepared and subjected to a polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 0.100 μm or less.

<Example 4>
A mixed solution was prepared by adding 100 parts by weight of heptane to 100 parts by weight of the mixed solution of the organopolysiloxane composition obtained in the same procedure as in Example 1, and the resulting mixed solution was mixed with a die coater (coating speed 40 mm / s, GAP 100 μm, coating pressure 28 kPa), applied to a support substrate, allowed to stand at room temperature for 30 seconds, and then cured by heating at 180 ° C. for 60 minutes in the air to form a cured silicone resin layer of 15 μm. In accordance with the same procedure as in Example 1, a glass laminate was prepared and subjected to polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 0.100 μm or less.

<Example 5>
The mixed solution was applied on a support substrate with a die coater, and then allowed to stand at room temperature for 10 minutes, and then heated and cured in the atmosphere at 180 ° C. for 60 minutes to form a 15 μm cured silicone resin layer. According to the procedure, a glass laminate was prepared and subjected to a polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 0.100 μm or less.

<Example 6>
A glass laminate was prepared and polished according to the same procedure as in Example 4 except that the coating speed of the die coater was changed from 40 mm / s to 80 mm / s and a cured silicone resin layer of 8 μm was formed. Then, the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 0.100 μm or less.

<Example 7>
The mixed solution was applied on a support substrate with a die coater, allowed to stand at room temperature for 10 minutes, and then heated and cured in air at 180 ° C. for 60 minutes to form an 8 μm cured silicone resin layer. According to the same procedure, a glass laminate was prepared and subjected to a polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 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 organopolysiloxane composition obtained by the same procedure as in Example 1, and the resulting mixed solution was mixed with a die coater (coating speed 40 mm / s, GAP 100 μm, coating pressure 20 kPa), applied to a support substrate, allowed to stand at room temperature for 30 seconds, and then cured by heating at 180 ° C. for 60 minutes in the air to form a cured silicone resin layer of 15 μm. In accordance with the same procedure as in Example 1, a glass laminate was prepared and subjected to polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 0.100 μm or less.

<Example 9>
The mixed solution was applied on a support substrate with a die coater, allowed to stand at room temperature for 10 minutes, and then heated and cured in air at 180 ° C. for 60 minutes to form an 8 μm cured silicone resin layer. According to the same procedure, a glass laminate was prepared and subjected to a polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 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 solution of the organopolysiloxane composition obtained by the same procedure as in Example 1, and the resulting mixed solution was mixed with a die coater (coating speed 40 mm / s, GAP 70 μm, coating pressure 15 kPa), applied on a support substrate, allowed to stand at room temperature for 30 seconds, and then cured by heating at 180 ° C. for 60 minutes in air to form a cured silicone resin layer of 15 μm. In accordance with the same procedure as in Example 1, a glass laminate was prepared and subjected to polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 0.100 μm or less.

<Example 11>
The mixed solution was applied on a support substrate with a die coater, and then allowed to stand at room temperature for 10 minutes and then heated and cured in the atmosphere at 180 ° C. for 60 minutes to form a 15 μm cured silicone resin layer. According to the procedure, a glass laminate was prepared and subjected to a polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 0.100 μm or less.

<Example 12>
The mixed solution was applied onto a support substrate with a die coater, and then allowed to stand at room temperature for 30 minutes, and then heated and cured in the atmosphere at 180 ° C. for 60 minutes to form a 15 μm cured silicone resin layer. According to the procedure, a glass laminate was prepared and subjected to a polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and was 0.100 μm or less.

<Comparative Example 1>
After applying the mixed solution on the support substrate with a die coater, the same procedure as in Example 1 was followed, except that the cured silicone resin layer having a thickness of 15 μm was formed by heating and curing in the atmosphere at 180 ° C. for 60 minutes. Then, a glass laminate was prepared and subjected to polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and exceeded 0.100 μm.

<Comparative Example 2>
After applying the mixed solution on the support substrate with a die coater, the same procedure as in Example 2 was followed, except that the cured silicone resin layer having a thickness of 15 μm was formed by heating and curing in the atmosphere at 180 ° C. for 60 minutes. Then, a glass laminate was prepared and subjected to polishing treatment, and the glass substrate subjected to the polishing treatment was separated. Various results are summarized in Table 1. The filtered center line waviness (W _CA ) of the second main surface of the glass substrate separated from the glass laminate was similar to the filtered center line waviness of the resin layer, and exceeded 0.100 μm.

In Table 1 below, the solid content concentration means the solid content concentration (concentration other than the solvent) in the mixed solution of the organopolysiloxane composition, and the resin layer _WCA is a support substrate with a resin layer before the glass substrate is laminated. It means the wavy center line undulation of the exposed surface of the resin layer inside. The filtered center line waviness was measured according to JIS B-0610 (1987). The cut-off value of the filtering waviness curve was 0.8 mm, and the measurement length was 40 mm.

As shown in Table 1 above, in an example in which the filtering center line waviness of the resin layer is 0.100 μm or less, the filtering center line waviness of the polishing surface of the glass substrate to be obtained is approximately the same as the value of the resin layer. It was 0.100 μm or less. From this result, the surface of the glass substrate obtained by this production method has a small undulation, and when a device such as a circuit electrode is produced on the glass substrate, the circuit electrode is disconnected or shorted as described in Patent Document 2. It was confirmed that the occurrence of this problem was further suppressed.
Moreover, it was confirmed from the comparison with Example 2 and 3 that the flatness of a resin layer is more excellent when the stationary time is long.
On the other hand, Comparative Examples 1 and 2 are embodiments in which the resin layer was produced without leaving the standing time as specifically described in Patent Document 1. In these comparative examples, the filtering center line waviness of the resin layer exceeds 0.100 μm, and the filtering center line waviness of the polishing surface of the resulting glass substrate also exceeds 0.100 μm. It was confirmed to be unsuitable as a glass substrate for production.

<Example 13>
In this example, an OLED was manufactured using the glass laminate manufactured in Example 1 and subjected to the polishing treatment.
More specifically, a molybdenum film was formed by a sputtering method on the second main surface of the glass substrate subjected to the polishing treatment in the glass laminate, and a gate electrode was formed by etching using a photolithography method. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD, indium tin oxide is formed by sputtering and photolithography is used. A pixel electrode was formed by etching.
Subsequently, on the second main surface side of the glass substrate, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [ (N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer were formed in this order, and then formed on the second main surface side of the glass substrate by sputtering. Aluminum was deposited, and a counter electrode was formed by etching using a photolithography method.Next, ultraviolet light was formed on the second main surface of the glass substrate on which the counter electrode was formed. Another glass substrate was bonded and sealed through a chemical adhesive layer, and the glass laminate having the organic EL structure on the glass substrate obtained by the above procedure was laminated with an electronic device member. Applies to the body.
Subsequently, after the sealed body side of the obtained glass laminate is vacuum-adsorbed to a surface plate, a 0.1 mm thick stainless steel product is formed at the interface between the glass substrate and the silicone resin layer at the corner of the glass laminate. A blade was inserted, and the support substrate with a resin layer was separated from the glass laminate to obtain an OLED panel (corresponding to an electronic device, hereinafter referred to as panel A). When an IC driver was connected to the manufactured panel A and driven under normal temperature and normal pressure, display unevenness was not observed in the driving region. Further, even when driven in a high temperature and high humidity environment (80 ° C., 80% RH), display unevenness was not recognized.

<Example 14>
In this example, an LCD was manufactured using the glass laminate manufactured in Example 1 and subjected to the polishing treatment.
Two glass laminates are prepared. First, a molybdenum film is formed by sputtering on the second main surface of a glass substrate that has been subjected to polishing treatment in one glass laminate, and etching is performed using a photolithography method. A gate electrode was formed. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD, indium tin oxide was formed by sputtering and photolithography was used. A pixel electrode was formed by etching. Next, a polyimide resin liquid was applied on the second main surface of the glass substrate on which the pixel electrode was formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. The obtained glass laminated body is called glass laminated body A1.
Next, a chromium film was formed by sputtering on the second main surface of the glass substrate on which the other glass laminate had been subjected to polishing treatment, and a light-shielding layer was formed by etching using photolithography. Next, a color resist was further applied by a die coating method to the second main surface side of the glass substrate provided with the light shielding layer, and a color filter layer was formed by a photolithography method and thermal curing. Next, an indium tin oxide film was further formed on the second main surface side of the glass substrate by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid was applied to the second main surface of the glass substrate provided with the counter electrode by a die coating method, and columnar spacers were formed by a photolithography method and heat curing. Next, a polyimide resin solution was applied on the second main surface of the glass substrate on which the columnar spacers were formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. Next, after the sealing resin liquid is drawn in a frame shape on the second main surface side of the glass substrate by the dispenser method, and the liquid crystal is dropped in the frame by the dispenser method, the above-described glass laminate A1 is used. The 2nd main surface side of the glass substrate of a sheet of glass laminated body was bonded together, and the laminated body which has an LCD panel by ultraviolet curing and thermosetting was obtained. Hereinafter, the laminate having the LCD panel is referred to as a laminate B2 with a panel.
Next, LCD panel B (corresponding to an electronic device) composed of a substrate on which a TFT array is formed and a substrate on which a color filter is formed is peeled off from both sides of the laminated body B2 with a panel in the same manner as in Example 1. Got.
When an IC driver was connected to the manufactured LCD panel B and driven under normal temperature and normal pressure, no display unevenness was observed in the driving region. Further, even when driven in a high temperature and high humidity environment (80 ° C., 80% RH), display unevenness was not recognized.

<Comparative Example 3>
According to the procedure of Comparative Example 1, a glass laminate subjected to polishing treatment was produced.
Next, using the obtained glass laminate, an OLED panel was produced according to the same procedure as in Example 13.
When an IC driver was connected to the manufactured panel and driven under normal temperature and normal pressure, no display unevenness was observed in the driving area, but it was connected for a long time under a high temperature and high humidity environment (80 ° C., 80% RH). When continued, some display irregularities appeared.

10, 100 Glass laminate 12, 112 Support substrate 14, 114 Resin layer 14a Resin layer surface 16, 116 Glass substrate 16a, 116a Glass substrate first main surface 16b, 116b Glass substrate second main surface 18 Support with resin layer Substrate 20 Laminated body 22 with electronic device member 24 Electronic device member 24 Electronic device

Claims (12)

An exposed surface of the resin layer of the support substrate with a resin layer, which has a support substrate and a resin layer fixed to one surface thereof, and the exposed surface of the resin layer exhibits easy peelability, and a first main surface and a second main surface A laminating step of obtaining a glass laminate by closely laminating the support substrate with a resin layer and the glass substrate with the first main surface of the glass substrate having a thickness of 0.3 mm or less having a laminating surface;
A polishing step of polishing the second main surface of the glass substrate in the glass laminate;
A member forming step of forming an electronic device member on the polished second main surface of the glass substrate;
Separating the glass substrate on which the electronic device member is laminated and the support substrate with the resin layer, and obtaining an electronic device including the glass substrate and the electronic device member,
Surface waviness in the exposed surface of the resin layer is, Ri 0.100μm der Hereinafter filtered centerline waviness (W _CA),
The manufacturing method of an electronic device whose thickness of the said resin layer is 15 micrometers or less . Before the laminating step, a resin layer forming composition layer to be a resin layer is formed on the support substrate surface, and the support substrate including the resin layer forming composition layer is allowed to stand for a predetermined time, and then the resin The manufacturing method of the electronic device of Claim 1 which has the process of hardening the layer forming composition layer and forming the resin layer fixed on the support substrate. Resin of the resin layer is a silicone resin, a method for fabricating an electronic device according to claim 1 or 2. The method of manufacturing an electronic device according to claim 3 , wherein the silicone resin is a reaction cured product of an organoalkenylpolysiloxane and an organohydrogenpolysiloxane. The polishing is a chemical mechanical polishing (CMP), a method of manufacturing an electronic device according to any one of claims 1-4. The said glass substrate is a manufacturing method of the electronic device in any one of Claims 1-5 which consists of an alkali free glass containing the following in the mass percentage display of an oxide basis.
SiO ₂ : 50 to 66%
Al ₂ O _3: 10.5~24%
B ₂ O _3: 0~12%
MgO: 0 to 8%
CaO: 0 to 14.5%
SrO: 0 to 24%
BaO: 0 to 13.5%
MgO + CaO + SrO + BaO: 9 to 29.5%
ZrO ₂ : 0 to 5% The said glass substrate is a manufacturing method of the electronic device in any one of Claims 1-5 which consists of an alkali free glass containing the following in the mass percentage display of an oxide basis.
SiO _2: 58~66%
Al ₂ O ₃ : 15-22%
B ₂ O _3: 5~12%
MgO: 0 to 8%
CaO: 0 to 9%
SrO: 3 to 12.5%
BaO: 0 to 2%
MgO + CaO + SrO + BaO: 9 to 18% An exposed surface of the resin layer of the support substrate with a resin layer, the exposed surface of the resin layer exhibiting easy peelability, a first main surface, and a second main surface. A laminating step of obtaining a glass laminate by closely laminating the support substrate with a resin layer and the glass substrate, with the first main surface of a glass substrate having a surface of 0.3 mm or less having a thickness as the laminating surface,
A polishing step of polishing the second main surface of the glass substrate in the glass laminate;
Surface waviness in the resin layer surface state, and are less 0.100μm with filtered centerline waviness (W _CA), the thickness of the resin layer is 15μm or less, the glass laminate comprising a polished glass substrate Production method. Before the laminating step, a resin layer forming composition layer to be a resin layer is formed on the support substrate surface, and the support substrate including the resin layer forming composition layer is allowed to stand for a predetermined time, and then the resin The manufacturing method of the glass laminated body of Claim 8 which has the process of hardening the layer forming composition layer and forming the resin layer fixed on the support substrate. The method for producing a glass laminate according to claim 8 or 9 , wherein the resin of the resin layer is a silicone resin. The method for producing a glass laminate according to claim 10 , wherein the silicone resin is a reaction cured product of an organoalkenylpolysiloxane and an organohydrogenpolysiloxane. The manufacturing method of the glass laminated body in any one of Claims 8-11 whose said grinding | polishing is chemical mechanical grinding | polishing (CMP).