TWI613073B - Glass laminate, method of manufacturing the same, and support substrate with oxy-resin layer - Google Patents

Abstract

The invention relates to a glass laminated body, which is sequentially provided with a substrate supporting layer, a silicone resin layer, and a glass substrate layer, and the peel strength of the interface between the substrate supporting layer and the silicone resin layer is higher than that of silicon oxide. Peel strength at the interface between the resin layer and the glass substrate; among them, the siloxane resin of the siloxane resin layer is a crosslinked product of crosslinkable organic polysiloxane, the siloxane resin layer contains siloxane oil, and the siloxane resin layer One of the silicone resin and the silicone oil has an aromatic group, and the other has substantially no aromatic group.

Description

Glass laminated body, manufacturing method thereof, and supporting substrate with silicone resin layer Field of invention

The present invention relates to a glass laminate and a method for manufacturing the same, and more particularly to a glass laminate having a silicone resin layer containing a silicone oil and a method for manufacturing the same.

In addition, the present invention relates to a support substrate with a silicone resin layer, and more particularly to a support substrate with a silicone resin layer having a glass substrate laminated on its surface in a peelable manner and a method for manufacturing the same.

Background of the invention

In recent years, the thinning and lightening of components (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have progressed, and the thickness of glass substrates used for these components has also been reduced. Some progress. However, if the strength of the glass substrate is insufficient due to thinning, the disposability of the glass substrate will be reduced in the manufacturing process of the element.

At this point, a method of thinning the glass substrate by chemical etching treatment after forming a component for a device (such as a thin film transistor) on a glass substrate that is thicker than the final thickness is widely used.

However, in this method, for example, the thickness of one glass substrate is changed from When the thickness of the 0.7mm sheet is reduced to 0.2mm or 0.1mm, most of the original glass substrate material will be cut off by the etching solution, so it is not ideal from the viewpoint of productivity or the use of raw materials. Moreover, in the thinning method of the glass substrate performed by the chemical etching described above, when there are fine flaws on the surface of the glass substrate, fine recesses (etched holes) may be formed from the flaws as a starting point by the etching process, and become optical defect.

Recently, in order to cope with the above-mentioned problems, a method has been proposed, which is to prepare a glass laminate having a laminated glass substrate and a reinforcing plate, and to form a member for electronic components such as a display device on the laminated glass substrate. A method for separating a substrate from a supporting substrate (for example, refer to Patent Document 1 or Patent Document 2). The reinforcing plate has a support plate and a siloxane resin layer fixed on the support plate, and the siloxane resin layer and the thin glass substrate are releasably adhered. The reinforced sheet separated from the thin glass substrate by peeling off the interface between the siloxane resin layer and the thin glass substrate of the glass laminate can be laminated with a new thin glass substrate and reused as a glass laminate.

Meanwhile, Patent Document 2 (especially Example 7) specifically discloses a case where a silicone resin layer containing dimethylpolysiloxane is used as the silicone oil system.

Prior art literature Patent literature

Patent Document 1: International Publication No. 2007/018028

Patent Document 2: International Publication No. 2011/142280

Summary of invention

Regarding the glass laminates described in Patent Documents 1 and 2, higher heat resistance is required in recent years. With the increase in the functionality and complexity of electronic component members formed on a glass substrate of a glass laminate, the temperature for forming electronic component members needs to be higher, and the time of exposure to high temperatures also requires a long time. A lot. In addition, the glass substrate to be used is thinner, which makes handling more difficult.

The glass laminates described in Patent Documents 1 and 2 can withstand the treatment at 300 ° C. for 1 hour in the air. However, after research by the present inventors, when referring to Patent Documents 1 and 2, a glass laminate using a thinner glass substrate was treated at 350 ° C for 1 hour, the glass substrate was removed from the siloxane resin layer. When the surface is peeled off, the glass substrate may not be peeled off from the surface of the resin layer and a part of the glass substrate may be damaged, and a part of the resin in the resin layer may remain on the glass substrate. As a result, the productivity of electronic components may be reduced.

The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a glass laminate capable of suppressing an increase in peel strength of a glass substrate and a silicone resin layer and easily peeling the glass substrate even after a high-temperature heat treatment condition. Body and its manufacturing method.

Another object of the present invention is to provide a support substrate with a silicone resin layer used in the manufacture of the glass laminate.

The present inventors have completed the present invention as a result of intensive research in order to solve the above-mentioned problems.

That is, the first aspect of the present invention is a glass laminate, which is sequentially provided with a layer supporting a substrate, a layer of a silicone resin, and a layer of a glass substrate. The peeling strength of the interface between the layer and the siloxane resin layer is higher than that of the interface between the siloxane resin layer and the glass substrate; the siloxane resin layer of the siloxane resin layer is a crosslinked product of the silicone polysiloxane. The oxyresin layer contains a silicone oil, and one of the silicone resin and the silicone oil contained in the silicone resin layer has an aromatic group, and the other does not substantially have an aromatic group.

In the first aspect, the silicone oil has a phenyl group, and the content of the phenyl group in all the organic groups bonded to the silicon atom in the silicone oil is preferably 5 to 50 mole%.

In the first aspect, the content of the silicone oil is preferably 6 to 20 parts by mass relative to 100 parts by mass of the silicone resin layer.

In the first aspect, the viscosity of the silicone oil at 25 ° C is preferably 100 to 6000 cP.

In the first aspect, the thickness of the silicone resin layer is preferably 2 to 100 μm.

In the first aspect, a supporting substrate-based glass plate is preferred.

The second aspect of the present invention is a method for manufacturing the glass laminate of the first aspect, which is characterized in that a layer containing a crosslinkable organic polysiloxane and a silicone oil is formed on one side of a supporting substrate, and A cross-linkable organic polysiloxane is crosslinked to form a siloxane resin layer on a support substrate surface, and then a glass substrate is formed on the surface area of the siloxane resin layer.

A third aspect of the present invention is a support substrate with a siloxane resin layer, comprising a support substrate and a siloxane resin layer provided on the support substrate surface and having a peelable surface; wherein the silicon of the siloxane resin layer is The oxyresin is a crosslinked product of a crosslinkable organic polysiloxane. The siloxane resin layer contains a siloxane oil, and either the siloxane resin or the siloxane oil contained in the siloxane resin layer has an aromatic group. One is substantially free of aromatic groups.

In the third aspect, the silicone oil has a phenyl group, and the content of the phenyl group in all the organic groups bonded to the silicon atom in the silicone oil is preferably 5 to 50 mole%, and 5 to 30 mole%. Ear% is better.

In the third aspect, the content of the silicone oil is preferably 6 to 20 parts by mass based on 100 parts by mass of the silicone resin layer.

In the third aspect, the viscosity of the silicone oil at 25 ° C is preferably 100 to 6000 cP.

According to the present invention, it is possible to provide a glass laminate capable of suppressing an increase in peel strength of a glass substrate and a silicone resin layer and easily peeling the glass substrate even after a high-temperature heat treatment condition, and a method for manufacturing the same.

In addition, according to the present invention, it is also possible to provide a supporting substrate with a silicone resin layer used in the manufacture of the glass laminate.

10‧‧‧Glass laminate

12‧‧‧ support substrate

14‧‧‧silicone resin layer

14a‧‧‧ the first main surface of the silicone resin layer

16‧‧‧ glass substrate

16a‧‧‧The first main surface of the glass substrate

16b‧2nd main surface of glass substrate

18‧‧‧ Supporting substrate with silicone resin layer

20‧‧‧ Components for electronic components

22‧‧‧ Laminated body with components for electronic components

24‧‧‧ Glass substrate with components

FIG. 1 is a schematic sectional view of an embodiment of a glass laminate according to the present invention.

2 (A) to 2 (D) are schematic cross-sectional views showing an embodiment of a method for manufacturing a glass substrate with a member according to the present invention in the order of steps.

Forms used to implement the invention

Hereinafter, the form for implementing the present invention will be described with reference to the drawings. The present invention is not limited by the following embodiments, and various modifications and substitutions can be added to the following embodiments without departing from the scope of the present invention.

The glass laminated body of the present invention is sequentially provided with a layer supporting a substrate, a silicone resin layer, and a layer of a glass substrate. That is, there is a siloxane resin layer between the layer supporting the substrate and the layer of the glass substrate. Therefore, one side of the siloxane resin layer is connected to the layer supporting the substrate, and the other side is connected to the layer of the glass substrate.

One of the characteristic points of the glass laminate of the present invention may be as follows: the silicone resin layer contains silicone oil, only one of the silicone resin and the silicone oil of the silicone resin layer has an aromatic group, and the other has It does not substantially have an aromatic group. By introducing only an aromatic group into one of the silicone resin and the silicone oil, the compatibility between the two can be reduced. As a result, the silicone oil can overflow to the surface of the silicone resin layer in a short time, and even if the time from the formation of the silicone resin layer to the laminated glass substrate is short, it can still easily obtain a good performance compared to the glass substrate. As a result, the peelable silicone resin layer can suppress the increase in peel strength of the glass substrate and the silicone resin layer even after being heated at a high temperature. In addition, as described later, if a predetermined silicone oil is used, the transparency of the surface of the silicone resin layer can be more guaranteed, and the transparency of the surface of the peeled glass substrate can also be excellent.

Moreover, since the silicone resin layer of the present invention exhibits good peelability, even if the thickness of the glass substrate is reduced, the glass substrate is still difficult to crack when peeled after heating at high temperature.

FIG. 1 is a schematic cross-sectional view of an example of a glass laminate of the present invention.

As shown in FIG. 1, the glass laminate 10 is a laminate in which a layer supporting the substrate 12, a layer of the glass substrate 16, and a silicone resin layer 14 are interposed therebetween. The silicone resin layer 14 is one side of which is in contact with the layer supporting the substrate 12, while the other side is in contact with The first main surface 16 a of the glass substrate 16 is in contact with each other. In other words, the siloxane resin layer 14 is in contact with the first main surface 16 a of the glass substrate 16.

The two-layer portion composed of the layer supporting the substrate 12 and the silicone resin layer 14 can reinforce the glass substrate 16 in a member forming step of manufacturing a member for an electronic element such as a liquid crystal panel. In addition, a two-layered portion made in advance for manufacturing the glass laminate 10 and composed of a layer of the support substrate 12 and the silicone resin layer 14 is referred to as a support substrate 18 with a silicone resin layer.

This glass laminated body 10 can be used until the member formation process mentioned later. That is, the glass laminated body 10 can be used until a member for electronic components such as a liquid crystal display device is formed on the surface of the second main surface 16 b of the glass substrate 16. Thereafter, the glass laminated body on which the components for electronic components are formed will be separated into a support substrate 18 with a silicone resin layer and a glass substrate with a component, and the support substrate 18 with a silicone resin layer will not constitute an electronic component. part. A new glass substrate 16 can be laminated on the supporting substrate 18 with a silicone resin layer and reused as a new glass laminate 10.

The interface between the support substrate 12 and the silicone resin layer 14 has peel strength (x). If the interface between the support substrate 12 and the silicone resin layer 14 is subjected to a stress exceeding the drag direction of the peel strength (x), the support substrate The interface between 12 and the silicone resin layer 14 is peeled off. The interface between the silicone resin layer 14 and the glass substrate 16 has peeling strength (y). If the interface between the silicone resin layer 14 and the glass substrate 16 is subjected to a stress exceeding the dragging direction of the peeling strength (y), the silicone resin layer 14 The interface with the glass substrate 16 is peeled.

In the glass laminated body 10 (also shown as a laminated body with a member for electronic components described later), the peeling strength (x) is higher than the peeling strength (y). therefore, If stress is applied to the glass laminate 10 in the direction of dragging the supporting substrate 12 and the glass substrate 16, the glass laminate 10 of the present invention will peel off at the interface between the siloxane resin layer 14 and the glass substrate 16 and separate into a glass substrate. 16 and a supporting substrate 18 with a silicone resin layer.

The peel strength (x) is preferably sufficiently high in comparison with the peel strength (y). Increasing the peel strength (x) means increasing the adhesion of the siloxane resin layer 14 to the supporting substrate 12 and maintaining a relatively high adhesion to the glass substrate 16 after the heat treatment.

In order to improve the adhesion of the siloxane resin layer 14 to the support substrate 12, as described later, it is desirable to crosslink and harden the crosslinkable organic polysiloxane on the support substrate 12 to form the siloxane resin layer 14. The silicone resin layer 14 bonded to the supporting substrate 12 with a high bonding force can be formed by the adhesive force at the time of cross-linking and hardening.

On the other hand, it is common practice that the bonding force of the cured product of the crosslinkable organopolysiloxane after cross-linking and curing to the glass substrate 16 is lower than the bonding force generated during the above-mentioned cross-linking and curing. Therefore, it is preferable to crosslink and harden the crosslinkable organic polysiloxane on the supporting substrate 12 to form a siloxane resin layer 14, and then to layer the glass substrate 16 on the area of the siloxane resin layer 14 to manufacture the glass laminate 10.

Hereinafter, each layer (the supporting substrate 12, the glass substrate 16, and the silicone resin layer 14) constituting the glass laminate 10 will be described in detail first, and then the method of manufacturing the glass laminate and a glass substrate with a member will be described in detail.

[Support substrate]

The supporting base material 12 can support and reinforce the glass substrate 16 and prevent deformation, damage, breakage, and the like of the glass substrate 16 during the manufacturing of a component for an electronic component in a component forming step (a step for manufacturing a component for an electronic component) described later.

As the supporting substrate 12, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate can be used. Generally, the step of forming a member is accompanied by heat treatment. Therefore, the supporting substrate 12 is preferably formed of a material having a small linear expansion coefficient difference from that of the glass substrate 16, and is preferably formed of the same material as the glass substrate 16. The supporting substrate 12 is formed of glass. The board is better. In particular, the supporting substrate 12 is preferably a glass plate made of the same glass material as the glass substrate 16.

The thickness of the supporting substrate 12 may be thicker or thinner than that of the glass substrate 16. Ideally, the thickness of the supporting substrate 12 is selected based on the thickness of the glass substrate 16, the thickness of the silicone resin layer 14, and the thickness of the glass laminate 10. For example, the current component formation step is designed to handle a substrate with a thickness of 0.5 mm. When the sum of the thickness of the glass substrate 16 and the thickness of the silicone resin layer 14 is 0.1 mm, the thickness of the support substrate 12 is set to 0.4 mm. . The thickness of the supporting substrate 12 is preferably 0.2 to 5.0 mm under normal circumstances.

When the supporting substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons such as being easier to handle and difficult to break. In addition, from the reason that the glass plate thickness is 1.0 mm or less, for the reason that it does not break when peeling after the formation of the member for electronic components and a moderately flexible rigidity can be expected.

The difference between the average linear expansion coefficients of the supporting substrate 12 and the glass substrate 16 at 25 to 300 ° C is preferably 500 × 10 ^-7 / ° C or lower, more preferably 300 × 10 ^-7 / ° C or lower, and more preferably 200 × 10 ^-7 / ℃ or less. If the difference is too large, the glass laminate 10 may be warped sharply or the support base material 12 and the glass substrate 16 may be peeled off during heating and cooling in the component formation step. When the material of the supporting base material 12 is the same as that of the glass substrate 16, the above-mentioned problems can be suppressed.

[Glass base board]

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

The type of the glass substrate 16 may be a general type, and examples thereof include glass substrates for display devices such as LCDs and OLEDs. The glass substrate 16 has excellent chemical resistance, moisture permeability resistance, and low thermal shrinkage. As an index of thermal shrinkage, a linear expansion coefficient prescribed by JIS R 3102 (corrected in 1995) was used.

If the linear expansion coefficient of the glass substrate 16 becomes too large, since many steps for forming a member are accompanied by heat treatment, various problems are likely to occur. For example, when the TFT is formed on the glass substrate 16, if the glass substrate 16 on which the TFT has been formed is cooled under heating, the position of the TFT may be excessively shifted due to the thermal contraction of the glass substrate 16.

The glass substrate 16 is obtained by melting glass raw materials and molding the molten glass into a plate shape. The forming method may be a general method, and for example, a float glass method, a melting method, a slit overflow extraction method, a Fourcault method, a Lubber's method, or the like can be used. In addition, a particularly thin glass substrate 16 can be obtained by a re-stretching method. The re-stretching method is to heat the glass temporarily formed into a plate shape to a moldable temperature, and then stretch and thin it by means such as stretching. method.

The glass type of the glass substrate 16 is not particularly limited, and alkali-free borosilicate glass, borosilicate glass, soda lime glass, high-silica glass, and other oxide-based glasses containing silicon oxide as a main component are preferred. The oxide-based glass is preferably a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide.

As the glass of the glass substrate 16, a member for electronic components is used The kind of glass or glass suitable for its manufacturing steps. For example, in the glass substrate for liquid crystal panels, from the point that the dissolution of alkali metal components easily affects the liquid crystal, it is composed of glass (alkali-free glass) that does not substantially contain an alkali metal component (however, it usually contains an alkaline earth metal component) . In this way, the glass of the glass substrate 16 can be appropriately selected according to the type of the applicable element and its manufacturing steps.

From the viewpoint of thinning and / or lightening the glass substrate 16, the thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.15 mm or less, and even more preferably 0.10 mm or less. When the thickness is 0.3 mm or less, good flexibility can be imparted to the glass substrate 16. If it is 0.15 mm or less, the glass substrate 16 can be wound into a roll shape.

In addition, for reasons such as easy manufacture of the glass substrate 16 and easy handling of the glass substrate 16, the thickness of the glass substrate 16 is preferably 0.03 mm or more.

In addition, the glass substrate 16 may be composed of two or more layers. In this case, the materials forming each layer may be the same material or different materials. In this case, the "thickness of the glass substrate 16" indicates the total thickness of all the layers.

[Silicone resin layer]

The silicone resin layer 14 can prevent the positional displacement of the glass substrate 16 until the operation of separating the glass substrate 16 and the supporting substrate 12 is performed, and can prevent the glass substrate 16 and the like from being damaged by the separation operation. The surface of the silicone resin layer 14 that is in contact with the glass substrate 16 (the first principal surface of the silicone resin layer) 14 a is releasably adhered to the first principal surface 16 a of the glass substrate 16. The silicone resin layer 14 is bonded to the first main surface 16 a of the glass substrate 16 with a weak bonding force, and the peel strength (y) of the interface is lower than the peel strength of the interface between the silicone resin layer 14 and the supporting substrate 12 ( x).

That is, when the glass substrate 16 is separated from the support substrate 12, it is tied to a glass substrate. The interface between the first main surface 16 a of the plate 16 and the silicone resin layer 14 is peeled off, but it is difficult to peel off at the interface between the support substrate 12 and the silicone resin layer 14. Therefore, the siloxane resin layer 14 has a surface characteristic that the glass substrate 16 can be easily peeled off while being in close contact with the first main surface 16 a of the glass substrate 16. That is, the siloxane resin layer 14 is bonded to the first main surface 16 a of the glass substrate 16 with a certain degree of bonding force to prevent the positional displacement of the glass substrate 16 and the like, and at the same time, the glass can be peeled without damaging the glass substrate 16. The substrate 16 is bonded to such a degree that the substrate 16 is easily peeled off. In the present invention, the easily peelable property of the surface of the silicone resin layer 14 is referred to as peelability. On the other hand, the first main surface of the supporting substrate 12 and the silicone resin layer 14 are bonded with a bonding force that is relatively difficult to peel off.

The bonding force of the interface between the siloxane resin layer 14 and the glass substrate 16 can be changed before and after forming a member for an electronic component (that is, peeling) on the surface (the second main surface 16b) of the glass substrate 16 of the glass laminate 10. Strength (x) and peel strength (y) vary). However, even after the member for electronic components is formed, the peel strength (y) is still lower than the peel strength (x).

The layer of the silicone resin layer 14 and the glass substrate 16 is considered to be bonded with a weak adhesive force or a bonding force due to Van der Waals force. When the siloxane resin layer 14 is formed on the surface area of the glass substrate 16, when the siloxane resin of the siloxane resin layer 14 is sufficiently cross-linked to the extent that the adhesive force is not displayed, it is considered to be a combination caused by van der Waals force. Force combined. However, most of the silicone resin of the silicone resin layer 14 has a weak adhesion to a certain degree. Even if the adhesiveness is extremely low, it is thought that when the glass laminated body 10 is used to form a member for electronic components on the laminated body after manufacturing, the silicone resin of the silicone resin layer 14 is still adhered to the glass substrate 16 surface by a heating operation or the like. Bonding between the siloxane resin layer 14 and the glass substrate 16 Force rises.

Depending on the situation, the surface of the silicone resin layer 14 before lamination or the first main surface 16a of the glass substrate 16 before lamination may be treated to reduce the bonding force therebetween, and then lamination may be performed. Non-adhesive treatment is performed on the laminated surface, and then lamination is performed, thereby reducing the bonding force between the layer interface of the siloxane resin layer 14 and the glass substrate 16 and reducing the peel strength (y).

The silicone resin layer 14 is bonded to the surface of the supporting substrate 12 with a strong bonding force such as an adhesive force or an adhesive force. For example, as described above, by crosslinking and hardening the crosslinkable organic polysiloxane on the surface of the support substrate 12, the crosslinked silicone resin can be adhered to the surface of the support substrate 12 to obtain a high bonding force. In addition, a treatment (such as a treatment using a coupling agent) generated by applying a strong bonding force between the surface of the support substrate 12 and the silicone resin layer 14 can be applied to improve the relationship between the surface of the support substrate 12 and the silicone resin layer 14. Binding force.

The combination of the silicone resin layer 14 and the support substrate 12 with a high bonding strength indicates that the peel strength (x) of the interface between them is high.

The thickness of the siloxane resin layer 14 is not particularly limited, but is preferably 2 to 100 μm, more preferably 3 to 50 μm, and even more preferably 7 to 20 μm. If the thickness of the siloxane resin layer 14 is within the above range, even if bubbles and foreign objects are interposed between the siloxane resin layer 14 and the glass substrate 16, generation of wrinkle defects of the glass substrate 16 can be suppressed. In addition, if the thickness of the siloxane resin layer 14 is too thick, it takes time and materials to form it, which is uneconomical, and the heat resistance may decrease. When the thickness of the silicone resin layer 14 is too thin, the adhesion between the silicone resin layer 14 and the glass substrate 16 may be reduced.

The silicone resin layer 14 may be composed of two or more layers. At this time, The "thickness of the fat layer 14" indicates the total thickness of all the layers.

When the silicone resin layer 14 is composed of two or more layers, the resin forming each layer may be composed of a different crosslinked silicone resin.

The silicone resin contained in the silicone resin layer 14 is a crosslinked product of a crosslinkable organic polysiloxane, and the silicone resin forms a three-dimensional mesh structure.

The type of the crosslinkable organic polysiloxane is not particularly limited, and the structure is not particularly limited as long as it is crosslinked and hardened by a predetermined crosslinking reaction to form a crosslinked material (hardened material) constituting the siloxane resin. As long as it has a predetermined cross-linking property. The cross-linking form is not particularly limited, and a suitable known form may be adopted in accordance with the type of the cross-linkable group contained in the cross-linkable organopolysiloxane. Examples include: a hydrosilylation reaction, a condensation reaction, or a radical reaction using heat treatment, high energy ray treatment, or a radical polymerization initiator.

More specifically, when a crosslinkable organopolysiloxane has a radical-reactive group such as an alkenyl group or an alkynyl group, the cross-linking organopolysiloxane is hardened by cross-linking through a reaction between the radical-reactive groups of the radical reaction described above. (Crosslinked silicone resin).

When the crosslinkable organic polysiloxane has a silanol group, it is crosslinked by a condensation reaction between the silanol groups to become a cured product.

In addition, the crosslinkable organic polysiloxane includes an organic polysiloxane having an alkenyl group (vinyl group, etc.) bonded to a silicon atom (that is, an organic alkenyl polysiloxane), and an organic polysiloxane having a bond to a silicon atom. In the case of a hydrogen atom (silyl) -based organopolysiloxane (that is, an organohydrogenpolysiloxane), it is crosslinked by a hydrosilation reaction in the presence of a hydrosilation catalyst (for example, a platinum-based catalyst) to become Hardened.

Among them, the formation of the siloxane resin layer 14 is easy and the From the viewpoint of better releasability, it is preferable that the crosslinkable organic polysiloxane contains an organic polysiloxane having alkenyl groups at both ends and / or side chains (hereinafter also referred to as an organic polysiloxane as appropriate). Oxane A), and an organopolysiloxane having a hydrosilyl group at both end and / or side chains (hereinafter also referred to as an organopolysiloxane B as appropriate).

The alkenyl group is not particularly limited, and examples thereof include vinyl (vinyl), allyl (2-propenyl), butenyl, pentenyl, and hexenyl. Among them, from the viewpoint of good heat resistance It seems that vinyl is better.

Examples of the group other than the alkenyl group contained in the organopolysiloxane A and the hydrosilyl group contained in the organopolysiloxane B include an alkyl group (particularly, an alkyl group having 4 or less carbon atoms) .

The position of the alkenyl group in the organopolysiloxane A is not particularly limited. When the organopolysiloxane A is linear, the alkenyl group may exist in any of the M units and D units shown below. It may exist in both the M unit and the D unit. From the point of view of the hardening speed, it is preferable to exist in at least M units, and it is preferable to exist in both M units.

In addition, the so-called M unit and D unit are examples of basic structural units of organic polysiloxane. The M unit is a monofunctional siloxane unit having three organic groups bonded, and the D unit has two organic groups bonded. Bifunctional siloxane unit. In a siloxane unit, a siloxane bond is a bond in which two silicon atoms are bonded by one oxygen atom, and thus an oxygen atom of each silicon atom in the siloxane bond is regarded as 1/2. , Which is expressed as O _{1/2 in the} formula.

[Chemical 1]

The number of alkenyl groups in the organopolysiloxane A is not particularly limited. One to three molecules are preferred, and two are preferred.

The position of the silyl group in the organic polysiloxane B is not particularly limited. When the organopolysiloxane A is linear, the silyl group may exist in either of the M unit and the D unit, and may also exist. In both M and D units. From the standpoint of the hardening speed, it is preferable to exist at least in the D unit.

There is no particular limitation on the number of hydrosilyl groups in the organic polysiloxane B, and it is preferable to have at least 3 in one molecule, and 3 is more preferable.

There is no particular limitation on the mixing ratio of the organopolysiloxane A and the organopolysiloxane B. The hydrogen atom bonded to the silicon atom in the organopolysiloxane B and the total alkenyl group in the organopolysiloxane A are adjusted. The molar ratio (hydrogen atom / alkenyl) is preferably 0.7 to 1.05. Among them, it is better to adjust the mixing ratio to 0.8 to 1.0.

As the hydrosilylation catalyst, a platinum group metal catalyst is preferably used. As the platinum group metal catalyst, there are platinum-based, palladium-based, and rhodium-based catalysts. From the viewpoint of economics and reactivity, it is particularly preferable to use platinum-based catalysts. As the platinum group metal-based catalyst, a known substance can be used. Specifically, there are: platinum fine powder, platinum black, platinous chloride, platinic chloride and other chlorinated platinum acids, platinum tetrachloride, alcohol compounds of chloroplatinic acid, aldehyde compounds, or platinum Olefin complex, alkenyl siloxane complex, carbonyl complex, etc.

The amount used as a hydrosilylation catalyst is The total mass of organic polysiloxane B is 100 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass.

There is no particular limitation on the weight average molecular weight of the crosslinkable organic polysiloxane, and it has good handling properties and film formation properties, and it is better to use GPC (gel) from the viewpoint of inhibiting the decomposition of the siloxane resin under high temperature processing conditions. Chromatography) The polystyrene-equivalent weight average molecular weight obtained is preferably 1,000 to 5,000,000, and more preferably 2,000 to 3,000,000.

The viscosity of the crosslinkable organic polysiloxane is preferably 10 to 5000 mPa‧s, and more preferably 15 to 3000 mPa‧s. It should be noted that the value of the viscosity described in the present specification is a value measured at 25 ° C unless otherwise specified.

In addition, as the cross-linkable organic polysiloxane product name or model that has been specifically marketed, as for the cross-linkable organic polysiloxane having no aromatic group, for example: KNS-320A, KS-847 (both (Made by Shin-Etsu Silicone Co., Ltd.), TPR6700 (manufactured by Momentive Performance Materials Japan), vinyl siloxane "8500" (made by Arakawa Chemical Industries, Ltd.), and methyl hydrogenated polysiloxane "12031" (made by Arakawa Chemical Industries, Ltd.) ), A combination of vinyl siloxane "11364" (manufactured by Arakawa Chemical Industry Co., Ltd.) and a methyl hydrogenated polysiloxane "12031" (manufactured by Arakawa Chemical Co., Ltd.), and a vinyl siloxane "11365" (Arakawa Chemical Co., Ltd.) Industrial company) and methyl hydrogenated polysiloxane "12031" (manufactured by Arakawa Chemical Industries, Ltd.).

The silicone resin layer 14 contains a silicone oil. Silicone oil is different from the above-mentioned crosslinkable organic polysiloxane, and is a non-crosslinkable (non-reactive) organic polysiloxane that does not react with the crosslinkable organic polysiloxane and does not have crosslinkability.

The type of the silicone oil is not particularly limited, and examples thereof include dimethyl polysiloxane, Pure silicone oils such as methylphenylpolysiloxane and diphenylpolysiloxane; and modified silicone oils such as polyether group and halogen group introduced into the side chain or end of the pure silicone oil.

In terms of the commercially available product name or model of the silicone oil, examples of the silicone oil having an aromatic group (for example, phenyl group) include KTSF433 (manufactured by Momentive Performance Materials Japan), KF- 50, KF-53, KF-54 (made by Shin-Etsu Chemical Industry Co., Ltd.), and SH550 (made by Toray Dow Corning).

Examples of the silicone oil having no aromatic group include SH200 (manufactured by Toray Dow Corning) and KNS-330 (manufactured by Shin-Etsu Chemical Co., Ltd.).

There is no particular limitation on the viscosity of silicone oil. Under the condition that it easily spills onto the surface of the silicone resin layer 14 and the peelability of the glass substrate 16 is better, and the peeled glass substrate 16 is better in transparency, 100 ~ 6000cP is taken as Good, 100 ~ 3000cP is better, 125 ~ 1000cP is better.

There is no particular limitation on the content of the silicone oil in the silicone resin layer 14. In the case where the glass substrate 16 is excellent in peelability and the transparency of the peeled glass substrate is better, it is 6 to 20 masses based on 100 mass parts of the silicone resin. Parts is better, more preferably 6 to 15 parts by mass, and even more preferably 8 to 15 parts by mass.

Either one of the silicone resin constituting the silicone resin layer 14 and the silicone oil contained in the silicone resin layer 14 has an aromatic group, and the other does not substantially have an aromatic group. In other words, only one of the silicone resin and the silicone oil has an aromatic group. As mentioned above, as long as it is in this state, the compatibility between the silicone resin and the silicone oil is poor, so as a result, the silicone oil easily spills onto the surface of the silicone resin layer 14 and the glass substrate 16 is easy to be processed even after high-temperature heating treatment. Of stripping.

However, the so-called silicone resin or silicone oil does not substantially have an aromatic group and is intended to have an aromatic group in a range that does not affect the effects of the present invention. More specifically, it is intended to indicate that the silicone resin or silicone oil is compatible with The aromatic group content in all organic groups bonded to the silicon atom is less than 1 mole%.

The silicone resin or silicone oil having an aromatic group is intended to indicate that an aromatic group is contained in the above-mentioned content ratio or more.

The type of the aromatic group is not particularly limited, and examples thereof include a monovalent aromatic group (for example, an aromatic hydrocarbon group or an aromatic heterocyclic group). Among them, from the point of easy preparation of silicone resin or silicone oil, aromatic hydrocarbon groups are preferred, and phenyl groups are particularly preferred.

As the above aspect, there are more specifically two modes: the aspect A, the silicone oil has an aromatic group and the silicone resin does not substantially have an aromatic group; and the aspect B, the silicone resin has an aromatic group and the silicone oil is substantially Does not have aromatic groups. Among them, in the case where the preparation of the silicone resin layer 14 is easier, and the peelability of the glass substrate 16 is more excellent, the aspect A is preferred.

In the case of state A, the aryl group contained in the silicone oil is preferably a phenyl group. Among them, the glass substrate 16 after the high-temperature heat treatment has excellent peelability, and the glass substrate 16 that has been peeled off has better transparency. To be more excellent, the content of the aromatic group (especially the phenyl group) in all the organic groups bonded to the silicon atom in the silicone oil is preferably 5-50 mol%, and more preferably 5-30 mol%. 10 ~ 30 mole% is better.

However, in the case of aspect A, there is no particular limitation on the bonding position of the aromatic group in the silicone oil, and examples thereof include two ends and / or side chains. Examples of the group other than the phenyl group contained in the silicone oil include an alkyl group (for example, methyl, ethyl, and propyl).

On the other hand, in the case of the aspect B, the aryl group contained in the silicone resin is preferably a phenyl group. Among them, the glass substrate 16 after the high-temperature heat treatment has a better peelability. The content of the aromatic group (especially the phenyl group) in all organic groups bonded to the silicon atom is preferably 5 to 90 mole%, and more preferably 30 to 90 mole%. In the case of aspect B, examples of the group other than the phenyl group contained in the silicone resin include an alkyl group (for example, methyl, ethyl, propyl, etc.).

In addition, as the silicone oil having an aromatic group, under the point that the compatibility with the silicone resin is excellent, a methylphenyl silicone oil is suitably used.

Examples of the silicone resin having an aromatic group include a silicone resin obtained by crosslinking a crosslinkable organic polysiloxane having a phenyl group.

[Glass Laminate and Its Manufacturing Method]

The glass laminated body 10 of the present invention is the laminated body in which the support substrate 12, the glass substrate 16 and the silicone resin layer 14 are interposed therebetween as described above.

The manufacturing method of the glass laminated body 10 of the present invention is not particularly limited. In order to obtain a laminated body having a peel strength (x) higher than the peel strength (y), a predetermined cross-linkable organopolysiloxane is formed on the surface of the supporting substrate 12 A method of cross-linking and curing the alkane to form the siloxane resin layer 14 is preferred. That is, a layer containing a crosslinkable organic polysiloxane and a silicone oil is formed on the surface of the support substrate 12, and a crosslinkable organic polysiloxane is crosslinked on the surface of the support substrate 12 to form a silicon oxide. The resin layer 14 (crosslinked silicone resin), and then a method of manufacturing a glass laminate 10 on the silicone resin area layer glass substrate 16 of the silicone resin layer 14.

Once the crosslinkable organic polysiloxane is hardened on the surface of the supporting substrate 12, it can be connected by the interaction with the surface of the supporting substrate 12 during the curing reaction. As a result, the peeling strength between the silicone resin and the surface of the supporting substrate 12 is increased. Therefore, even if the glass substrate 16 and the supporting substrate 12 are made of the same material, a difference in peel strength between the silicone resin layer 14 and the two can be provided.

Hereinafter, a layer containing a crosslinkable organic polysiloxane and a silicone oil is formed on the surface of the support substrate 12, and a crosslinkable organic polysiloxane is crosslinked on the surface of the support substrate 12 to form a silicone resin layer. The step 14 is referred to as a resin layer forming step, and the step of forming the glass laminate 10 from the silicone resin area layer glass substrate 16 of the silicone resin layer 14 is referred to as a lamination step, and the steps are described in detail.

(Resin layer forming step)

In the resin layer forming step, a layer containing a crosslinkable organic polysiloxane and a silicone oil is formed on the surface of the support substrate 12, and the crosslinkable organic polysiloxane is crosslinked on the surface of the support substrate 12. Forming a siloxane resin layer 14.

In order to form a layer containing a crosslinkable organic polysiloxane and a silicone oil on the supporting substrate 12, a coating composition in which a crosslinkable organic polysiloxane and a silicone oil are dissolved in a solvent is used. The composition is coated on the supporting substrate 12 to form a solution layer, and then the solvent is removed to form a layer containing a crosslinkable organic polysiloxane and a silicone oil. The thickness of the layer containing the crosslinkable organic polysiloxane and the silicone oil can be controlled by adjusting the concentration of the crosslinkable organic polysiloxane and the silicone oil in the composition.

The solvent is not particularly limited as long as it is a solvent that can easily dissolve the crosslinkable organopolysiloxane and silicone oil under the working environment and can be easily volatilized and removed. Specific examples include butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF, and chloroform.

Coating cross-linking organic polysilicon on the surface of support substrate 12 The method of the composition of oxane and silicone oil is not specifically limited, A well-known method can be used. For example: spray coating method, die coating method, spin coating method, dip coating method, roll coating method, bar coating method, screen printing method, gravure coating method, and the like.

Thereafter, if necessary, a drying process for removing the solvent may be performed. The drying method is not particularly limited, and examples thereof include a method of removing a solvent under reduced pressure, and a method of heating at a temperature at which the crosslinkable organic polysiloxane is not cured.

Next, a crosslinkable organic polysiloxane is crosslinked on the support substrate 12 to form a siloxane resin layer 14. More specifically, as shown in FIG. 2 (A), in this step, a silicone resin layer 14 is formed on at least one surface of the supporting substrate 12.

The method of hardening (cross-linking) can be appropriately selected according to the cross-linking form of the cross-linkable organopolysiloxane as described above, such as heat treatment or light exposure treatment. Among them, when the crosslinkable organic polysiloxane is crosslinked by a hydrosilylation reaction, a condensation reaction, and a radical reaction, a silicone resin excellent in adhesion and heat resistance to the glass substrate 16 can be obtained. In one aspect, the silicone resin layer 14 is preferably manufactured by thermosetting.

The details of the thermal hardening are described below.

The temperature condition for thermally curing the crosslinkable organic polysiloxane is not particularly limited as long as it can improve the heat resistance of the siloxane resin layer 14 and control the peel strength (y) after lamination with the glass substrate 16 as described above. , Preferably at 150 ~ 300 ℃, more preferably at 180 ~ 250 ℃. In addition, the heating time is usually 10 to 120 minutes, and preferably 30 to 60 minutes. If the heat curing temperature is too low, the heat resistance or the flatness of the silicone resin layer 14 will be reduced; Once it is too high, the peel strength (y) will become too low; in either case, the adhesion between the glass substrate 16 and the silicone resin layer 14 may be weakened.

In addition, the crosslinkable organopolysiloxane may be cured after being pre-cured (pre-cured) and then post-cured (this curing). By performing the pre-hardening, the silicone resin layer 14 having excellent heat resistance can be obtained. The pre-hardening should be performed immediately after the solvent is removed. At that time, the steps of removing the solvent from the layer to form a layer containing a crosslinkable organic polysiloxane and a silicone oil and a step of performing the pre-hardening are not particularly distinguished.

(Lamination step)

The lamination step is to laminate a glass substrate 16 on the siloxane resin surface of the siloxane resin layer 14 obtained in the above-mentioned resin layer forming step, so as to obtain a layer having a supporting substrate 12, a siloxane resin layer 14, and glass in this order. A step of the glass laminate 10 of the substrate 16. More specifically, as shown in FIG. 2 (B), the surface of the silicone resin layer 14 opposite to the supporting substrate 12 side (the first main surface of the silicone resin layer) 14a and the glass substrate 16 have The first main surface 16 a of the first main surface 16 a and the second main surface 16 b is used as a buildup layer, and the silicone resin layer 14 and the glass substrate 16 are laminated to obtain a glass laminate 10.

The method of laminating the glass substrate 16 on the silicone resin layer 14 is not particularly limited, and a known method can be adopted.

For example, a method of superposing the glass substrate 16 on the surface of the silicone resin layer 14 under a normal pressure environment. Alternatively, after the glass substrate 16 is superimposed on the surface of the siloxane resin layer 14 as required, the glass substrate 16 may be crimped to the siloxane resin layer 14 by using a roller or a press. By using crimping by a roller member or a press, it is easier to remove the gas mixed between the silicone resin layer 14 and the glass substrate 16 Soaked, so ideal.

Compression bonding by a vacuum lamination method or a vacuum pressing method is preferable because it can suppress the incorporation of bubbles and ensure good adhesion. If the pressure bonding is performed under a vacuum, even if there are tiny bubbles remaining, there is an advantage that the bubbles do not grow due to heating and the wrinkle defects that are not easily implicated in the glass substrate 16.

When the glass substrate 16 is laminated, the surface of the glass substrate 16 that is in contact with the silicone resin layer 14 should be sufficiently washed and laminated in an environment with high cleanliness. The higher the degree of cleanliness, the better the flatness of the glass substrate 16 is, which is desirable.

In addition, after the glass substrate 16 is laminated, a pre-annealing treatment (heating treatment) may be performed as required. By performing this pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the silicone resin layer 14 can be improved, and an appropriate peel strength (y) can be achieved, and it is difficult to produce electronic components during a member formation step described later. The positional deviation of components can improve the productivity of electronic components.

The conditions for the pre-annealing process may be appropriately selected according to the type of the silicone resin layer 14 used. From the viewpoint of making the peel strength (y) between the glass substrate 16 and the silicone resin layer 14 more appropriate, It should be heat-treated for more than 5 minutes (ideally in 5-30 minutes) at 300 ℃ or higher (ideally in 300 ~ 400 ℃).

The formation of the siloxane resin layer 14 is not limited to the above method.

For example, when using a support substrate 12 whose material has a higher adhesion to the surface of the silicone resin than the glass substrate 16, the cross-linkable organic polysiloxane can be hardened on any peelable surface to produce a film of the silicone resin. The thin film is sandwiched between the glass substrate 16 and the supporting substrate 12 and laminated at the same time.

In addition, when the crosslinkable organic polysiloxane is hardened, When the glass substrate 16 is sufficiently low and its adhesiveness is sufficiently high enough to the support substrate 12, the cross-linkable organic polysiloxane can be hardened between the glass substrate 16 and the support substrate 12 to form the siloxane resin layer 14.

In addition, even when the supporting base material 12 is made of the same glass material as the glass substrate 16, a treatment for improving the adhesion of the surface of the supporting base material 12 can be performed to increase the peeling strength of the silicone resin layer 14. For example: chemical methods (primer treatment) such as silane coupling agent that chemically increase the fixing force, physical methods such as flame treatment to increase the surface active group, and sandblasting treatment by increasing the surface roughness Mechanical treatment methods to increase grip.

(Glass laminate)

The glass laminated body 10 of the present invention can be used in various applications, such as applications for manufacturing electronic components such as a panel for a display device described later, PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed on the surface. In this application, the glass laminate 10 is often exposed to high temperature conditions (for example, 350 ° C. or higher) (for example, 1 hour or longer).

Here, the display device panel 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.

[Glass substrate with member and manufacturing method thereof]

In the present invention, the laminated body is used to produce a glass substrate with a member (a glass substrate with a member for an electronic component) including a glass substrate and a member for an electronic component.

The manufacturing method of the glass substrate with a member is not particularly limited. It seems that the productivity of the sub-components is excellent. It is preferable to use the following method: forming a member for electronic components on the glass substrate in the above-mentioned glass laminate to manufacture a laminated body with a member for electronic components, and using a silicone resin layer A method for separating a glass substrate side interface from a laminated body with a member for electronic components and a glass substrate with a member and a supporting substrate with a silicone resin layer as a peeling surface.

Hereinafter, the step of forming a member for electronic components on a glass substrate in the above-mentioned glass laminate to manufacture a laminate with a member for electronic components is referred to as a member forming step; the glass substrate side interface of the silicone resin layer is used as a peeling surface, The step of separating from a laminated body with a member for electronic components into a glass substrate with a member and a supporting substrate with a silicone resin layer is called a separation step.

The materials and procedures used in each step are detailed below.

(Member formation step)

The member forming step is a step of forming a member for an electronic component on the glass substrate 16 in the glass laminated body 10 obtained in the above-mentioned laminating step. More specifically, as shown in FIG. 2 (C), the electronic component member 20 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 to obtain a laminated body 22 to which the electronic component member is attached.

First, the electronic component member 20 used in this step will be described in detail, and then the step procedure will be described in detail.

(Member for electronic components (functional device))

The electronic component member 20 is a member formed on the glass substrate 16 in the glass laminate 10 and constituting at least a part of an electronic component. More specifically, as the electronic component member 20, for example, it can be used in a panel for a display device, Components such as electronic components such as solar cells, thin-film secondary batteries, or semiconductor wafers with circuits formed on the surface (for example, components for display devices, components for solar cells, components for thin-film secondary batteries, and circuits for electronic components).

For example, as a solar cell member, transparent types such as tin oxide of a positive electrode, a silicon layer represented by a p-layer / i-layer / n-layer, and a metal of a negative electrode may be mentioned in the silicon type, and others may correspond to, for example, Various components such as compound type, dye-sensitized type, and quantum dot type.

In addition, as a member for a thin film secondary battery, in a lithium ion type, transparent electrodes such as metals of positive and negative electrodes or metal oxides, lithium compounds of an electrolyte layer, metals of a current collecting layer, and resins as a sealing layer can be mentioned. Others include various members corresponding to nickel-hydrogen type, polymer type, and ceramic electrolyte type.

In addition, as a circuit for electronic parts, CCD and CMOS can be exemplified by metals such as conductive parts and silicon oxide or silicon nitride provided by insulating parts. Other examples include pressure sensors and acceleration sensors. Various sensors, various components such as rigid printed circuit boards, flexible printed circuit boards, and rigid flexible printed circuit boards.

(Step Procedure)

The manufacturing method of the above-mentioned laminated body 22 with a member for an electronic component is not particularly limited, and it can be applied to the second main body of the glass substrate 16 of the glass laminated body 10 by a known method according to the type of the constituent member of the electronic component member. A member 20 for an electronic component is formed on the surface of the surface 16b.

In addition, the electronic component member 20 may be all members (hereinafter referred to as “all members”) that are not all formed on the second main surface 16 b of the glass substrate 16 and may be all members. A part of a component (hereinafter referred to as a "partial component"). The glass substrate with a part of the component peeled from the siloxane resin layer 14 can be made into a glass substrate with a full component (corresponding to an electronic component described later) in a subsequent step.

In addition, other electronic component members may be formed on the peeling surface (first main surface 16a) of the glass substrate that is peeled from the silicone resin layer 14 and has all the members. Alternatively, the laminated body with the entire member may be assembled, and then the support substrate 12 may be peeled off from the laminated body with the entire member to manufacture an electronic component. In addition, it is also possible to assemble using two laminated members with all components, and then peel off the two supporting substrates 12 from the laminated member with all components to manufacture a member-attached glass substrate having two glass substrates. .

For example, in the case of manufacturing an OLED, for example, in order to form an organic layer on the surface of the glass substrate 16 of the glass laminate 10 opposite to the silicone resin layer 14 side (equivalent to the second main surface 16b of the glass substrate 16). The EL structure is subjected to the following various layer formation and processing: forming a transparent electrode; further depositing a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer on the surface on which the transparent electrode has been formed, and forming a back electrode ; And, using a sealing plate for sealing and the like. Specific examples of such layer formation or treatment include film formation treatment, vapor deposition treatment, and subsequent treatment of a sealing plate.

For example, when manufacturing a TFT-LCD, there may be various steps such as the following: a TFT forming step, using a CVD method and sputtering on the second main surface 16b of the glass substrate 16 of the glass laminate 10 using a resist solution The method is to form a thin film transistor (TFT) by patterning a metal film and a metal oxide film formed by a general film forming method. In the CF formation step, the second main body of the glass substrate 16 of the other glass laminated body 10 is formed. Use a resist solution for patterning on the surface 16b Forming a color filter (CF); and a laminating step, the laminated body with TFT obtained in the TFT forming step and the laminated volume layer with CF obtained in the CF forming step.

In the TFT formation step and the CF formation step, a TFT or CF may be formed on the second main surface 16 b of the glass substrate 16 using a well-known photolithography technique or etching technique. In this case, a resist liquid may be used as the coating liquid for pattern formation.

Before forming the TFT and CF, the second main surface 16b of the glass substrate 16 can be cleaned according to demand. As a washing method, a well-known dry cleaning or wet washing can be used.

In the bonding step, the thin-film transistor-forming surface of the TFT-attached multilayer body and the color filter-forming surface of the CF-attached multilayer body are opposed to each other, and a sealant (for example, a UV-curable sealant for cell formation) is used for attachment. Together. Thereafter, a liquid crystal material is injected into a unit cell formed by 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 titration injection method.

(Separation step)

As shown in FIG. 2 (D), the separation step uses the interface between the siloxane resin layer 14 and the glass substrate 16 as a peeling surface, and separates it from the laminated body 22 with the electronic component member obtained in the above-mentioned member formation step. A step of laminating a glass substrate 16 (a glass substrate with a member) and a supporting substrate 12 on which the electronic component member 20 is laminated to obtain a glass substrate 24 with a member having the electronic component member 20 and the glass substrate 16.

When peeling, when the electronic component member 20 on the glass substrate 16 forms a part of all the constituent members required, the remaining constituent members may be separated after separation. The component is formed on the glass substrate 16.

The method of peeling the glass substrate 16 and the support base material 12 is not specifically limited. Specifically, for example, on the premise that a sharp blade is inserted into the interface between the glass substrate 16 and the silicone resin layer 14 to provide a peeling gap, a mixed fluid of water and compressed air is sprayed to perform peeling. Ideally, it is provided on the platen with the supporting base material 12 with the laminated body 22 with the member for electronic components on the upper side and the side with the electronic component member 20 on the lower side, and vacuum-adsorbs the member 20 with the electronic component on the platen. (When the two-area layer has a supporting substrate, it is performed sequentially.) In this state, the blade is first penetrated at the interface between the glass substrate 16 and the silicone resin layer 14. After that, the support substrate 12 side is adsorbed by a plurality of vacuum adsorption pads, and the vacuum adsorption pad is sequentially raised from the vicinity of the place where the blade is inserted. In this way, an air layer can be formed on the interface between the silicone resin layer 14 and the glass substrate 16 or the condensation failure surface of the silicone resin layer 14, and the air layer can be expanded to the entire surface of the interface or the condensation failure surface, and it is easy. The support substrate 12 is peeled off.

Moreover, the support base material 12 can be laminated | stacked with a new glass substrate, and the glass laminated body 10 of this invention can be manufactured.

When separating the glass substrate 24 with the component from the multilayer body 22 with the component for electronic components, by controlling the spraying or humidity performed by the ionizer, the electrostatic adsorption of the fragments of the silicone resin layer 14 can be suppressed. On the attached glass substrate 24.

The manufacturing method of the above-mentioned glass substrate 24 with components is suitable for manufacturing a small display device used in a mobile terminal such as a mobile phone or a PDA. The display device is mainly an LCD or an OLED. The LCD includes a TN type, an STN type, a FE type, a TFT type, a MIM type, an IPS type, and a VA type. basically, It can be applied to any display device of passive driving type and active driving type.

Examples of the glass substrate 24 with a member manufactured by the above method include a panel for a display device having a glass substrate and a member for a display device, a solar cell having a glass substrate and a member for a solar cell, a glass substrate and a film. Films for secondary battery components, secondary batteries, and electronic components including glass substrates and components for electronic components. The display device panel includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

Examples

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

In the following Examples 1 to 5, and Comparative Examples 1 to 2, as the glass substrate, a glass plate made of alkali-free borosilicate glass (200 mm in length, 200 mm in width, 0.2 mm in thickness, and a linear expansion coefficient of 38 × 10) was used. ^-7 / ° C, trade name "AN100" manufactured by Asahi Glass Co., Ltd.). Also, as a supporting substrate, a glass plate (240 mm in length, 240 mm in width, 0.5 mm in thickness, 0.5 mm in thickness, linear expansion coefficient of 38 × 10 ^-7 / ° C.) made of alkali-free borosilicate glass was also used. "AN100").

<Example 1>

First, the support substrate with a thickness of 0.5 mm was washed with pure water, and then washed with UV to clean it.

Next, an organic alkenyl polysiloxane having vinyl groups at both ends (vinyl silicone, manufactured by Arakawa Chemical Industries, Ltd., 8500) and a methyl hydrogenated polysiloxane having a hydrosilyl group in the molecule (Arakawa Chemical Industries, Ltd.) Company, 12031) Blend. The molar ratio of all the vinyl groups in the organic alkenyl polysiloxane to the hydrogen atom bonded to the silicon atom in the methyl hydrogenated polysiloxane is 1: 1. Based on 100 parts by mass of the resin component, 5 parts by weight of a platinum-based catalyst (Arakawa Chemical Industries, Ltd., CAT12070) was added. Then, methylphenyl silicone oil (KF-50 manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 100 cP) and heptane were added to prepare a solution containing a cross-linkable organic polysiloxane. This solution was applied to the first main surface of the support substrate with a spin coater (number of rotations: 300 rpm, 15 seconds), and a layer containing uncured cross-linkable organic polysiloxane and silicone oil was placed on On a support substrate (application amount: 20 g / m ² ).

In addition, the amount of methylphenylsilicone used was set to 8 parts by mass based on 100 parts by mass of the total mass of the organic alkenyl polysiloxane and methyl hydrogenated polysiloxane. The amount of heptane used was 100 parts by mass based on 100 parts by mass of the total mass of the organic alkenyl polysiloxane and methyl hydrogenated polysiloxane. Moreover, the phenyl content in the methylphenyl silicone oil is 5 mol% relative to all organic groups bonded to silicon atoms in the silicone oil.

Next, it was hardened by heating at 230 ° C. for 10 minutes in the atmosphere, and a 10 μm-thick silicone resin layer was formed on the first main surface of the supporting substrate. In this aspect, the silicone resin of the silicone resin layer does not have an aromatic group, and the methylphenyl silicone oil of the silicone oil has an aromatic group (phenyl group). The silicone resin layer is transparent.

Thereafter, the glass substrate and the silicone resin layer of the supporting substrate were bonded by vacuum pressing at room temperature to obtain a glass laminate A.

In the obtained glass laminated body A, the support substrate and the glass substrate system did not generate bubbles and were in close contact with the silicone resin layer, which had no wrinkle-like defects and smoothness. good.

Next, the glass laminate A was heat-treated at 350 ° C for 60 minutes under a nitrogen gas atmosphere and cooled to room temperature. As a result, it was confirmed that there is no separation of the support substrate and the glass substrate of the glass laminate A or the silicone resin layer. Changes in appearance such as foaming or whitening.

Then, insert a 0.1mm thick stainless steel blade at the interface between the glass substrate and one of the four corners of the glass laminated body A to form a notched part while inserting a stainless steel blade at the interface, and use a vacuum suction pad. The glass substrate and the supporting substrate are adhered to the non-peeling surfaces of the substrate, and external forces are applied to each other in a direction where the glass substrate and the supporting substrate are separated, so that the glass substrate and the supporting substrate are separated without damage. Here, the inserting of the blade is performed while spraying a deionizing fluid on the interface from an ionizing means (manufactured by Keynes Corporation). Specifically, the vacuum suction pad is lifted while continuously spraying a destaticizing fluid from an ionizing means toward the formed gap.

The silicone resin layer was separated from the glass substrate together with the supporting substrate. From this result, it was confirmed that the peel strength (x) of the interface between the supporting substrate layer and the silicone resin layer was higher than that of the silicone resin layer and the glass substrate. Interface peel strength (y). The surface of the peeled glass substrate is transparent.

<Example 2>

Except using methyl phenyl silicone oil (Koshi-50, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 3000cp) instead of methyl phenyl silicone oil (KF-50, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 100 cP). In the same manner as in Example 1, a glass laminate B was obtained.

However, compared with all organic groups bonded to silicon atoms in silicone oil, The methylphenyl silicone oil used has a phenyl content of 5 mol%.

In addition, the appearance of the siloxane resin layer is also transparent after manufacturing, and the glass substrate is also transparent after being laminated thereon.

In the obtained glass laminated body B, the supporting base material and the glass substrate system were closely adhered to the silicone resin layer without generating bubbles, and there was no wrinkle-like defect, and the smoothness was also good.

Next, the glass laminate B was subjected to the same heat treatment as in Example 1. As a result, it was confirmed that there was no separation of the support substrate of the glass laminate B from the glass substrate, or the appearance of foaming or whitening of the silicone resin layer. Variety.

Then, the glass laminate B was separated from the supporting substrate and the glass substrate in the same manner as in Example 1. The glass substrate and the supporting substrate were separated without damage. The siloxane resin layer is separated from the glass substrate together with the supporting substrate. From this result, it was confirmed that the peeling strength (x) of the interface between the substrate supporting layer and the silicone resin layer is higher than the peeling strength (y) of the interface between the silicone resin layer and the glass substrate. The surface of the peeled glass substrate is transparent.

<Example 3>

In addition to using methyl phenyl silicone oil (Koshitsu Chemical Industry Co., Ltd., KF-54, viscosity 400cp) instead of methyl phenyl silicone oil (Koshitsu Chemical Industry Co., Ltd., KF-50, viscosity 100 cP), In the same manner as in Example 1, a glass laminate C was obtained.

The phenyl content in the methylphenyl silicone oil used is 25 mol% relative to all organic groups bonded to silicon atoms in the silicone oil.

In addition, the appearance of the siloxane resin layer was slightly turbid after the production, and the glass substrate became transparent after the glass substrate was laminated thereon.

In the obtained glass laminated body C, the supporting substrate and the glass substrate are closely adhered to the silicone resin layer without generating bubbles, and have no wrinkle-like disadvantages and excellent smoothness.

Next, the glass laminate C was subjected to the same heat treatment as in Example 1. As a result, it was confirmed that there was no separation of the support substrate of the glass laminate C from the glass substrate, or the appearance of foaming or whitening of the silicone resin layer. Variety.

Thereafter, the glass laminate C was separated from the supporting substrate and the glass substrate in the same manner as in Example 1. The glass substrate and the supporting substrate were separated without damage. The siloxane resin layer is separated from the glass substrate together with the supporting substrate. From this result, it was confirmed that the peeling strength (x) of the interface between the substrate supporting layer and the silicone resin layer is higher than the peeling strength (y) of the interface between the silicone resin layer and the glass substrate. However, the surface of the peeled glass substrate was slightly white and cloudy.

<Example 4>

Except for using methylphenyl silicone oil (manufactured by Toray Dow Corning Corporation, SH550, viscosity 125cp) instead of methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 cP), the same procedure as in Example 1 was used. The glass laminated body D was obtained by the same method.

The phenyl content in the methylphenyl silicone oil used is 25 mol% relative to all organic groups bonded to silicon atoms in the silicone oil.

In addition, the appearance of the siloxane resin layer was slightly turbid after the production, and the glass substrate became transparent after the glass substrate was laminated thereon.

In the obtained glass laminated body D, the supporting substrate and the glass substrate are closely adhered to the silicone resin layer without generating bubbles, and have no wrinkle-like defects and good smoothness.

Next, the glass laminated body E was subjected to the same heat treatment as in Example 1, and it was confirmed that there were no external appearance changes such as separation of the supporting substrate of the glass laminated body D from the glass substrate, or foaming or whitening of the silicone resin layer.

Then, the glass laminate D was separated from the supporting substrate and the glass substrate in the same manner as in Example 1. The glass substrate and the supporting substrate were separated without damage. The siloxane resin layer is separated from the glass substrate together with the supporting substrate. From this result, it was confirmed that the peeling strength (x) of the interface between the substrate supporting layer and the silicone resin layer is higher than the peeling strength (y) of the interface between the silicone resin layer and the glass substrate. However, the surface of the peeled glass substrate was slightly white and cloudy.

<Example 5>

In addition to using methyl phenyl silicone oil (manufactured by Momentive Performance Materials Japan contract company, TSF433, viscosity 450 cp) instead of methyl phenyl silicone oil (made by Shin-Etsu Chemical Industry Co., Ltd., KF-50, viscosity 100 cP), In the same manner as in Example 1, a glass laminate E was obtained.

The phenyl content in the methylphenyl silicone oil used is 25 mol% relative to all organic groups bonded to silicon atoms in the silicone oil.

In addition, the appearance of the siloxane resin layer was slightly turbid after the appearance, and the glass substrate became transparent after being laminated thereon.

In the obtained glass laminated body E, the supporting substrate and the glass substrate are closely adhered to the silicone resin layer without generating bubbles, and have no wrinkle-like disadvantages and excellent smoothness.

Next, the glass laminate E was subjected to the same heat treatment as in Example 1. As a result, it was confirmed that there was no separation of the support substrate of the glass laminate E from the glass substrate, or the appearance of foaming or whitening of the silicone resin layer. Variety.

Then, the glass laminate E was separated from the supporting substrate and the glass substrate in the same manner as in Example 1. The glass substrate and the supporting substrate were separated without damage. The siloxane resin layer is separated from the glass substrate together with the supporting substrate. From this result, it was confirmed that the peeling strength (x) of the interface between the substrate supporting layer and the silicone resin layer is higher than the peeling strength (y) of the interface between the silicone resin layer and the glass substrate. However, the surface of the peeled glass substrate was slightly white and cloudy.

The viscosity and the phenyl content of the silicone oil used in Examples 1 to 5 are shown below.

<Comparative example 1>

A glass laminate X was obtained in the same manner as in Example 1 except that methylphenyl silicone oil (KF-50, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 100 cP) was not used.

The obtained glass laminate X was separated from the supporting substrate and the glass substrate in the same manner as in Example 1. As a result, the silicone resin layer and the glass substrate were difficult to peel off and the glass substrate was cracked.

<Comparative example 2>

In addition to using 0.5 parts by weight of methyl silicone oil (manufactured by Toray Dow Corning, SH200, viscosity 200 cP) instead of methyl phenyl silicone oil (Shin-Etsu Chemical Industry Except for the company, KF-50, viscosity 100 cP), a glass laminate Y was obtained in the same manner as in Example 1. However, this aspect is equivalent to the aspect of Example 7 of the previous document (WO2011 / 142280), and both the silicone resin and the silicone oil do not contain an aromatic group.

The obtained glass laminate Y was separated from the supporting substrate and the glass substrate in the same manner as in Example 1. As a result, the silicone resin layer and the glass substrate were difficult to separate and the glass substrate was cracked.

In Examples 1 to 5, even after the high-temperature heat treatment was performed, the thin glass substrate could be easily peeled off. Meanwhile, the surfaces (peeling surfaces) of the peeled glass substrates in Examples 1 and 2 remained transparent, and in Examples 3 to 5, they were slightly cloudy. This is speculated that in Examples 3 to 5, a part of the silicone oil overflowing the surface of the silicone resin layer was transferred to the glass substrate. From these results, it was confirmed that in the case of the silicone oil used in Examples 1 and 2, the cleanness of the surface of the peeled glass substrate was better.

On the other hand, in Comparative Example 1 in which no silicone oil was used, and Comparative Example 2 in which both the silicone resin and the silicone oil did not contain an aromatic group, the peelability was poor.

<Example 6>

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

First, silicon nitride, silicon oxide, and amorphous silicon were sequentially formed on the second main surface of the glass substrate of the glass laminate A by a plasma CVD method. Next, a low concentration of boron is implanted into the amorphous silicon layer by an ion doping device, and a hydrogen treatment is performed at 450 ° C. for 60 minutes in a nitrogen gas environment to perform a dehydrogenation treatment. Then, the crystallization process of the amorphous silicon layer is performed by a laser annealing apparatus. Pick up Next, N-type and P-type TFT regions are formed by implanting low-concentration phosphorus into the amorphous silicon layer using an etching and ion doping device using photolithography. Next, a gate insulating film is formed by forming a silicon oxide film by plasma CVD on the second main surface side of the glass substrate, and then molybdenum is formed by sputtering and then formed by etching using photolithography. Gate electrode. Next, high-concentration boron and phosphorus are implanted into respective desired regions of the N-type and P-type by a photolithography method and an ion doping device to form a source region and a drain region. Then, an interlayer insulating film is formed on the second main surface side of the glass substrate by using a silicon oxide film formed by a plasma CVD method, and an aluminum film is formed by a sputtering method and an etching method by a photolithography method is used. TFT electrode. Next, in a hydrogen gas environment, a heat treatment is performed at 450 ° C. for 60 minutes to perform a hydrogenation treatment, and then a silicon nitride film formed by a plasma CVD method is used to form a passivation layer. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by a photolithography method. Next, an indium tin oxide film is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.

Next, the following layers were sequentially formed on the second main surface side of the glass substrate by a vapor deposition method: 4,4 ', 4 "-shen (3-methylphenylphenylamino) triphenylamine as Hole injection layer, bis [(N-naphthyl) -N-phenyl] benzidine as a hole transport layer, and 40-vol% of 2,6 mixed with 8-quinolinol aluminum complex (Alq ₃ ) -Bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-1,5-dicarbonitrile (BSN-BCN) as the light-emitting layer and Alq ₃ as Electron transport layer. Next, aluminum is formed by a sputtering method, and a counter electrode is formed by etching using a photolithography method. Then, an ultraviolet curing type adhesive layer is interposed on the second main surface side of the glass substrate. Laminate another glass substrate and seal it. The organic EL structure is formed on the glass substrate by the above procedure. The glass laminate A (hereinafter referred to as panel A) having the organic EL structure on the glass substrate is the attached electron of the present invention. A laminated body of a component for an element (a panel for a display device with a supporting substrate).

Next, when the sealing body side of the panel A is vacuum-sucked to the fixed plate, a 0.1 mm thick stainless steel blade is inserted at the interface between the glass substrate and the silicone resin layer at the corner of the panel A, and the glass substrate is The interface with the silicone resin layer provides a peeling gap. Then, when the surface of the supporting substrate of the panel A is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the blade is inserted from an ionizing means (manufactured by Keynes Corporation) while spraying a destaticizing fluid on the interface. Next, the vacuum adsorption pad was raised while continuously spraying a destaticizing fluid from the ionization means toward the formed gap. As a result, only the glass substrate on which the organic EL structure is formed can be left on the fixed plate, and the supporting substrate with the silicone resin layer can be peeled off.

Next, the peeled surface of the separated glass substrate was cleaned in the same manner as in Example 1, and the separated glass substrate was cut and separated into a plurality of small cells by using a laser cutter or a scribe method ( cell), the glass substrate on which the organic EL structure is formed and the counter substrate are assembled, and a module forming step is performed to produce an OLED. The OLED produced by the above method has no problem in characteristics.

<Example 7>

In this example, the glass laminate A obtained in Example 1 was used to manufacture an LCD.

First, two glass laminates A were prepared, and silicon nitride and oxygen were sequentially formed on the second main surface of a glass substrate of one glass laminate A1 by plasma CVD. Siliconized and amorphous silicon. Next, a low concentration of boron is implanted into the amorphous silicon layer by an ion doping device, and a hydrogen treatment is performed at 450 ° C. for 60 minutes in a nitrogen gas environment to perform a dehydrogenation treatment. Then, the crystallization process of the amorphous silicon layer is performed by a laser annealing apparatus. Secondly, N-type and P-type TFT regions are formed by implanting low-concentration phosphorus into the amorphous silicon layer by using a photolithographic etching and ion doping device. Next, a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by a sputtering method and formed by etching using a photolithography method. Gate electrode. Then, boron and phosphorus are implanted into the desired regions of the N-type and P-type with high concentration by photolithography and an ion doping device to form a source region and a drain region. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by a silicon oxide film formed by a plasma CVD method, an aluminum film is formed by a sputtering method, and a TFT is formed by etching using a photolithography method. electrode. Next, in a hydrogen gas environment, a heat treatment is performed at 450 ° C. for 60 minutes to perform a hydrogenation treatment, and then a passivation layer is formed by forming a silicon nitride film by a plasma CVD method. Then, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by a photolithography method. Next, an indium tin oxide film is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.

Next, another glass laminated body A2 was heat-treated at 450 ° C. for 60 minutes in an atmospheric environment. Then, a chromium film is formed on the second main surface of the glass substrate of the glass laminate A by a sputtering method, and a light-shielding layer is formed by etching using a photolithography method. Next, the second main surface side of the glass substrate is coated with a dye resist by a die coating method, and a color filter layer is formed by photolithography and thermal curing. Next, an indium tin oxide film is formed by a sputtering method, and a counter electrode is formed. again Then, a UV-curable resin solution was applied to the second main surface side of the glass substrate by a die coating method, and a columnar spacer was formed by photolithography and thermal curing. Next, a polyimide resin solution is applied by a roll coating method, and an alignment layer is formed by thermal curing, and rubbing is performed.

Next, the sealing resin liquid is drawn into a frame shape by a dispensing method, and liquid crystals are dropped in the frame by a dispensing method, and then the two glass laminates A glass are formed using the above-mentioned glass laminate A1 in which pixel electrodes are formed. The second main surface sides of the substrates are bonded to each other, and an LCD panel is obtained by ultraviolet curing and thermal curing.

Next, the second main surface of the glass laminated body A1 was vacuum-adsorbed on the fixed plate, and a 0.1 mm thick stainless steel blade was inserted at the interface between the glass substrate and the silicone resin layer at the corner of the glass laminated body A2 to give Peeling notch between the first main surface of the glass substrate and the peelable surface of the silicone resin layer. Here, the inserting of the blade is performed while spraying a destaticizing fluid to the interface from an ionizing means (manufactured by Keynes Corporation). Then, the vacuum suction pad was raised while continuously spraying a destaticizing fluid from the ionization means toward the formed gap. Then, when the second main surface of the supporting substrate of the glass laminate A2 is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. As a result, only the LCD empty cell with the supporting substrate of the glass laminate A1 remaining on the fixed plate, and the supporting substrate with the siloxane resin layer can be peeled off.

Next, the second main surface of the glass substrate having the color filter formed on the first main surface was vacuum-adsorbed to the fixed plate, and the interface between the glass substrate and the silicone resin layer at the corner of the glass laminate A1 was 0.1 mm thick The stainless steel blade has a peeling notch on the first main surface of the glass substrate and the peelable surface of the silicone resin layer. Then, the supporting substrate of the glass laminate A1 is adsorbed on a vacuum adsorption pad. In the case of the second main surface, the suction pad is raised. As a result, only the LCD cell may remain on the fixing plate, and the supporting substrate on which the silicone resin layer is fixed may be peeled off. In this way, a large number of LCD cells made of a glass substrate having a thickness of 0.1 mm can be obtained.

Next, the LCD cell is divided into a plurality of LCD cells by a cutting step. A step of sticking a polarizing plate is performed on each completed LCD cell, and then a module forming step is performed to obtain an LCD. The LCD thus obtained did not cause problems in characteristics.

<Example 8>

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

First, molybdenum is formed on the second main surface of the glass substrate of the glass laminate A by a sputtering method, and a gate electrode is formed by etching using a photolithography method. Next, a silicon nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then an indium gallium zinc oxide film is formed by a sputtering method. The etched etching forms an oxide semiconductor layer. Next, a silicon nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a channel protection layer, and then a molybdenum film is formed by a sputtering method, and a photolithography method is used. The source electrode and the drain electrode are formed by etching. Next, heat treatment was performed at 450 ° C for 60 minutes in the atmosphere. Next, on the second main surface side of the glass substrate, a silicon nitride film is formed by a plasma CVD method to form a passivation layer, and then an indium tin oxide film is formed by a sputtering method, and a photolithography method is used. The etching forms pixel electrodes.

Next, the following layers were sequentially formed on the second main surface side of the glass substrate by a vapor deposition method: 4,4 ', 4 "-ginseng (3-methylphenylphenylamino) triphenylamine As a hole injection layer, bis [(N-naphthyl) -N-phenyl] benzidine as a hole transport layer, and 8-quinolinol aluminum complex (Alq ₃ ) was mixed with 40% by volume of 2, 6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-1,5-dicarbonitrile (BSN-BCN) as the light-emitting layer, and Alq ₃ serves as an electron transport layer. Next, aluminum is formed into a film by a sputtering method, and a counter electrode is formed by etching using a photolithography method. Next, an ultraviolet curing type adhesive is placed on the second main surface side of the glass substrate. Layer another glass substrate and seal it. Through the above procedure, an organic EL structure is formed on the glass substrate. A glass laminate A (hereinafter referred to as a panel A) having an organic EL structure on the glass substrate is attached to the present invention. A laminated body of a member for an electronic component (a panel for a display device with a supporting substrate).

Next, when the sealing body side of the panel A is vacuum-adsorbed on the fixed plate, a 0.1 mm thick stainless steel blade is inserted at the interface between the glass substrate and the silicone layer in the corner of the panel A, and the glass substrate The interface with the silicone resin layer provides a peeling gap. Then, when the surface of the supporting substrate of the panel A is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the difference of the blades is performed while spraying a deionizing fluid on the interface from an ionizing means (manufactured by Keynes Corporation). Then, the vacuum suction pad is raised while continuously spraying the static elimination fluid from the ionization means toward the formed gap. As a result, the glass substrate on which the organic EL structure is formed can be left only on the fixed plate, and the supporting substrate with the silicone resin layer can be peeled off.

Next, the peeled surface of the glass substrate separated in the same manner as in Example 1 was cleaned, and the separated glass substrate was cut and separated into a plurality of unit cells using a laser cutter or a scribing method. The glass substrate on which the organic EL structure is formed is assembled with the counter substrate, and the module formation step is performed to produce the glass substrate. OLED. The OLED thus obtained did not cause problems in characteristics.

This application is based on Japanese Patent Application No. 2012-230092 filed on October 17, 2012, and the contents thereof are incorporated herein by reference.

10‧‧‧Glass laminate

12‧‧‧ support substrate

14‧‧‧silicone resin layer

14a‧‧‧ the first main surface of the silicone resin layer

16‧‧‧ glass substrate

16a‧‧‧The first main surface of the glass substrate

16b‧2nd main surface of glass substrate

18‧‧‧ Supporting substrate with silicone resin layer

Claims (10)

A glass laminated body is provided with a support substrate layer, a siloxane resin layer, and a glass substrate layer in this order, and the peel strength of the interface between the support substrate layer and the siloxane resin layer is higher than that of the siloxane resin layer. Peel strength at the interface with the glass substrate; wherein the silicone resin layer is a crosslinked product of the silicone resin-based crosslinkable organic polysiloxane, the silicone resin layer contains silicone oil, and the silicone resin layer The contained silicone resin does not substantially have an aromatic group. The aforementioned silicone oil has a phenyl group. In the aforementioned silicone oil, among all organic groups bonded to silicon atoms, the phenyl content rate is 5 to 50 mol%. For example, the glass laminate of claim 1, wherein the content of the silicone oil and fat in the silicone resin layer is 6 to 20 parts by mass relative to 100 mass parts of the silicone resin. For example, the glass laminate of claim 1 or 2, wherein the viscosity of the aforementioned silicone oil at 25 ° C is 100-6000 cP. For example, the glass laminate of claim 1 or 2, wherein the thickness of the aforementioned silicone resin layer is 2 to 100 μm. The glass laminate according to claim 1 or 2, wherein the aforementioned supporting substrate is a glass plate. A method for producing a glass laminate according to any one of claims 1 to 5, which method comprises forming a cross-linkable organic polymer on one side of a supporting substrate. A layer of a siloxane and a siloxane oil, and cross-linking the crosslinkable organic polysiloxane on the support substrate surface to form a siloxane resin layer, and then a glass substrate on the surface area of the siloxane resin layer. A support substrate with a siloxane resin layer, comprising a support substrate and a siloxane resin layer provided on the support substrate surface and having a peelable surface; wherein the siloxane resin of the siloxane resin layer is crosslinkable organic In the crosslinked product of polysiloxane, the silicone resin layer contains silicone oil, and the silicone resin contained in the silicone resin layer does not substantially have an aromatic group, the silicone oil has a phenyl group, and in the silicone oil, Among all the organic groups bonded to the silicon atom, the phenyl content is 5 to 50 mole%. For example, the support substrate with a siloxane resin layer as claimed in claim 7, wherein the content of the phenyl group in all the organic groups bonded to the silicon atom in the aforementioned siloxane oil is 5-30 mol%. For example, the support substrate with a silicone resin layer as claimed in claim 7 or 8, wherein the content of the silicone oil is 6-20 parts by mass relative to 100 mass parts of the silicone resin in the aforementioned silicone resin layer. For example, the support substrate with a silicone resin layer of claim 7 or 8, wherein the viscosity of the aforementioned silicone oil at 25 ° C. is 100 to 6000 cP.